# Patent

## Title
Hardening resin composition and color conversion material using the same

## Abstract

The invention provides a resin composition having an excellent dispersibility of a phosphor, and when the resin composition is processed and used as a color conversion material, to give a hardened material having a high heat resistance, resistance to thermal yellowing, light resistance, transparency and refractive index, and an excellent adhesion to allow color conversion of light emitted from an optical semiconductor stably and without a flare spot over a long period of time. The invention also relates to a hardening resin composition having at least one of epoxy and oxetanyl.

## Background
CROSS-REFERENCE TO RELATED APPLICATION
This application is a 371 application of an international PCT application serial no. PCT/JP2012/053694, filed on Feb. 16, 2012, which claims the priority benefit of Japan application no. 2011-033970, filed on Feb. 18, 2011. The entirety of each of the above-mentioned patent applications is hereby incorporated by reference herein and made a part of this specification.
TECHNICAL FIELD
The invention relates to a hardening resin composition that contains a silicon compound having an epoxy group and is prepared by composing a phosphor, and is useful for an application such as a coating agent, an optical material and an electronic material, and relates to a hardened material obtained by hardening the hardening resin composition.
BACKGROUND ART
A light emitting diode (LED) has rapidly spread recently. With regard to a light emitting apparatus, such as the light emitting diode (LED) that has widely spread for use in a large display such as a TV and a PC, an information terminal for a touch panel, a cell phone and a smartphone, and lighting, a trend is to achieve high brightness. In such a current situation, high performance is also required for a sealing material used for the devices.
A method has been tried so far for performing resin sealing of an LED or the like by using as the sealing material a novolak-based epoxy resin, a cycloaliphatic epoxy resin or an acrylic resin, and hardening with acid anhydride or a polymerization initiator (see Patent literature Nos. 1 and 2, for example). However, the resins are deteriorated by heat or ultraviolet light from a light emitting device not to allow maintenance of high transparency, and thus have a disadvantage of causing colorization.
As a sealing material having a high transparency, a dimethyl silicone-based resin has been used (see Patent literature Nos. 3 and 4, for example). The resins are hardened by condensation between silanol groups, a hydrosilylation reaction between a carbon-to-carbon double bond and a SiH group using a platinum catalyst, a reactive functional group such as an epoxy group, or the like.
A resin mainly formed of dimethyl silicone can keep a higher transparency over a long period of time, even when exposed to heat or light, in comparison with a conventional epoxy resin, and therefore has been widely used as the sealing material for the LED or the like. However, the resin has problems such as a low adhesion to a base material, a lower refractive index of the resin in comparison with a value required as the sealing material, tackiness on a surface of a resin hardened material during LED manufacture, and easy scratching of a surface due to softness of a hardened film, and thus a further improvement has been required for the resin.
On the other hand, a siloxane-based resin synthesized by a sol-gel process has bee also studied as an LED sealing material (Patent literature Nos. 5 and 6). However, while the resin has a high surface hardness, the resin has a crack caused during hardening, distortion of a film by shrinkage during hardening, a low compatibility with other molecules, and therefore is not dissolved to be transparent without adding a large amount of diluent to cause a low viscosity, and thus the phosphor is easily settled out. Moreover, when a large amount of diluent formed of an organic component is added, a ratio of silicon in a resin composition decreases, and if exposed to heat or light for a long period of time, the resin has a problem such as a decrease in transparency.
Various types have been proposed for an optical semiconductor device package and a method for manufacturing the package. Above all, with regard to a resin composition containing a phosphor, a sheet for sealing an optical semiconductor, or the like, when the phosphor is uniformly dispersed into the resin composition, a fluctuation in chromaticity is minimized, and high brightness can be maintained (see Patent literature Nos. 7, 8 and 9, for example).
Thus, when a resin composition in which dispersibility of the phosphor is improved, or a processed sheet for sealing the semiconductor is used, an optical semiconductor package having a higher brightness can be produced. However, when the resin composition is provided as the sheet for sealing the semiconductor, a method for manufacturing the optical semiconductor package is limited.
Moreover, in a case where the phosphor is dispersed into the resin composition, the phosphor sinks during molding, and therefore is unevenly distributed. In a case where a plurality of color conversion materials are used, specific gravity of each material is different, and therefore the materials are not uniformly dispersed. Thus, the case has a problem of generation of color unevenness.
Furthermore, in a case where a device that emits light having a short wavelength, such as an ultraviolet light-emitting device, is used, the resin into which the phosphor is dispersed deteriorates by light from the device, and thus the case also has a problem of causing a change of color.
Accordingly, a liquid resin composition containing the phosphor is required to have an excellent dispersibility of the phosphor, and simultaneously in a case where the resin composition is processed and used as the color conversion material, to have a high heat resistance, resistance to thermal yellowing, transparency or surface hardness, and an excellent adhesion to a base material. However, a resin composition having a balance among various characteristics described above has not existed yet. Therefore, a resin composition having a good balance among the characteristics is desired.
On the other hand, a sealing process in manufacture of the optical semiconductor package has been applied by thermosetting so far in many cases, in which several hours are required in order to sufficiently harden the composition. In such a situation, a need is present for requiring a material that can increase a production rate.
CITATION LIST
Patent Literature
Patent literature No. 1: JP S61-112334 A.
Patent literature No. 2: JP H02-289611 A.
Patent literature No. 3: JP 2003-273292 A.
Patent literature No. 4: JP 2006-299099 A.
Patent literature No. 5: JP 2004-238589 A.
Patent literature No. 6: JP 2004-359933 A.
Patent literature No. 7: JP 2003-37295 A.
Patent literature No. 8: JP 2009-84511 A.
Patent literature No. 9: JP 2010-123802 A.
SUMMARY OF INVENTION
Technical Problem
An object of the invention is to provide a resin composition having an excellent dispersibility of a phosphor, and simultaneously when the composition is processed and used as a color conversion material, to give a hardened material having a high heat resistance, resistance to thermal yellowing, light resistance or transparency, an excellent surface hardness and an excellent adhesion to a base material to allow color conversion of light emitted from an optical semiconductor stably without a flare spot over a long period of time.
Solution to Problem
The present inventors have diligently continued to conduct research for achieving the object. As a result, the present inventors have found that the object can be achieved by using a hardening resin composition having a constitution described below, and thus have completed the invention.
More specifically, the invention has the constitution described below.
Item 1. A hardening resin composition containing (A) to (E) below:

    (A) a silicon compound that is obtained by performing a hydrosilylation reaction among compound (a), compound (b), and when necessary, compound (c) below, and has at least one of epoxy and oxetanyl, wherein
    compound (a) is at least one of silicone and silsesquioxane having two or more of SiH in one molecule,
    compound (b) is a compound having at least one of epoxy and oxetanyl, and alkenyl having 2 to 18 carbons in one molecule, and compound (c) is at least one of silicone and silsesquioxane having two or more of alkenyl in one molecule;
    (B) a phosphor;
    (C) an epoxy resin;
    (D) a hardening agent; and
    (E) an antioxidant.


Item 2. The hardening resin composition according to item 1, wherein compound (a) is at Least one kind selected from the group of compounds represented by formula (a-1) to formula (a-10) below, compound (b) is at least one kind selected from the group of compounds represented by formula (b-1) to formula (b-3) below, and compound (c) in a case where compound (c) is used when necessary is at least one kind selected from the group of compounds represented by formula (c-1) and (c-2).







In formula (a-1) to formula (a-10), R is a group independently selected from alkyl having 1 to 45 carbons, cycloalkyl having 4 to 8 carbons, aryl having 6 to 14 carbons and arylalkyl having 7 to 24 carbons; in the alkyl having 1 to 45 carbons, arbitrary hydrogen may be replaced by fluorine, and arbitrary non-adjacent —CH2— may be replaced by —O— or —CH═CH—; in a benzene ring in the aryl and the arylalkyl, arbitrary hydrogen may be replaced by halogen or alkyl having 1 to 10 carbons, and in the alkyl having 1 to 10 carbons, arbitrary hydrogen may be replaced by fluorine, and arbitrary non-adjacent —CH2— may be replaced by —O— or —CH═CH—; the number of carbons of alkylene in the arylalkyl is 1 to 10, and arbitrary non-adjacent —CH2— may be replaced by —O—; R1 and R2 are a group independently selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl; R3 is a group independently selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl; at least two of X, in one molecules of each compound, are hydrogen, and the rest of X is a group independently selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl; and n is an integer from 0 to 100, and m is an integer from 3 to 10.




In formulas (b-1) to (b-3), at least one of R4 and R5 is alkenyl having 2 to 10 carbons, and one of —CH2— in the alkenyl may be replaced by —O— or 1,4-phenylene, and the other is hydrogen or alkyl having 1 to 6 carbons.




In formula (c-1) and formula (c-2), R and R3 are a group defined in a manner similar to
the definitions of R and R3 in formula (a-6) and formula (a-7) above, R1 is a group independently selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl, Y is a group independently selected from vinyl and allyl, and n is an integer from 0 to 100.
Item 3. The hardening resin composition according to item 1 or 2, wherein compound (a) is a silsesquioxane derivative represented by formula (a-1-1) below.




Item 4. The hardening resin composition according to any one of items 1 to 3, wherein compound (b) is one kind or two kinds selected from the group of compounds represented by formula (b-1-1), formula (b-2-1), formula (b-2-2), formula (b-3-1) and formula (b-3-2) below.




Item 5. The hardening resin composition according to any one of items 1 to 4, wherein compound (c) is represented by formula (c-1-1) or formula (c-2-1) below.




Item 6. The hardening resin composition according to any one of items 1 to 5, wherein the silicon compound represented by (A) and having the epoxy group is polysilsesquioxane represented by formula (α).




In formula (α), p is an integer from 1 to 100, q and r each are a value satisfying expressions: 0≦q≦1.95 and 0.1≦r≦4, s is a value satisfying an expression: 0≦s≦3, and q, r and s each are a value satisfying an expression: 2q+r+s≦4.
Item 7. The hardening resin composition according to any one of items 1 to 5, wherein the silicon compound having the epoxy and represented by (A) is silsesquioxane represented by formula (β).




Item 8. The hardening resin composition according to any one of items 1 to 7, wherein the phosphor represented by (B) is a phosphor for a white LED.
Item 9. The hardening resin composition according to any one of items 1 to 8, wherein the epoxy resin represented by (C) is an epoxy resin represented by formula (γ1) or (γ2), and has at least one of the epoxy resins.




Item 10. The hardening resin composition according to any one of items 1 to 9, wherein the hardening agent represented by (D) is a thermal cationic polymerization agent or a photocationic polymerization initiator.
Item 11. The hardening resin composition according to any one of items 1 to 10, wherein the antioxidant represented by (E) is a phenolic antioxidant, or a phosphorus-based antioxidant and a phenolic antioxidant.
Item 12. A hardened material in a form of a film, a sheet or a coating film, obtained by applying onto a transparent base material the hardening resin composition according to any one of items 1 to 11, and hardening an applied product by heating or light irradiation.
Item 13. A color conversion material containing the hardened material according to item 12.
Item 14. An optical semiconductor device including the color conversion material according to item 13.
Advantageous Effects of Invention
A hardening resin composition of the invention has an excellent dispersibility of a phosphor, and a hardened material of the hardening resin composition has a high heat resistance, resistance to thermal yellowing, transparency, light resistance and refractive index, and an excellent adhesion to a base material, and has stress-relaxation properties. Therefore, neither a crack nor distortion is caused in a hardened film during hardening, a surface of the hardened film is flat, and has a proper surface hardness. A color conversion material containing the hardened material can perform color conversion of light emitted from an optical semiconductor stably without a flare spot over a long period of time. Moreover, in manufacturing of an optical semiconductor device package, the hardening resin composition can be provided in the form of a varnish or the like, and further a sealing resin can be hardened quickly by light irradiation, and thus the resin composition is handled with easiness.


DESCRIPTION OF EMBODIMENTS
Terms used in the invention will be explained.
A compound represented by formula (I) may be occasionally described as compound (I). Any compound represented by any other formula may be occasionally abbreviated and referred to in a similar manner.
A term “arbitrary” in the invention means any of not only positions but also the numbers. Then, an expression “arbitrary A may be replaced by B or C” means inclusion of a case where at least one of A is replaced by B, a case where at least one of A is replaced by C, and also a case where at least one of A is replaced by B, and simultaneously at least one of other A is replaced by C.
In addition, setting in which arbitrary —CH2— in alkyl or alkylene may be replaced by —O— does not include a case where all of plurality of consecutive —CH2— are replaced by —O—.
In Examples, data displayed on an electronic balance are expressed in terms of g (gram) being a mass unit. Percent by mass or a mass ratio is expressed in terms of data based on such a numeric value.
Hardening Resin Composition
A hardening resin composition of the invention contains, as being hardenable by heating or light irradiation, (A) a silicon compound having at least one of epoxy and oxetanyl, (B) a phosphor, (C) an epoxy resin, (D) a hardening agent, and when necessary, can contain a silane coupling agent.
(A) Silicon Compound Having an Epoxy Group
An organosilicon compound having an epoxy group contained in the hardening resin composition according to the invention is obtained by a hydrosilylation reaction between compound (a) and compound (b), or a hydrosilylation reaction among compound (a), compound (b) and compound (c), as described below.
Compound (a) is at least one of silicone and silsesquioxane having two or more Si—H groups in one molecule, preferably, silsesquioxane. Molecular weight of compound (a) is preferably 100 to 500,000, particularly preferably, 1,000 to 100,000.
Compound (b) is a compound having at least one of epoxy and oxetanyl, and alkenyl having 2 to 18 carbons in one molecule, preferably, has one or more of at least one of epoxy and oxetanyl in one molecule.
Compound (c) is at least one of silicone and silsesquioxane having two or more of alkenyl in one molecule. Molecular weight of compound (c) is preferably 100 to 500,000, particularly preferably, 150 to 10,000.
A ratio of constitutional units from compound (a), compound (b) and compound (c), respectively, in (A) the silicon compound having at least one of epoxy and oxetanyl to be used in the invention, when a mole fraction of each compound is defined to be ω, ψ and φ, respectively, preferably satisfies expressions:

{ω×the number of SiH groups included in one molecule of compound (a)}≦{ψ×the number of alkenyl included in one molecule of compound (b)}+{φ×the number of alkenyl included in one molecule of compound (c)}.

With regard to the hydrosilylation reaction among compound (a), compound (b) and compound (c), compound (a), compound (b) and compound (c) may be simultaneously added to perform the hydrosilylation reaction, but preferably, first, a hydrosilylation reaction between compound (a) and compound (c) is allowed so as to be “the number of moles of SiH groups included in (a)>the number of moles of alkenyl included in (c),” and then an excessive amount of compound (b) is added to allow a hydrosilylation reaction between an unreacted SiH group and alkenyl of compound (b).
The hydrosilylation reaction is preferably performed in a solvent. The solvent used for the hydrosilylation reaction is not particularly limited, if the solvent does not adversely affect progress of the reaction. Specific examples of preferred solvents include a hydrocarbon solvent such as hexane and heptane, an aromatic hydrocarbon solvent such as benzene, toluene and xylene, an ether solvent such as diethyl ether, tetrahydrofuran (THF) and dioxane, a halogenated hydrocarbon solvent such as methylene chloride and carbon tetrachloride, and an ester solvent such as ethyl acetate.
The solvents may be used alone or in combination with a plurality of the solvents. Among the solvents, an aromatic hydrocarbon solvent is preferred, and in the solvents, toluene is most preferred.
The hydrosilylation reaction may be performed at room temperature. Heating may be applied in order to accelerate polymerization. Cooling may be applied in order to control development of heat by polymerization, undesired polymerization or the like. In hydrosilylation polymerization, a catalyst can be used when necessary.
When a hydrosilylation catalyst is added, polymerization can be progressed more easily. As the hydrosilylation catalyst, a Karstedt catalyst, a Speier catalyst, hexachloroplatinic acid or the like can be preferably utilized.
The hydrosilylation catalysts have a high reactivity, and therefore the reaction can be sufficiently progressed by adding a small amount thereof. An amount of use is preferably 10−9 to 1 mol %, further preferably, 10−7 to 10−3 mol % in terms of a ratio of a transition metal contained in the catalyst to a hydroxyl group.
Specific examples of compound (a) include compounds represented by formula (a-1) to formula (a-10) below.







In formula (a-1), formula (a-2), formula (a-3), formula (a-4), formula (a-5), formula (a-9) and formula (a-10), R is a group independently selected from alkyl having 1 to 45 carbons, cycloalkyl having 4 to 8 carbons, aryl having 6 to 14 carbons and arylalkyl having 7 to 24 carbons.
In the alkyl having 1 to 45 carbons, arbitrary hydrogen may be replaced by fluorine, and arbitrary non-adjacent —CH2— may be replaced by —O— or —CH═CH—.
In a benzene ring in the aryl having 6 to 14 carbons and the arylalkyl having 7 to 24 carbons, arbitrary hydrogen may be replaced by halogen or alkyl having 1 to 10 carbons. In the alkyl having 1 to 10 carbons, arbitrary hydrogen may be replaced by fluorine, and arbitrary non-adjacent —CH2— may be replaced by —O— or —CH═CH—.
The number of carbons of alkylene in the arylalkyl is 1 to 10, and arbitrary non-adjacent —CH2— may be replaced by —O—.
R is preferably a group independently selected from cyclopentyl, cyclohexyl, phenyl, and alkyl having 1 to 10 carbons. In the alkyl having 1 to 10 carbons, arbitrary hydrogen may be replaced by fluorine, and arbitrary non-adjacent —CH2— may be replaced by —O—. Moreover, in the phenyl, arbitrary hydrogen may be replaced by halogen such as fluorine, or alkyl having 1 to 10 carbons.
R is further preferably cyclopentyl, cyclohexyl, or phenyl in which arbitrary hydrogen may be replaced by chlorine, fluorine, methyl, methoxy or trifluoromethyl, still further preferably, cyclohexyl or phenyl, most preferably, phenyl.
In formula (a-1), formula (a-2), formula (a-3), formula (a-5), formula (a-8), formula (a-9) and formula (a-10), R1 and R2 are a group independently selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl. Examples of the alkyl having 1 to 4 carbons are methyl, ethyl, propyl, 2-methylethyl, butyl and t-butyl. Preferred examples of R1 or R2 are methyl and phenyl. R4 and R5 are preferably an identical group.
In formula (a-6) and formula (a-7), R3 is a group independently selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl. Examples of the alkyl having 1 to 4 carbons are methyl, ethyl, propyl, 2-methylethyl, butyl and t-butyl.
In formula (a-1) to formula (a-10), in one molecule of each compound, at least two of X are hydrogen, and the rest of X is a group independently selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl.
In formula (a-6), formula (a-9) and formula (a-10), n is an integer from 0 to 100, and in formula (a-7), m is an integer from 3 to 10.
As compound (a), a compound represented by formula (a-1-1) below is further preferred.




In formula (a-1-1), Ph stands for phenyl. A compound represented by formula (a-1-1) can be prepared by the method described in WO 2004/024741 A. Moreover, other compounds can also be obtained by publicly known methods.
Specific examples of compound (b) include a compound represented by formula (b-1), formula (b-2) or formula (b-3) below.




In formulas (b-1), (b-2) and (b-3), one of R4 and R5 is alkenyl having 2 to 10 carbons, and one of —CH2— in the alkenyl may be replaced by —O— or 1,4-phenylene, and the other is hydrogen or alkyl having 1 to 6 carbons.
Specific examples of further preferred compound (b) include a compound represented by formula (b-1-1), formula (b-2-1), formula (b-2-2), formula (b-3-1) or formula (b-3-2) below.




In addition, as a compound represented by formula (b-2-2), EOXTVE sold by Maruzen Petrochemical Co., Ltd. can be used, and as a compound represented by formula (b-3-1), CELLOXIDE 2000 sold by Daicel Chemical Industries, Ltd. can be used.
Specific examples of compound (c) include a compound represented by formula (c-1) or formula (c-2) below.




In formula (c-1), R3 is a group defined in a manner similar to the definitions of R3 in formula (a-6) or formula (a-7) above, and a preferred group is also defined in a similar manner.
In formula (c-2), R and R1 are a group independently selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl. In formula (c-1) and formula (c-2), Y is a group independently selected from vinyl and allyl. In formula (c-1), n is an integer from 0 to 100.
As compound (c), a compound represented by formula (c-1) or (c-2-1) below is further preferred. In formula (c-1), R3 is independently selected from methyl or phenyl, and n is an integer from 0 to 100.




Specific examples of compounds represented by formula (c-1-1) include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane and vinyl terminated polydimethylsiloxane at both terminals.
(A) The silicon compound having the epoxy group used for the invention is preferably polysilsesquioxane represented by formula (α) below.




(A) The silicon compound having the epoxy group used for the invention is further preferably polysilsesquioxane represented by formula (β) below.




In formula (β), p is an integer from 1 to 100, and preferably, q and r each are a value satisfying expressions: 0≦q≦1.95 and 0.1≦r≦4, s is a value satisfying an expression: 0≦s≦3, and q, r and s each are a value satisfying an expression: 2q+r+s≦4, and q, r and s each satisfy expressions: 0.3≦q≦1, 2≦r≦3.5, and 0≦s≦1.
Content of (A) the silicon compound having at least one of epoxy and oxetanyl in the hardening resin composition according to the invention is preferably 20 to 90% by mass, further preferably, 50 to 80% by mass, based on the total amount of the hardening resin composition. When the content is adjusted in the above range, the composition exhibits excellent characteristics with regard to heat resistance, transparency, resistance to yellowing, resistance to thermal yellowing, light resistance, surface hardness, adhesion and optical cation hardening properties.
(B) Phosphor
The hardening resin composition of the invention contains a phosphor. The phosphor is preferably inorganic particles used as a phosphor for a light emitting diode (LED), further preferably, a phosphor for a white LED.
Specific examples of the phosphors include (Y,Gd)3(Al,Ga)5O12:Ce3+ that is referred to as YAG and widely utilized, (Ba,Sr,Ca)2SiO4:Eu2+, and CaAlSiN3:Eu2+ being a nitride phosphor.
Content of (B) the phosphor in the hardening resin composition according to the invention is preferably 5 to 50% by mass because the content is deeply related to transmittance of light transmitted through the color conversion material, and color.
If the content of the phosphor in the hardening resin composition is 50% by mass or less, the transmittance does not decrease and the brightness does not decrease, and if the content is 5% by mass or more, the color of transmitted light does not change.
(C) Epoxy Resin
The hardening resin composition of the invention can contain an epoxy resin. In the invention, a compound including an oxetane compound being 4-membered ring cyclic ether or an oxetane resin may be occasionally referred to as the epoxy resin.
Specific examples of the epoxy resins include a hydrogenated bisphenol A epoxy resin, and a compound represented by formula (γ1) or (γ2) below.




As the epoxy resin represented by formula (γ1) among types of the compounds, for example, Aron Oxetane DOX (trade name) made by Toagosei Co., Ltd. is sold, and easily available.
Moreover, the epoxy resin represented by formula (γ2) is commercially available, for example, as CELLOXIDE (trade name) 2021 P made by Daicel Chemical Industries, Ltd., and is easily available.
Content of (C) the epoxy resin in the hardening resin composition according to the invention is preferably 0.1 to 80% by mass, further preferably, 1 to 40% by mass, based on the total amount of the hardening resin composition. When the content is adjusted in the above range, adhesion of the hardening resin to the substrate can be improved, and viscosity of the hardening resin composition can also be adjusted.
(D) Hardening Agent
A hardening agent may be appropriately selected according to a kind of (A) the silicon compound having at least one of epoxy and oxetanyl to be used. For example, in the case of the compounds represented by formulas (a-1) to (a-10) above, the hardening agent may be appropriately selected according to a kind of X to be used, and ordinarily, a cationic polymerization initiator is preferably used.
Specific examples of the cationic polymerization initiators include an active energy-ray cationic polymerization initiator that generates cationic species or Lewis acid by active energy rays such as ultraviolet light, and a thermal cationic polymerization initiator that generates cationic species or Lewis acid by heat.
Specific examples of the active energy-ray cationic polymerization initiators include a metal fluoroboron complex, a boron trifluoride complex compound, a bis(perfluoroalkylsulfonyl)methane metal salt, an aryl diazonium compound, a dicarbonyl chelate of elements of Groups IIIa to Va in the Periodic Table, a thiopyrylium salt, MF6 (elements of Group VIb in the Periodic Table in the form of an anion; wherein M is selected from phosphorus, antimony and arsenic), an aryl sulfonium complex salt, an aromatic iodonium complex salt, an aromatic sulfonium complex salt and a bis[4-(diphenylsulfonio)phenyl]sulfide-bis-hexafluoro metal salt. In addition thereto, a mixed ligand metal salt of an iron compound can also be used.
Moreover, specific examples of the active energy-ray cationic polymerization initiators include an aryl sulfonium complex salt, an aromatic sulfonium or iodonium salt of a halogen-containing complex ion, and an aromatic onium salt of elements of Groups II, Va and VIa in the Periodic Table. Some of the salts can be obtained as a commercial item.
Specific examples of the thermal cationic polymerization initiators include a cationic catalyst or protonic acid catalyst, such as a triflic acid salt and boron trifluoride, and a triflic acid salt is particularly preferred. Specific examples of the triflic acid salts include triflic acid diethyl ammonium, triflic acid diisopropyl ammonium and triflic acid ethyldiisopropyl ammonium.
On one hand, some of aromatic onium salts used as the active energy-ray cationic polymerization initiator generate cationic species by heat, and can also be used as the thermal cationic polymerization initiator.
Among the cationic polymerization initiators, an aromatic onium salt is preferred in view of an excellent balance among handling properties, latency and hardening properties. Among the aromatic onium salts, a diazonium salt, an iodonium salt, a sulfonium salt and a phosphonium salt are preferred in view of an excellent balance between handling properties and latency.
The cationic polymerization initiators may be used alone or in combination with two or more kinds.
Hardening Agent; Metal Chelate Compound
As the hardening agent, a metal chelate compound can be used. As the metal chelate compound, a composite catalyst between an organoaluminum compound and an organosilicon compound having a silanol group or a composite catalyst between an organoaluminum compound and an organosilicon compound having an alkoxy group can be used.
Specific examples of the organoaluminum compounds include an aluminum complex such as trisacetylacetonato aluminum, trisethylacetonato aluminum, tris(salicylaldehydato) aluminum and tris(o-carbonylphenolate)aluminum, an aluminum metal salt such as aluminum stearate and aluminum benzoate, and aluminum alkoxide.
Content of (D) the hardening agent in the hardening resin composition according to the invention is not particularly limited, but in order for a hardening reaction to sufficiently progress to allow obtaining of a target hardened material without causing a decrease in physical properties of the hardened material and without causing coloring to the hardened material, the content is preferably 0.007 to 10.0% by mass, further preferably, 0.01 to 1.0% by mass, based on the total amount of (A) the silicon compound having at least one of epoxy and oxetanyl, and (C) the epoxy resin.
(E) Antioxidant
An antioxidant is preferably contained in the hardening resin composition according to the invention from viewpoints of heat resistance and weather resistance. When the composition contains the antioxidant, oxidation deterioration during heating can be prevented, and coloring can be suppressed. Examples of the antioxidants include a phenolic antioxidant and a phosphorus-based antioxidant.
A ratio of compounding the antioxidant in the hardening resin composition according to the invention is preferably 0.1 to 2.0 in terms of a mass ratio on the basis of the total amount of the hardening resin composition.
Specific examples of the antioxidants include monophenols, bisphenols, polymer-type phenols, phosphites and oxaphosphaphenanthrene oxides.
Specific examples of the monophenols include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol and stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate.
Specific examples of the bisphenols include 2,2′-methylenebis(4-methyl-6-t-butylphenol), 2,2′-methylenebis(4-ethyl-6-t-butylphenol), 4,4′-thiobis(3-methyl-6-t-butylphenol), 4,4′-butylidenebis(3-methyl-6-t-butylphenol) and 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane.
Specific examples of the polymer-type phenols include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyepropionate]methane, bis[3,3′-bis(4′-hydroxy-3′-t-butylphenyl butyric acid]glycol ester, 1,3,5-tris(3′,5′-di-t-butyl-4′-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione and tocopherol.
Specific examples of the phosphites include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl di-isodecyl phosphite, tris(nonylphenyl)phosphite, diisodecyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl)phosphite, cyclic neopentanetetrailbis(octadecyl)phosphite, cyclic neopentanetetraylbis(2,4-di-t-butylphenyl)phosphite, cyclic neopentanetetraylbis(2,4-di-t-butyl-4-methylphenyl)phosphite and bis[2-t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite.
Specific examples of the oxaphosphaphenanthrene oxides include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
The antioxidants can be used alone, respectively, but is particularly preferably used in combination with a phenolic antioxidant and a phosphorus-based antioxidant.
Specific examples of commercially available antioxidants include “IRGANOX 1010 (trade name)” and “IRGAFOS 168 (trade name),” both made by BASF Japan Ltd. The antioxidants can be used alone, respectively, and can also be mixed and used.
Silane Coupling Agent
The hardening resin composition of the invention preferably further contains a silane coupling agent in addition to the components represented by (A) to (E) described above. When the composition contains the silane coupling agent, dispersibility of the phosphor can be improved. Specific examples of the silane coupling agents include a compound represented by a general formula below.

R6zSi(OR7)4-z 

In the formula above, R6 is a group having a reactive functional group represented by FG-R8—, FG is an epoxy, amino group or vinyl group or (meth)acryl, and R8 is linear or cyclic alkylene having 1 to 10 carbons, or phenylene. R7 is alkyl having 1 to 4 carbons. Z is an integer from 0 to 3.
As the silane coupling agent in the hardening resin composition according to the invention, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane {“Sila-Ace (registered trade name) S530” made by JNC Corporation} is particularly preferred from viewpoints of transparency and storage stability in the hardening resin composition.
Content of the silane coupling agent in the hardening resin composition according to the invention is preferably 0 to 40% by mass, further preferably, 2 to 20% by mass, based on the total amount of the hardening resin composition. When the content is adjusted in the above range, adhesion of the hardening resin composition to the substrate is improved to exhibit a high transparency.
Surface Treatment of a Phosphor
The phosphor used for the hardening resin composition according to the invention is preferably subjected to surface treatment by the silane coupling agent in order to improve dispersibility, transparency, weather resistance, moisture resistance, or the like. The silane coupling agents may be used alone in one kind, or in combination with two or more kinds arbitrarily and at an arbitrary ratio.
An amount of the silane coupling agent used onto a surface of the phosphor is not particularly limited, unless advantageous effects of a resin hardened material according to the invention are significantly adversely affected, but the amount is preferably in the range of 0.1 to 5% by mass based on the mass of the phosphor.
If the amount of the silane coupling agent used is in the range of 0.1% by mass or more based on the mass of the phosphor, a surface coating does not become incomplete, and dispersibility, transparency, weather resistance and moisture resistance can be improved, and if the amount is in the range of 5% by mass or less, light-emitting characteristics of the phosphor is not adversely affected.
Organic Solvent
The hardening resin composition of the invention may further contain an organic solvent. Here, specific examples of the organic solvents include a hydrocarbon solvent such as hexane and heptane, an aromatic hydrocarbon solvent such as benzene, toluene and xylene, an ether solvent such as diethyl ether, tetrahydrofuran (THF) and dioxane, a halogenated hydrocarbon solvent such as methylene chloride and carbon tetrachloride, an ester solvent such as ethyl acetate, and a ketone solvent such as acetone and 2-butanone. The solvents may be used alone or in combination with a plurality of kinds.
Content of the organic solvent in the hardening resin composition according to the invention is preferably 0 to 30% by mass, further preferably, 1 to 20% by mass, based on the total amount of the hardening resin composition. When the content is adjusted in the above range, viscosity of the hardening resin composition can be decreased.
Stabilizer; Ultraviolet Light Absorber
An ultraviolet light absorber may be compounded with the hardening resin composition according to the invention in order to improve light resistance. As the ultraviolet light absorber, a general ultraviolet light absorber for plastics can be used. A compounding ratio in the hardening resin composition according to the invention is preferably 0.0001 to 0.1 in teens of a mass ratio on the basis of the total amount of the hardening resin composition.
Specific examples of the ultraviolet light absorbers include salicylic acids, benzophenones, benzotriazoles and hindered amines.
Specific examples of the salicylic acids include phenyl salicylate, p-t-butylphenyl salicylate and p-octylphenyl salicylate.
Specific examples of the benzophenones include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone and 2-hydroxy-4-methoxy-5-sulfobenzophenone.
Specific examples of the benzotriazoles include 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-5′-tert-butylphenyl)benzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)benzotriazole, 2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-amylphenyl)benzotriazole and 2-{(2′-hydroxy-3′,′′, 4′′,5′′,6′′-tetrahydrophthalimidomethyl)-5′-methylphenyl}benzotriazole.
Specific examples of the hindered amines include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and bis(1,2,2,6,6-pentamethyl-4-piperidyl[{3,5-bis(1,1-dimethylethyl-4-hydroxyphenyl}methyl]butyl)malonate.
Preparation of a Hardened Material
A hardened material obtained by hardening a hardening resin composition according to the invention can be prepared, for example, by a method described below.
Liquid (I) and liquid (II) described below are prepared.
Liquid (I) to be prepared by mixing (A) a silicon compound having at least one of epoxy and oxetanyl, an arbitrary amount of (C) an epoxy resin or oxetane resin, (B) a phosphor subjected to surface treatment, and an arbitrary amount of a silane coupling agent and a stabilizer.
Liquid (II) to be prepared by mixing (D) a hardening agent, an arbitrary amount of (C) an epoxy resin or oxetane resin, and arbitrary amount of a silane coupling agent, and when necessary, the organic solvent described above.
Preparation of a Hardened Material by Thermosetting
Liquid (I) and liquid (II) that are prepared, respectively, are stirred and mixed, and then decompressed and defoamed. Then, the resultant mixture is poured into a mold, heated at 125° C. for 1 hour, and finally heated at 150° C. for 2 to 3 hours to allow thermosetting.
Preparation of a Hardened Material by Light Hardening
In a similar manner, liquid (I) and liquid (II) that are prepared are stirred and mixed, and decompressed and defoamed. A coating film obtained by applying the resultant mixture onto a substrate surface is irradiated with light such as ultraviolet light or visible light, and thus a hardened material can be obtained.
An amount of light (amount of exposure) when the coating film is irradiated with ultraviolet light, visible light or the like is appropriately determined according to the resin composition. When measurement is carried out using Digital UV Intensity Meter UIT-201 attached with photodetector UVD-365PD made by Ushio, Inc., the amount of light is preferably in the range of 10 to 3,000 mJ/cm2, further preferably, 50 to 2,000 mJ/cm2, still further preferably, 100 to 1,000 mJ/cm2. Moreover, a wavelength of ultraviolet light, visible light or the like for irradiation is preferably in the range of 200 to 500 nanometers, further preferably, in the range of 300 to 450 nanometers.
In addition, an exposure system is not particularly limited, if an apparatus is mounted with a high pressure mercury lamp , an ultra-high pressure mercury lamp, a metal halide lamp, a halogen lamp or the like, and irradiates ultraviolet light, visible light or the like in the range of 250 to 500 nanometers.
Moreover, when necessary, a hardened film obtained by hardening by irradiation with light may be further heated. For example, when the film is heated at 50 to 150° C. for 10 to 60 minutes, strength of the hardened film can be further increased.
An additive, such as the ultraviolet light absorber may be mixed in the hardening resin composition of the invention.
With regard to transparency of a hardened material obtained by hardening a hardening resin composition according to the invention, when transmittance of the hardened material before and after heat resistance testing is measured with a UV-Vis spectrophotometer, and evaluated by a yellowness index (YI value) and a retention ratio of luminous transmittance, the yellowness index (YI value) and the retention ratio of luminous transmittance at 150° C. are preferably 2 or less, and 90% or more, respectively. When the values are within the above ranges, respectively, the values indicate that the hardened material is colorless and has a high transparency, and thus such a hardened material can be particularly preferably utilized in a field such as the sealing agent for the optical semiconductor in which transparency is required.
When the hardened material obtained by allowing thermosetting or light hardening of the hardening resin composition according to the invention is molded into the form of a film, a sheet or a coating film to form a molded object, the hardened material can be used in various applications.
Specific examples of the applications of the hardened material include a wavelength conversion film, a sealing material for an optical semiconductor and a color conversion material for an optical lens, a sealing material for a semiconductor, an insulating film, a sealant and an adhesive. The color conversion material containing the hardened material according to the invention can be used for an optical semiconductor device.
The coating film of the invention is obtained by applying the hardening resin composition of the invention onto a base material.
EXAMPLES
The invention will be explained in greater detail based on Examples. In addition, the invention is not limited by Examples described below.
Measuring Apparatus and Measuring Method
Number average molecular weight and weight average molecular weight of compound (A) were measured according to a gel permeation chromatography (GPC) method. Specifically, measurement was carried out by diluting silicone and silsesquioxane with tetrahydrofuran (THF) for a concentration of silicone and silsesquioxane to be about 0.05 to about 0.10% by mass, connecting columns KF-805L and KF-804L made by Showa Denko K.K. in series in the above order and using the connected columns, and using THF as a developer according to the gel permeation chromatography (GPC) method, and the molecular weight was determined by calculating a polymethylmethacrylate equivalent.
Synthesis of a Silicon Compound Having an Epoxy Group
Synthesis Example 1
Compound (ab) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (21.0 g) prepared by the method disclosed in WO 2004/024741 A, and dry toluene (20 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C.
A Pt catalyst (21 μL) was added using a microsyringe, CELLOXIDE 2000 (product name) (10 g) (made by Daicel Chemical Industries, Ltd.) was slowly added dropwise from the dropping funnel, and the resultant mixture was stirred for 3 hours. Contents in the reaction vessel were transferred into an evaporator and concentrated therein, and thus a crude crystal was obtained. Acetone was added to the crude crystal obtained to prepare a 20% by mass solution.
Furthermore, 3% by mass of activated carbon was added to the crude crystal, and the resultant mixture was stirred for 1 hour. Then, the activated carbon was filtered off, hexane in 10 times the amount of crude crystal was added, and the resultant mixture was stirred at 25° C. for 2 hours. Then, the resultant mixture was filtered, and a filtrate was concentrated using an evaporator. Hexane in 1.25 times the amount of crude crystal obtained was added, and the resultant mixture was heated to 60° C. and the crystal was dissolved, and then subjected to recrystallization at 25° C. A crystal obtained (yield 22 g, percent yield: 76%) obtained was found to be compound (ab) as a result of measurement by NMR (DRX500 (500 MHz), made by Bruker Corporation).
Synthesis Example 2
Compound (abc1) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (80 g) prepared by the method disclosed in WO 2004/024741 A, and dry toluene (80 g) were charged into a reaction vessel having an internal volume of 500 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 110° C. A Pt catalyst (16 μL) and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (11.5 g) (made by AZmax, Co.) were added.
The resultant reaction mixture was heated to a reflux temperature and stirred for 3 hours. The reaction temperature was decreased to 80° C., a Pt catalyst (16 μL) and CELLOXIDE 2000 (trade name) (30.5 g) (made by Daicel Chemical Industries, Ltd.) were added, and the resultant mixture was stirred for 3 hours. The reaction mixture was cooled to room temperature, 4 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 700 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (trade name) (20 g) (made by Kyowa Chemical Industry Co., Ltd.). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 110 g of a colorless glassy concentrate (abc1) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,500 and weight average molecular weight (Mw) was 7,300.
Synthesis Example 3
Compound (abc1+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (50 g) and dry toluene (75 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 110° C. A Pt catalyst (16 μL) and divinyl disiloxane (7.2 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 3 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (16 .μ) and CELLOXIDE 2000 (trade name) (20.5 g) (made by Daicel Chemical Industries, Ltd.) were added, and the resultant mixture was stirred for 2 hours.
Subsequently, FM-1105 (trade name) including hydrosilyl groups at both terminals (9.8 g)(made by JNC Corporation) was added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 4 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (trade name) (15 g) (made by Kyowa Chemical Industry Co., Ltd.). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 79 g of a colorless glassy concentrate (abc1+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,300 and weight average molecular weight (Mw) was 7,000.
Synthesis Example 4
Compound (abc2) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry toluene (50 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 110° C. A Pt catalyst (5 μL) and divinyl disiloxane (4.3 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 3 hours.
The reaction temperature was decreased to 80° C., EOXTVE (trade name) (6.55 g) (made by Maruzen Petrochemical Co., Ltd.) was added, and the resultant mixture was stirred for 3 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 300 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (trade name) (5 g) (made by Kyowa Chemical Industry Co., Ltd.). Hexane (200 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 38 g of a colorless glassy concentrate (abc2) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,500 and weight average molecular weight (Mw) was 7,300.
Synthesis Example 5
Compound (abc2+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry toluene (50 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 110° C. A Pt catalyst (5 μL) and divinyl disiloxane (4.3 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 3 hours.
The reaction temperature was decreased to 80° C., EOXTVE (trade name) (6.6 g) (made by Maruzen Petrochemical Co., Ltd.) was added, and the resultant mixture was stirred for 5 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
Subsequently, FM-1105 including hydrosilyl groups at both terminals (5.9 g), and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 300 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (trade name) (5 g) (made by Kyowa Chemical Industry Co., Ltd.). Hexane (200 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 48 g of a colorless glassy concentrate (abc2+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,300 and weight average molecular weight (Mw) was 7,000.
Synthesis Example 6
Compound (abc3) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry toluene (50 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 110° C. A Pt catalyst (5 μL) and divinyl disiloxane (4.29 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 3 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and allyl oxetane (7.2 g) were added, and the resultant mixture was stirred for 5 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 300 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (trade name) (5 g) (made by Kyowa Chemical Industry Co., Ltd.). Hexane (200 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 38 g of a colorless glassy concentrate (abc3) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,500 and weight average molecular weight (Mw) was 7,300.
Synthesis Example 7
Compound (abc3+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry toluene (50 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 110° C. A Pt catalyst (5 μL) and divinyl disiloxane (4.3 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 3 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and allyl oxetane (7.2 g) were added, and the resultant mixture was stirred for 5 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
Subsequently, FM-1105 including hydrosilyl groups at both terminals (5.9 g), and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 300 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (trade name) (5 g) (made by Kyowa Chemical Industry Co., Ltd.). Hexane (200 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 48 g of a colorless glassy concentrate (abc3+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,300 and weight average molecular weight (Mw) was 7,000.
Synthesis Example 8
Compound (abc4) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry toluene (50 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 110° C. A Pt catalyst (5 μL) and divinyl disiloxane (4.29 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 3 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and EOXTVE (3.3 g) were added, and the resultant mixture was stirred for 3 hours. Subsequently, CELLOXIDE 2000 (2.9 g) was added, and the resultant mixture was stirred for 3 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 300 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (trade name) (5 g) (made by Kyowa Chemical Industry Co., Ltd.). Hexane (200 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 38 g of a colorless glassy concentrate (abc4) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,500 and weight average molecular weight (Mw) was 7,300.
Synthesis Example 9
Compound (abc4+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry toluene (50 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 110° C. A Pt catalyst (5 μL) and divinyl disiloxane (4.3 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 3 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and EOXTVE (3.3 g) were added, and the resultant mixture was stirred for 3 hours. Subsequently, CELLOXIDE 2000 (2.9 g) was added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
Subsequently, FM-1105 including hydrosilyl groups at both terminals (5.9 g), and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 300 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (trade name) (5 g) (made by Kyowa Chemical Industry Co., Ltd.). Hexane (200 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 48 g of a colorless glassy concentrate (abc4+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,300 and weight average molecular weight (Mw) was 7,000.
Synthesis Example 10
Compound (abc5) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry toluene (50 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 110° C. A Pt catalyst (5 μL) and divinyl disiloxane (4.3 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 3 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL ) and allyl oxetane (3.6 g) were added, and the resultant mixture was stirred for 3 hours. Subsequently, CELLOXIDE 2000 (2.9 g) was added, and the resultant mixture was stirred for 3 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Thus, 38 g of a colorless glassy concentrate (abc5) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,500 and weight average molecular weight (Mw) was 7,300.
Synthesis Example 11
Compound (abc5+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry toluene (50 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 110° C. A Pt catalyst (5 μL) and divinyl disiloxane (4.3 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 3 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL ) and allyl oxetane (3.6 g) were added, and the resultant mixture was stirred for 3 hours. Subsequently, CELLOXIDE 2000 (2.9 g) was added, and the resultant mixture was stirred for 3 hour.
Subsequently, FM-1105 including hydrosilyl groups at both terminals (5.9 g), and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 300 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (trade name) (5 g) (made by Kyowa Chemical Industry Co., Ltd.). Hexane (200 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 48 g of a colorless glassy concentrate (abc5+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,300 and weight average molecular weight (Mw) was 7,000.
Synthesis Example 12
Compound (abd1) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (42 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals DMS-V05 (18.4 g) (weight average molecular weight (Mw): 2,500, made by AZmax, Co.) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and CELLOXIDE 2000 (9.7 g) were added, and the resultant mixture was stirred for 3 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (7 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 56 g of a colorless glassy concentrate (abd1) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 9,200 and weight average molecular weight (Mw) was 79,000.
Synthesis Example 13
Compound (abd1+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (45 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals DMS-V05 (18.4 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and CELLOXIDE 2000 (9.7 g) were added, and the resultant mixture was stirred for 3 hours.
Subsequently, FM-1105 (5.9 g) and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 2 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (7 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 65 g of a colorless glassy concentrate (abd1+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 8,700 and weight average molecular weight (Mw) was 75,000.
Synthesis Example 14
Compound (abd2) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (42 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals DMS-V05 (18.4 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and EOXTVE (11.1 g) were added, and the resultant mixture was stirred for 5 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 56 g of a colorless glassy concentrate (abd2) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 9,200 and weight average molecular weight (Mw) was 79,000.
Synthesis Example 15
Compound (abd 2es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (45 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals DMS-V05 (18.4 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and EOXTVE (11.1 g) were added, and the resultant mixture was stirred for 5 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
Subsequently, FM-1105 (5.9 g) and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 2 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (7 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 65 g of a colorless glassy concentrate (abd2+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 8,700 and weight average molecular weight (Mw) was 75,000.
Synthesis Example 16
Compound (abd3) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (42 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals DMS-V05 (18.4 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and allyl oxetane (12.2 g) were added, and the resultant mixture was stirred for 3 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 56 g of a colorless glassy concentrate (abd3) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 9,200 and weight average molecular weight (Mw) was 79,000.
Synthesis Example 17
Compound (abd3+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (45 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals DMS-V05 (18.4 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and allyl oxetane (11.1 g) were added, and the resultant mixture was stirred for 3 hours.
Subsequently, FM-1105 (5.9 g) and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 2 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (7 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 65 g of a colorless glassy concentrate (abd3+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 8,700 and weight average molecular weight (Mw) was 75,000.
Synthesis Example 18
Compound (abd4) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (45 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals DMS-V05 (18.4 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and EOXTVE (5.6 g) were added, and the resultant mixture was stirred for 3 hours. Subsequently, CELLOXIDE 2000 (4.9 g) was added, and the resultant mixture was stirred for 3 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 56 g of a colorless glassy concentrate (abd4) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 9,200 and weight average molecular weight (Mw) was 79,000.
Synthesis Example 19
Compound (abd4+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (45 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals DMS-V05 (18.4 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and EOXTVE (5.6 g) were added, and the resultant mixture was stirred for 3 hours. Subsequently, CELLOXIDE 2000 (4.9 g) was added and the resultant mixture was stirred for 3 hours.
Subsequently, FM-1105 (5.9 g) and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 2 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 65 g of a colorless glassy concentrate (abd4+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 8,700 and weight average molecular weight (Mw) was 75,000.
Synthesis Example 20
Compound (abd5) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (45 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals DMS-V05 (18.4 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and allyl oxetane (6.1 g) were added, and the resultant mixture was stirred for 3 hours. Subsequently, CELLOXIDE 2000 (4.9 g) was added, and the resultant mixture was stirred for 3 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 56 g of a colorless glassy concentrate (abd5) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 9,200 and weight average molecular weight (Mw) was 79,000.
Synthesis Example 21
Compound (abd5+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (45 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals DMS-V05 (18.4 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and allyl oxetane (6.1 g) were added, and the resultant mixture was stirred for 3 hours. Subsequently, CELLOXIDE 2000 (4.9 g) was added and the resultant mixture was stirred for 3 hours.
Subsequently, FM-1105 (5.9 g) and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 2 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 65 g of a colorless glassy concentrate (abd5+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 8,700 and weight average molecular weight (Mw) was 75,000.
Synthesis Example 22
Compound (abel) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (45 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2205 (8.1 g) (weight average molecular weight (Mw): 700, made by JNC Corporation) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and CELLOXIDE 2000 (trade name) (8.6 g) (made by Daicel Chemical Industries, Ltd.) were added, and the resultant mixture was stirred for 5 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (trade name) (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 45 g of a colorless glassy concentrate (abe1) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,900 and weight average molecular weight (Mw) was 8,400.
Synthesis Example 23
Compound (abe 1+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (45 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2205 (8.1 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and CELLOXIDE 2000 (8.6 g) were added, and the resultant mixture was stirred for 3 hours.
Subsequently, FM-1105 (5.9 g) and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 2 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (7 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 56 g of a colorless glassy concentrate (abe1 +es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,500 and weight average molecular weight (Mw) was 7,600.
Synthesis Example 24
Compound (abe2) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (45 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2205 (8.1 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and EOXTVE (9.83 g) were added, and the resultant mixture was stirred for 5 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (trade name) (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 46 g of a highly transparent and colorless glassy concentrate (abe2) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,900 and weight average molecular weight (Mw) was 8,400.
Synthesis Example 25
Compound (abf2+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (45 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2205 (8.1 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and EOXTVE (9.8 g) were added, and the resultant mixture was stirred for 3 hours.
Subsequently, FM-1105 (5.9 g) and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 2 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (7 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 56 g of a colorless glassy concentrate (abe2+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,500 and weight average molecular weight (Mw) was 7,600.
Synthesis Example 26
Compound (abe3) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (45 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2205 (8.1 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction mixture was stirred at the reflux temperature (80° C.) for 2 hours. Subsequently, a Pt catalyst (5 μL) and allyl oxetane (10.8 g) were added, and the resultant mixture was stirred for 5 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 46 g of a highly transparent and colorless glassy concentrate (abe3) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,900 and weight average molecular weight (Mw) was 8,400.
Synthesis Example 27
Compound (abe3+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (45 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2205 (8.1 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and allyl oxetane (10.8 g) were added, and the resultant mixture was stirred for 3 hours.
Subsequently, FM-1105 (5.9 g) and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 2 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (7 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 56g of a colorless glassy concentrate (abe3+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,500 and weight average molecular weight (Mw) was 7,600.
Synthesis Example 28
Compound (abe4) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (45 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2205 (8.1 g) (weight average molecular weight (Mw): 700, made by JNC Corporation) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and EOXTVE (4.9 g) were added, and the resultant mixture was stirred for 3 hours. Subsequently, CELLOXIDE 2000 (trade name) (4.3 g) (made by Daicel Chemical Industries, Ltd.) was added, and the resultant mixture was stirred for 3 hours. The resultant reaction mixture was cooled to room temperature, 1g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 45 g of a highly transparent and colorless glassy concentrate (abe4) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,900 and weight average molecular weight (Mw) was 8,400.
Synthesis Example 29
Compound (abe4+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (45 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2205 (8.1 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and EOXTVE (4.9 g) were added, and the resultant mixture was stirred for 3 hours. Subsequently, CELLOXIDE 2000 (4.3 g) was added, and the resultant mixture was stirred for 3 hours.
Subsequently, FM-1105 (5.9 g) and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 2 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 55 g of a colorless glassy concentrate (abe4+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,500 and weight average molecular weight (Mw) was 7,600.
Synthesis Example 30
Compound (abe5) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (51 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2205 (8.1 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and allyl oxetane (5.4 g) were added, and the resultant mixture was stirred for 3 hours. Subsequently, CELLOXIDE 2000 (4.3 g) was added, and the resultant mixture was stirred for 2 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 46 g of a highly transparent and colorless glassy concentrate (abe5) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,900 and weight average molecular weight (Mw) was 8,400.
Synthesis Example 31
Compound (abe5+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (45 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2205 (8.1 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and allyl oxetane (5.4 g) were added, and the resultant mixture was stirred for 3 hours. Subsequently, CELLOXIDE 2000 (trade name) (4.3 g) was added, and the resultant mixture was stirred for 3 hours.
Subsequently, FM-1105 (5.9 g) and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 2 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 55 g of a colorless glassy concentrate (abe5+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 3,500 and weight average molecular weight (Mw) was 7,600.
Synthesis Example 32
Compound (abfl) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (51 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (2 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2203 (7.4 g) (weight average molecular weight (Mw): 400, made by JNC Corporation) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and CELLOXIDE 2000 (6.9 g) were added, and the resultant mixture was stirred for 5 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (4 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 47 g of a highly transparent and colorless glassy concentrate (abf1) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 4,800 and weight average molecular weight (Mw) was 11,600.
Synthesis Example 33
Compound (abfl+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (51 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (2 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2203 (7.4 g) (weight average molecular weight (Mw): 400, made by JNC Corporation) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and CELLOXIDE 2000 (6.9 g) were added, and the resultant mixture was stirred for 3 hours.
Subsequently, FM-1105 (5.9 g) and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 2 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 51 g of a colorless glassy concentrate (abf1+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 4,600 and weight average molecular weight (Mw) was 11,000.
Synthesis Example 34
Compound (abf2) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (51 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (0.8 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2203 (7.4 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and EOXTVE (7.9 g) were added, and the resultant mixture was stirred for 5 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 300 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (4 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 43 g of a highly transparent and colorless glassy concentrate (abf2) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 4,800 and weight average molecular weight (Mw) was 11,600.
Synthesis Example 35
Compound (abf2+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (51 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (0.8 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2203 (7.4 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and EOXTVE (7.9 g) were added, and the resultant mixture was stirred for 3 hours.
Subsequently, FM-1105 (5.9 g) and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 2 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 53 g of a colorless glassy concentrate (abf2+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 4,600 and weight average molecular weight (Mw) was 11,000.
Synthesis Example 36
Compound (abf3) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (51 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2203 (7.4 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and allyl oxetane (8.6 g) were added, and the resultant mixture was stirred for 5 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (4 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 44 g of a highly transparent and colorless glassy concentrate (abf3) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 4,800 and weight average molecular weight (Mw) was 11,600.
Synthesis Example 37
Compound (abf3+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (51 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2203 (7.4 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and allyl oxetane (8.6 g) were added, and the resultant mixture was stirred for 3 hours.
Subsequently, FM-1105 (5.9 g) and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 2 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 53 g of a colorless glassy concentrate (abf3+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 4,600 and weight average molecular weight (Mw) was 11,000.
Synthesis Example 38
Compound (abf4) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (51 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2203 (7.4 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μl) and EOXTVE (3.9 g) were added, and the resultant mixture was stirred for 3 hours. Subsequently, CELLOXIDE 2000 (3.4 g) was added, and the resultant mixture was stirred for 3 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 42 g of a highly transparent and colorless glassy concentrate (abf4) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 4,800 and weight average molecular weight (Mw) was 11,600.
Synthesis Example 39
Compound (abf4+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (51 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μl) and vinyl terminated polydimethylsiloxane at both terminals FM-2203 (7.4 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and EOXTVE (3.9 g) were added, and the resultant mixture was stirred for 3 hours. Subsequently, CELLOXIDE 2000 (3.4 g) was added, and the resultant mixture was stirred for 3 hours.
Subsequently, FM-1105 (5.9 g) and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 2 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 ((5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 53 g of a colorless glassy concentrate (abf4+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 4,600 and weight average molecular weight (Mw) was 11,000.
Synthesis Example 40
Compound (abf5) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (51 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 μL) and vinyl terminated polydimethylsiloxane at both terminals FM-2203 (7.4 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and allyl oxetane (4.3 g) were added, and the resultant mixture was stirred for 3 hours. Subsequently, CELLOXIDE 2000 (trade name) (3.6 g) was added, and the resultant mixture was stirred for 3 hours. The resultant reaction mixture was cooled to room temperature, 1 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 43 g of a highly transparent and colorless glassy concentrate (abf5) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 4,800 and weight average molecular weight (Mw) was 11,600.
Synthesis Example 41
Compound (abf5+es) was manufactured according to a formula below.




Under a nitrogen atmosphere, compound (A) (30 g) and dry ethyl acetate (51 g) were charged into a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was sealed with dry nitrogen. While the resultant mixture was stirred with a magnetic stirrer, the mixture was heated for a reaction temperature to be 80° C. A Pt catalyst (1 and vinyl terminated polydimethylsiloxane at both terminals FM-2203 (7.4 g) were added. The resultant reaction mixture was heated to a reflux temperature and stirred for 2 hours.
The reaction temperature was decreased to 80° C., a Pt catalyst (5 μL) and ally oxetane (4.3 g) were added, and the resultant mixture was stifled for 3 hours. Subsequently, CELLOXIDE 2000 (3.4 g) was added, and the resultant mixture was stirred for 3 hours.
Subsequently, FM-1105 (5.9 g) and CELLOXIDE 2000 (3.2 g) were added, and the resultant mixture was stirred for 1 hour. The resultant reaction mixture was cooled to room temperature, 2 g of activated carbon was added, and the resultant mixture was stirred overnight.
The activated carbon was removed by filtration. The resultant filtrate was transferred into an evaporator and concentrated therein. Then, 500 mL of hexane was added to a concentrate obtained to allow dissolution at 50° C. Purification was performed by chromatography using Kyoward 500 (5 g). Hexane (300 mL) was further added to allow washing of a purified material. A solution obtained was concentrated using an evaporator, and thus 53 g of a colorless glassy concentrate (abf5+es) was obtained. When the concentrate was analyzed by GPC, number average molecular weight (Mn) was 4,600 and weight average molecular weight (Mw) was 11,000.
Surface Treatment of a Phosphor with a Silane Coupling Agent
Under a nitrogen atmosphere, 2 g of a yellow phosphor YAG (Y,Gd)3(Al,Ga)5O12:Ce), 0.2 g of silane coupling agent (Silaplane 5530 (trade name), made by Chisso Corporation), and 100 mL of 95% ethanol were added to a reaction vessel having an internal volume of 200 mL and equipped with a thermometer, a dropping funnel and a reflux condenser, and the resultant mixture was stirred at 80° C. for 1 hour. After a reaction, a solvent was distilled off under reduced pressure at 100° C., and thus a phosphor subjected to surface modification was obtained.
Main Materials Used in the Present Examples
Silicon Compound Having an Epoxy Group
Compounds (ab), (abc1), (abc1+es), (abc2), (abc2+es), (abc3), (abc3+es), (abc4), (abc4+es), (abc5), (abc5+es), (abd1), (abd1+es), (abd2), (abd2+es), (abd3), (abd3+es), (abd4), (abd4+es), (abd5), (abd5+es), (abe1), (abe1+es), (abet), (abe2+es), (abe3), (abe3+es), (abe4), (abe4+es), (abe5), (abe5+es), (abf1), (abf1+es), (abf2), (abf2+es), (abf3), (abf3+es), (abf4), (abf4+es), (abf5), and (abf5+es), as manufactured in Synthesis Examples
Phosphor
Yellow phosphor YAG subjected to surface modification with a silane coupling agent (Silaplane 5530 (trade name), made by Chisso Corporation)
Hardening Agent
Thermal cationic polymerization initiator: TA-100, made by San-Apro Ltd.
Photocationic polymerization initiator: HS-1PG, made by San-Apro Ltd.
Epoxy Resin Including No Benzene Ring and No Silicon Atom in a Molecule
Oxetane resin: Aron Oxetane (trade name) DOX, made by Toagosei Co., Ltd.
Epoxy resin: CELLOXIDE (trade name) CEL2021P, made by Daicel Chemical Industries, Ltd.
Silane Coupling Agent
Silane coupling agent 5530 (trade name), made by Chisso Corporation Stabilizer
Antioxidant: IRGANOX 1010 (trade name), made by Ciba Japan K.K.
Antioxidant: IRGAFOS 168 (trade name), made by Ciba Japan K.K.
(Preparation of Hardened Materials 1 to 128)
A mixture of a stabilizer, an epoxy resin including no benzene ring and no silicon atom in a molecule, and a compound prepared in Synthetic Example was put into a screw vial, including compound (ab), (abc1), (abc1+es), (abc2), (abc2+es), (abc3), (abc3+es), (abc4), (abc4+es), (abc5), (abc5+es), (abd1), (abd1+es), (abd2), (abd2+es), (abd3), (abd3+es), (abd4), (abd4+es), (abd5), (abd5+es), (abe1), (abe1+es), (abe2), (abe2+es), (abe3), (abe3+es), (abe4), (abe4+es), (abe5), (abe5+es), (abf1), (abf1+es), (abf2), (abf2+es), (abf3), (abf3+es), (abf4), (abf4+es), (abf5) or (abf5+es) prepared in Synthesis Example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40 or 41, and subsequently a thermal cationic polymerization initiator was added therein as a hardening agent. The screw vial was set to Planetary Centrifugal Mixer (Thinky Mixer ARE-250 (trade name), made by Thinky Corporation), mixing and defoaming were performed, and thus a varnish was prepared.
The varnish was coated onto a biaxially oriented polyester film (50 μm, made by Mitsubishi Chemical Polyester Film Co., Ltd.) at a thickness of 100 micrometers with avoiding involvement of foam, a coated film was placed in an oven warmed at 100° C. to allow hardening. Heating was performed in the order of 100° C. for 1 hour, and 150° C. for 3 hours, and thus an epoxy silsesquioxane film was obtained. A film obtained was cut using a cutter knife, and a sample for measuring each of physical properties was prepared.
(Preparation of Hardened Materials 129 to 328)
Hardened materials 129 to 328 were prepared in a manner similar to preparation of hardened materials 1 to 128 except the hardening agent was changed to a photocationic polymerization initiator.
A mixture of an antioxidant, an epoxy resin, and a compound prepared in Synthetic Example was put into a screw vial, including a compound prepared in Synthesis Example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40 or 41, and subsequently a cationic polymerization initiator was added therein. The screw vial was set to Planetary Centrifugal Mixer (Thinky Mixer ARE-250 (trade name), made by Thinky Corporation), mixing and defoaming were performed, and thus a varnish was prepared.
The varnish was coated onto a biaxially oriented polyester film (50 um, made by Mitsubishi Chemical Polyester Film Co., Ltd.) at a thickness of 100 micrometers with avoiding involvement of foam.
When ultraviolet ray irradiation equipment J-CURE 1500 (trade name), made by JAPAN TECHNOLOGY SYSTEM Corporation, was used, and the varnish was irradiated with i-rays having an intensity of 500 mJ/cm2, an epoxy silsesquioxane film was obtained. A film obtained was cut using a cutter knife, and a sample for measuring each of physical properties was prepared.
(Preparation of comparative hardened materials 1 to 14) As a compound, at least one of an epoxy resin (CELLOXIDE CEL2021P (trade name), made by Daicel Chemical Industries, Ltd.), and octakis, made by Mayaterials, Inc., being a silsesquioxane derivative having an alicyclic epoxy group, was used, and as a hardening agent, a photocationic polymerization initiator was used, and thus a varnish was obtained in compositions as presented in Table 9 and Table 18. A film was prepared under conditions similar to the conditions for preparation of hardened materials 129 to 328.
Tables 1 to 9 and Tables 10 to 18 present compositions of hardened materials 1 to 328 and comparative hardened materials 1 to 14.













TABLE 1









Silane







coupling
Hardening
Antioxidant



Silicon-based
Epoxy including
agent
agent
Irganox1010:Irgafos168



polymer derivative
no silicon
(S530)
(TA-100)
1:3





















Hardened
ab (60)
DOX (40)
—
(0.01)
(1.0)


material 1


Hardened
ab (60)
DOX (35)
(5)
(0.01)
(1.0)


material 2


Hardened
ab (50)
CEL-2021P (50)
—
(0.01)
(1.0)


material 3


Hardened
ab (50)
CEL-2021P (45)
(5)
(0.01)
(1.0)


material 4


Hardened
abc1 (70)
DOX (30)
—
(0.01)
(1.0)


material 5


Hardened
abc1 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 6


Hardened
abc1 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 7


Hardened
abc1 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 8


Hardened
[abc1 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 9


Hardened
[abc1 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 10


Hardened
[abc1 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 11


Hardened
[abc1 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 12


Hardened
abc2 (70)
DOX (30)
—
(0.01)
(1.0)


material 13


Hardened
abc2 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 14


Hardened
abc2 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 15


Hardened
abc2 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 16


Hardened
[abc2 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 17


Hardened
[abc2 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 18


Hardened
[abc2 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 19


Hardened
[abc2 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 20





















TABLE 2








Silane

Antioxidant



Silicon-based
Epoxy
coupling
Hardening
Irganox1010:



polymer
including
agent
agent
Irgafos168



derivative
no silicon
(S530)
(TA-100)
1:3







Hardened
abc3 (70)
DOX (30)
—
(0.01)
(1.0)


material 21







Hardened
abc3 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 22







Hardened
abc3 (70)
CEL-2021P (30)
—
(0.01)
(1.0)


material 23







Hardened
abc3 (70)
CEL-2021P (25)
(5)
(0.01)
(1.0)


material 24







Hardened
[abc3 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 25







Hardened
[abc3 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 26







Hardened
[abc3 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 27







Hardened
[abc3 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 28







Hardened
abc4 (70)
DOX (30)
—
(0.01)
(1.0)


material 29







Hardened
abc4 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 30







Hardened
abc4 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 31







Hardened
abc4 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 32







Hardened
[abc4 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 33







Hardened
[abc4 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 34







Hardened
[abc4 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 35







Hardened
[abc3 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 36







Hardened
abc5 (70)
DOX (30)
—
(0.01)
(1.0)


material 37







Hardened
abc5 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 38







Hardened
abc5 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 39







Hardened
abc5 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 40





















TABLE 3








Silane

Antioxidant



Silicon-based
Epoxy
coupling
Hardening
Irganox1010:



polymer
including
agent
agent
Irgafos168



derivative
no silicon
(S530)
(TA-100)
1:3







Hardened
[abc5 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 41







Hardened
[abc5 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 42







Hardened
[abc5 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 43







Hardened
[abc5 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 44







Hardened
abd1 (70)
DOX (30)
—
(0.01)
(1.0)


material 45







Hardened
abd1 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 46







Hardened
abd1 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 47







Hardened
abd1 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 48







Hardened
[abd1 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 49







Hardened
[abd1 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 50







Hardened
[abd1 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 51







Hardened
[abd1 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 52







Hardened
abd2 (70)
DOX (30)
—
(0.01)
(1.0)


material 53







Hardened
abd2 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 54







Hardened
abd2 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 55







Hardened
abd2 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 56







Hardened
[abd2 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 57







Hardened
[abd2 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 58







Hardened
[abd2 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 59







Hardened
[abd2 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 60





















TABLE 4








Silane

Antioxidant



Silicon-based
Epoxy
coupling
Hardening
Irganox1010:



polymer
including
agent
agent
Irgafos168



derivative
no silicon
(S530)
(TA-100)
1:3







Hardened
abd3 (70)
DOX (30)
—
(0.01)
(1.0)


material 61







Hardened
abd3 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 62







Hardened
abd3 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 63







Hardened
abd3 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 64







Hardened
[abd3 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 65







Hardened
[abd3 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 66







Hardened
[abd3 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 67







Hardened
[abd3 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 68







Hardened
abd4 (70)
DOX (30)
—
(0.01)
(1.0)


material 69







Hardened
abd4 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 70







Hardened
abd4 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 71







Hardened
abd4 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 72







Hardened
[abd4 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 73







Hardened
[abd4 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 74







Hardened
[abd4 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 75







Hardened
[abd4 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 76







Hardened
abd5 (70)
DOX (30)
—
(0.01)
(1.0)


material 77







Hardened
abd5 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 78







Hardened
abd5 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 79







Hardened
abd5 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 80





















TABLE 5








Silane

Antioxidant



Silicon-based
Epoxy
coupling
Hardening
Irganox1010:



polymer
including
agent
agent
Irgafos168



derivative
no silicon
(S530)
(TA-100)
1:3







Hardened
[abd5 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 81







Hardened
[abd5 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 82







Hardened
[abd5 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 83







Hardened
[abd5 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 84







Hardened
abe1 (70)
DOX (30)
—
(0.01)
(1.0)


material 85







Hardened
abe1 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 86







Hardened
abe1 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 87







Hardened
abe1 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 88







Hardened
[abe1 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 89







Hardened
[abe1 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 90







Hardened
[abe1 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 91







Hardened
[abe1 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 92







Hardened
abe2 (70)
DOX (30)
—
(0.01)
(1.0)


material 93







Hardened
abe2 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 94







Hardened
abe2 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 95







Hardened
abe2 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 96







Hardened
[abe2 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 97







Hardened
[abe2 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 98







Hardened
[abe2 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 99







Hardened
[abe2 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 100





















TABLE 6








Silane

Antioxidant



Silicon-based
Epoxy
coupling
Hardening
Irganox1010:



polymer
including
agent
agent
Irgafos168



derivative
no silicon
(S530)
(TA-100)
1:3







Hardened
abe3 (70)
DOX (30)
—
(0.01)
(1.0)


material 101







Hardened
abe3 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 102







Hardened
abe3 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 103







Hardened
abe3 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 104







Hardened
[abe3 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 105







Hardened
[abe3 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 106







Hardened
[abe3 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 107







Hardened
[abe3 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 108







Hardened
abe4 (70)
DOX (30)
—
(0.01)
(1.0)


material 109







Hardened
abe4 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 110







Hardened
abe4 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 111







Hardened
abe4 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 112







Hardened
[abe4 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 113







Hardened
[abe4 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 114







Hardened
[abe4 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 115







Hardened
[abe4 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 116







Hardened
abe5 (70)
DOX (30)
—
(0.01)
(1.0)


material 117







Hardened
abe5 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 118







Hardened
abe5 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 119







Hardened
abe5 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 120





















TABLE 7








Silane

Antioxidant



Silicon-based
Epoxy
coupling
Hardening
Irganox1010:



polymer
including
agent
agent
Irgafos168



derivative
no silicon
(S530)
(TA-100)
1:3







Hardened
[abe5 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 121







Hardened
[abe5 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 122







Hardened
[abe5 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 123







Hardened
[abe5 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 124







Hardened
abf1 (70)
DOX (30)
—
(0.01)
(1.0)


material 125







Hardened
abf1 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 126







Hardened
abf1 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 127







Hardened
abf1 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 128







Hardened
[abf1 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 129







Hardened
[abf1 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 130







Hardened
[abf1 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 131







Hardened
[abf1 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 132







Hardened
abf2 (70)
DOX (30)
—
(0.01)
(1.0)


material 133







Hardened
abf2 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 134







Hardened
abf2 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 135







Hardened
abf2 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 136







Hardened
[abf2 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 137







Hardened
[abf2 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 138







Hardened
[abf2 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 139







Hardened
[abf2 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 140





















TABLE 8








Silane

Antioxidant



Silicon-based
Epoxy
coupling
Hardening
Irganox1010:



polymer
including
agent
agent
Irgafos168



derivative
no silicon
(S530)
(TA-100)
1:3







Hardened
abf3 (70)
DOX (30)
—
(0.01)
(1.0)


material 141







Hardened
abf3 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 142







Hardened
abf3 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 143







Hardened
abf3 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 144







Hardened
[abf3 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 145







Hardened
[abf3 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 146







Hardened
[abf3 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 147







Hardened
[abf3 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 148







Hardened
abf4 (70)
DOX (30)
—
(0.01)
(1.0)


material 149







Hardened
abf4 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 150







Hardened
abf4 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 151







Hardened
abf4 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 152







Hardened
[abf4 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 153







Hardened
[abf4 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 154







Hardened
[abf4 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 155







Hardened
[abf4 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 156







Hardened
abf5 (70)
DOX (30)
—
(0.01)
(1.0)


material 157







Hardened
abf5 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 158







Hardened
abf5 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 159







Hardened
abf5 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 160







Hardened
[abf5 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 161







Hardened
[abf5 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 162







Hardened
[abf5 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 163







Hardened
[abf5 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 164





















TABLE 9









Antioxidant




Silicon-based
Epoxy
Hardening
Irganox 1010:




polymer
including
agent
Irgafos 168




derivative
no silicon
(TA-100)
1:3
Remarks







Comparative

CEL-2021P (100)
(0.01)
(1.0)



hardened







material 1







Comparative

CEL-2021P (100)
(0.30)
(1.0)



hardened







material 2







Comparative
T8-CEL2000(50)
CEL-2021P (50)
(0.01)
(1.0)
The silicon


hardened




derivative


material 3




was not







dissolved.


Comparative
T8-CEL2000(30)
CEL-2021P (70)
(0.01)
(1.0)
The


hardened




antioxidant


material 4




was not







dissolved.


Comparative
T8-CEL2000(30)
CEL-2021P (70)
(0.05)
(1.0)



hardened







material 5







Comparative
T8-CEL2000(30)
DOX (70)
(0.01)
(1.0)
The silicon


hardened




derivative


material 6




was not







dissolved.


Comparative
T8-CEL2000(31)
DOX (47)
(0.01)
(1.0)



hardened

CEL-2021P (22)





material 7





















TABLE 10








Silane

Antioxidant



Silicon-based
Epoxy
coupling
Hardening
Irganox1010:



polymer
including
agent
agent
Irgafos168



derivative
no silicon
(S530)
(HS-1PG)
1:3







Hardened
ab (60)
DOX (40)
—
(0.02)
(1.0)


material 165







Hardened
ab (60)
DOX (35)
(5)
(0.02)
(1.0)


material 166







Hardened
ab (50)
CEL-2021P (50)
—
(0.03)
(1.0)


material 167







Hardened
ab (50)
CEL-2021P (45)
(5)
(0.03)
(1.0)


material 168







Hardened
abc1 (70)
DOX (30)
—
(0.01)
(1.0)


material 169







Hardened
abc1 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 170







Hardened
abc1 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 171







Hardened
abc1 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 172







Hardened
[abc1 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 173







Hardened
[abc1 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 174







Hardened
[abc1 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 175







Hardened
[abc1 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 176







Hardened
abc2 (70)
DOX (30)
—
(0.01)
(1.0)


material 177







Hardened

DOX (25)
(5)
(0.01)
(1.0)


material 178







Hardened
abc2 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 179







Hardened
abc2 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 180







Hardened
[abc2 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 181







Hardened
[abc2 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 182







Hardened
[abc2 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 183







Hardened
[abc2 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 184





















TABLE 11








Silane

Antioxidant



Silicon-based
Epoxy
coupling
Hardening
Irganox1010:



polymer
including
agent
agent
Irgafos168



derivative
no silicon
(S530)
(HS-1PG)
1:3







Hardened
abc3 (70)
DOX (30)
—
(0.01)
(1.0)


material 185







Hardened
abc3 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 186







Hardened
abc3 (70)
CEL-2021P (30)
—
(0.01)
(1.0)


material 187







Hardened
abc3 (70)
CEL-2021P (25)
(5)
(0.01)
(1.0)


material 188







Hardened
[abc3 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 189







Hardened
[abc3 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 190







Hardened
[abc3 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 191







Hardened
[abc3 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 192







Hardened
abc4 (70)
DOX (30)
—
(0.01)
(1.0)


material 193







Hardened
abc4 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 194







Hardened
abc4 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 195







Hardened
abc4 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 196







Hardened
[abc4 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 197







Hardened
[abc4 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 198







Hardened
[abc4 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 199







Hardened
[abc3 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 200







Hardened
abc5 (70)
DOX (30)
—
(0.01)
(1.0)


material 201







Hardened
abc5 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 202







Hardened
abc5 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 203







Hardened
abc5 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 204





















TABLE 12








Silane

Antioxidant



Silicon-based
Epoxy
coupling
Hardening
Irganox1010:



polymer
including
agent
agent
Irgafos168



derivative
no silicon
(S530)
(HS-1PG)
1:3







Hardened
[abc5 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 205







Hardened
[abc5 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 206







Hardened
[abc5 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 207







Hardened
[abc5 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 208







Hardened
abd1 (70)
DOX (30)
—
(0.01)
(1.0)


material 209







Hardened
abd1 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 210







Hardened
abd1 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 211







Hardened
abd1 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 212







Hardened
[abd1 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 213







Hardened
[abd1 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 214







Hardened
[abd1 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 215







Hardened
[abd1 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 216







Hardened
abd2 (70)
DOX (30)
—
(0.01)
(1.0)


material 217







Hardened
abd2 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 218







Hardened
abd2 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 219







Hardened
abd2 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 220







Hardened
[abd2 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 221







Hardened
[abd2 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 222







Hardened
[abd2 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 223







Hardened
[abd2 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 224





















TABLE 13








Silane

Antioxidant



Silicon-based
Epoxy
coupling
Hardening
Irganox1010:



polymer
including
agent
agent
Irgafos168



derivative
no silicon
(S530)
(HS-1PG)
1:3







Hardened
abd3 (70)
DOX (30)
—
(0.01)
(1.0)


material 225







Hardened
abd3 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 226







Hardened
abd3 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 227







Hardened
abd3 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 228







Hardened
[abd3 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 229







Hardened
[abd3 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 230







Hardened
[abd3 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 231







Hardened
[abd3 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 232







Hardened
abd4 (70)
DOX (30)
—
(0.01)
(1.0)


material 233







Hardened
abd4 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 234







Hardened
abd4 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 235







Hardened
abd4 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 236







Hardened
[abd4 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 237







Hardened
[abd4 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 238







Hardened
[abd4 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 239







Hardened
[abd4 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 240







Hardened
abd5 (70)
DOX (30)
—
(0.01)
(1.0)


material 241







Hardened
abd5 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 242







Hardened
abd5 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 243







Hardened
abd5 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 244





















TABLE 14








Silane

Antioxidant



Silicon-based
Epoxy
coupling
Hardening
Irganox1010:



polymer
including
agent
agent
Irgafos168



derivative
no silicon
(S530)
(HS-1PG)
1:3







Hardened
[abd5 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 245







Hardened
[abd5 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 246







Hardened
[abd5 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 247







Hardened
[abd5 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 248







Hardened
abe1 (70)
DOX (30)
—
(0.01)
(1.0)


material 249







Hardened
abe1 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 250







Hardened
abe1 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 251







Hardened
abe1 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 252







Hardened
[abe1 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 253







Hardened
[abe1 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 254







Hardened
[abe1 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 255







Hardened
[abe1 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 256







Hardened
abe2 (70)
DOX (30)
—
(0.01)
(1.0)


material 257







Hardened
abe2 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 258







Hardened
abe2 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 259







Hardened
abe2 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 260







Hardened
[abe2 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 261







Hardened
[abe2 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 262







Hardened
[abe2 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 263







Hardened
[abe2 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 264





















TABLE 15








Silane

Antioxidant



Silicon-based

coupling
Hardening
Irganox1010:



polymer
Epoxy including
agent
agent
Irgafos168



derivative
no silicon
(S530)
(HS-1PG)
1:3







Hardened
abe3 (70)
DOX (30)
—
(0.01)
(1.0)


material 265







Hardened
abe3 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 266







Hardened
abe3 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 267







Hardened
abe3 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 268







Hardened
[abe3 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 269







Hardened
[abe3 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 270







Hardened
[abe3 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 271







Hardened
[abe3 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 272







Hardened
abe4 (70)
DOX (30)
—
(0.01)
(1.0)


material 273







Hardened
abe4 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 274







Hardened
abe4 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 275







Hardened
abe4 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 276







Hardened
[abe4 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 277







Hardened
[abe4 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 278







Hardened
[abe4 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 279







Hardened
[abe4 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 280







Hardened
abe5 (70)
DOX (30)
—
(0.01)
(1.0)


material 281







Hardened
abe5 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 282







Hardened
abe5 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 283







Hardened
abe5 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 284






















TABLE 16









Silane

Antioxidant



Silicon-based
Epoxy
coupling
Hardening
Irganox1010:



polymer
including
agent
agent
Irgafos168



derivative
no silicon
(S530)
(HS-1PG)
1:3





















Hardened
[abe5 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 285


Hardened
[abe5 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 286


Hardened
[abe5 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 287


Hardened
[abe5 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 288


Hardened
abf1 (70)
DOX (30)
—
(0.01)
(1.0)


material 289


Hardened
abf1 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 290


Hardened
abf1 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 291


Hardened
abf1 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 292


Hardened
[abf1 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 293


Hardened
[abf1 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 294


Hardened
[abf1 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 295


Hardened
[abf1 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 296


Hardened
abf2 (70)
DOX (30)
—
(0.01)
(1.0)


material 297


Hardened
abf2 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 298


Hardened
abf2 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 299


Hardened
abf2 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 300


Hardened
[abf2 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 301


Hardened
[abf2 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 302


Hardened
[abf2 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 303


Hardened
[abf2 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 304






















TABLE 17









Silane

Antioxidant



Silicon-based
Epoxy
coupling
Hardening
Irganox1010:



polymer
including
agent
agent
Irgafos168



derivative
no silicon
(S530)
(HS-1PG)
1:3





















Hardened
abf3 (70)
DOX (30)
—
(0.01)
(1.0)


material 305


Hardened
abf3 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 306


Hardened
abf3 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 307


Hardened
abf3 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 308


Hardened
[abf3 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 309


Hardened
[abf3 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 310


Hardened
[abf3 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 311


Hardened
[abf3 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 312


Hardened
abf4 (70)
DOX (30)
—
(0.01)
(1.0)


material 313


Hardened
abf4 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 314


Hardened
abf4 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 315


Hardened
abf4 (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 316


Hardened
[abf4 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 317


Hardened
[abf4 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 318


Hardened
[abf4 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 319


Hardened
[abf4 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 320


Hardened
abf5 (70)
DOX (30)
—
(0.01)
(1.0)


material 321


Hardened
abf5 (70)
DOX (25)
(5)
(0.01)
(1.0)


material 322


Hardened
abf5 (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 323


Hardened
abf5 (80)
CEL-2021P(15)
(5)
(0.01)
(1.0)


material 324


Hardened
[abf5 + es] (70)
DOX (30)
—
(0.01)
(1.0)


material 325


Hardened
[abf5 + es] (70)
DOX (25)
(5)
(0.01)
(1.0)


material 326


Hardened
[abf5 + es] (80)
CEL-2021P (20)
—
(0.01)
(1.0)


material 327


Hardened
[abf5 + es] (80)
CEL-2021P (15)
(5)
(0.01)
(1.0)


material 328






















TABLE 18










Antioxidant




Silicon-based
Epoxy
Hardening
Irganox 1010:



polymer
including
agent
Irgafos 168



derivative
no silicon
(HS-1PG)
1:3
Remarks





















Comparative

CEL-2021P (100)
(0.01)
(1.0)



hardened


material 8


Comparative

CEL-2021P (100)
(0.30)
(1.0)


hardened


material 9


Comparative
T8-CEL2000(50)
CEL-2021P (50)
(0.01)
(1.0)
The silicon


hardened




derivative was


material 10




not dissolved.


Comparative
T8-CEL2000(30)
CEL-2021P (70)
(0.01)
(1.0)
The


hardened




antioxidant


material 11




was not







dissolved.


Comparative
T8-CEL2000(30)
CEL-2021P (70)
(0.05)
(1.0)


hardened


material 12


Comparative
T8-CEL2000(30)
DOX (70)
(0.01)
(1.0)
The silicon


hardened




derivative was


material 13




not dissolved.


Comparative
T8-CEL2000(31)
DOX (47)
(0.01)
(1.0)


hardened

CEL-2021P (22)


material 14









Physical properties of films obtained from hardened materials 1 to 328 and comparative hardened materials 1 to 14 were evaluated according methods described below. The results are presented in Tables 19 to 24 with regard to physical properties of films obtained from hardened materials 1 to 164 (Examples 1 to 164), and physical properties of films obtained from comparative hardened materials 1 to 7 (Comparative Examples 1 to 7), and presented in Tables 25 to 30 with regard to physical properties of films obtained from hardened materials 165 to 328 (Examples 165 to 328), and physical properties of films obtained from comparative hardened materials 8 to 14 (Comparative Examples 8 to 14).
Transparency in an Initial Stage
Luminous transmittance (at a wavelength of 400 nanometers) of each film was measured by means of a UV-Vis spectrophotometer (V-660, made by JASCO Corporation). The luminous transmittance was evaluated based on the following criteria:
A: 90% or more in luminous transmittance;
B: 70% or more and less than 90% in luminous transmittance; and
C: less than 70% in luminous transmittance.
Resistance to Thermal Yellowing
Moreover, a retention ratio {(luminous transmittance after heat treatment for 1,000 hours/luminous transmittance in an initial stage)×100} at a wavelength of 400 nanometers was calculated and evaluated. Moreover, a yellowness index (YI value) of a hardened material was calculated and evaluated as follows:
AA: less than 1 in a YI value;
A: 1 or more and less than 1.5 in a YI value;
B: 1.5 or more and less than 2.0 in a YI value; and
C: 2 or more in a YI value.
Heat Resistance Testing
Heat resistance testing was conducted according to a method described below, and heat resistance was evaluated. Two 100 μm-thick films were prepared, luminous transmittance of each film was measured by means of a UV-Vis spectrophotometer (V-660, made by JASCO Corporation), and transmittance at a wavelength of 400 nanometers was described as transmittance in an initial stage.
Each film was put into an oven at 150° C. (forced convection oven: DRM420DA, made by Advantech Toyo Co., Ltd.), and treated for 1,000 hours. Then, luminous transmittance (at a wavelength of 400 nanometers) of a hardened material before and after testing was measured by means of a UV-Vis spectrophotometer (V-660, made by JASCO Corporation). A retention ratio at the wavelength was evaluated from the luminous transmittance obtained based on the following criteria:
AA: 95% or more in a retention ratio of luminous transmittance;
A: 90% or more in a retention ratio of luminous transmittance;
B: 70 or more and less than 90% in a retention ratio of luminous transmittance; and
C: less than 70% in a retention ratio of luminous transmittance.
Hardening Properties
Kinds of varnishes prepared in preparation steps of hardened materials 165 to 328 and comparative hardened materials 8 to 14 were exposed with light, and then hardening properties of films obtained were evaluated based on the following criteria:
A: tack-free and hard;
B: tack-free but a film being wrinkled; and
C: tacky.
Adhesion Testing
Kinds of varnishes prepared in preparation steps of hardened materials 1 to 328 and comparative hardened materials 1 to 14 were applied onto glass substrates, and 100 μm-thick films were prepared under conditions similar to the conditions described above. A hardened film obtained was evaluated according to cross cut peeling testing (cross cut testing). Adhesion testing was conducted according to a cross cut tape method for 100 squares each having a space interval of 1 mm, and adhesion was evaluated based on the following criteria:
AA: 0 to 3 in the number of peeled squares;
A: 4 to 10 in the number of peeled squares;
B: 11 to 30 in the number of peeled squares; and
C: 31 to 100 in the number of peeled squares.












TABLE 19








Retention ratio
Resistance to




Transmit-
of transmittance
yellowing by



tance in
by heat
heat



initial
resistance
resistance



stage
testing at
testing at
Adhesion



400 nm
150° C.
150° C.
testing




















Example 1
A
A
A
A


Example 2
A
A
A
A


Example 3
A
A
A
A


Example 4
A
A
A
A


Example 5
A
AA
AA
AA


Example 6
A
AA
AA
AA


Example 7
A
AA
AA
AA


Example 8
A
AA
AA
AA


Example 9
A
AA
AA
AA


Example 10
A
AA
AA
AA


Example 11
A
AA
AA
AA


Example 12
A
AA
AA
AA


Example 13
A
AA
AA
AA


Example 14
A
AA
AA
AA


Example 15
A
AA
AA
AA


Example 16
A
AA
AA
AA


Example 17
A
AA
AA
AA


Example 18
A
AA
AA
AA


Example 19
A
AA
AA
AA


Example 20
A
AA
AA
AA


Example 21
A
AA
AA
AA


Example 22
A
AA
AA
AA


Example 23
A
AA
AA
AA


Example 24
A
AA
AA
AA


Example 25
A
AA
AA
AA


Example 26
A
AA
AA
AA


Example 27
A
AA
AA
AA


Example 28
A
AA
AA
AA


Example 29
A
AA
AA
AA


Example 30
A
AA
AA
AA


Example 31
A
AA
AA
AA


Example 32
A
AA
AA
AA


Example 33
A
AA
AA
AA


Example 34
A
AA
AA
AA


Example 35
A
AA
AA
AA





















TABLE 20








Retention ratio
Resistance to




Transmit-
of transmittance
yellowing by



tance in
by heat
heat



initial
resistance
resistance



stage
testing at
testing at
Adhesion



400 nm
150° C.
150° C.
testing




















Example 36
A
AA
AA
AA


Example 37
A
AA
AA
AA


Example 38
A
AA
AA
AA


Example 39
A
AA
AA
AA


Example 40
A
AA
AA
AA


Example 41
A
AA
AA
AA


Example 42
A
AA
AA
AA


Example 43
A
AA
AA
AA


Example 44
A
AA
AA
AA


Example 45
A
AA
AA
AA


Example 46
A
AA
AA
AA


Example 47
A
AA
AA
AA


Example 48
A
AA
AA
AA


Example 49
A
AA
AA
AA


Example 50
A
AA
AA
AA


Example 51
A
AA
AA
AA


Example 52
A
AA
AA
AA


Example 53
A
AA
AA
AA


Example 54
A
AA
AA
AA


Example 55
A
AA
AA
AA


Example 56
A
AA
AA
AA


Example 57
A
AA
AA
AA


Example 58
A
AA
AA
AA


Example 59
A
AA
AA
AA


Example 60
A
AA
AA
AA


Example 61
A
AA
AA
AA


Example 62
A
AA
AA
AA


Example 63
A
AA
AA
AA


Example 64
A
AA
AA
AA


Example 65
A
AA
AA
AA


Example 66
A
AA
AA
AA


Example 67
A
AA
AA
AA


Example 68
A
AA
AA
AA


Example 69
A
AA
AA
AA


Example 70
A
AA
AA
AA





















TABLE 21








Retention ratio
Resistance to




Transmit-
of transmittance
yellowing by



tance in
by heat
heat



initial
resistance
resistance



stage
testing at
testing at
Adhesion



400 nm
150° C.
150° C.
testing




















Example 71
A
AA
AA
AA


Example 72
A
AA
AA
AA


Example 73
A
AA
AA
AA


Example 74
A
AA
AA
AA


Example 75
A
AA
AA
AA


Example 76
A
AA
AA
AA


Example 77
A
AA
AA
AA


Example 78
A
AA
AA
AA


Example 79
A
AA
AA
AA


Example 80
A
AA
AA
AA


Example 81
A
AA
AA
AA


Example 82
A
AA
AA
AA


Example 83
A
AA
AA
AA


Example 84
A
AA
AA
AA


Example 85
A
AA
AA
AA


Example 86
A
AA
AA
AA


Example 87
A
AA
AA
AA


Example 88
A
AA
AA
AA


Example 89
A
AA
AA
AA


Example 90
A
AA
AA
AA


Example 91
A
AA
AA
AA


Example 92
A
AA
AA
AA


Example 93
A
AA
AA
AA


Example 94
A
AA
AA
AA


Example 95
A
AA
AA
AA


Example 96
A
AA
AA
AA


Example 97
A
AA
AA
AA


Example 98
A
AA
AA
AA


Example 99
A
AA
AA
AA


Example 100
A
AA
AA
AA


Example 101
A
AA
AA
AA


Example 102
A
AA
AA
AA


Example 103
A
AA
AA
AA


Example 104
A
AA
AA
AA


Example 105
A
AA
AA
AA





















TABLE 22








Retention ratio
Resistance to




Transmit-
of transmittance
yellowing by



tance in
by heat
heat



initial
resistance
resistance



stage
testing at
testing
Adhesion



400 nm
150° C.
at 150° C.
testing




















Example 106
A
AA
AA
AA


Example 107
A
AA
AA
AA


Example 108
A
AA
AA
AA


Example 109
A
AA
AA
AA


Example 110
A
AA
AA
AA


Example 111
A
AA
AA
AA


Example 112
A
AA
AA
AA


Example 113
A
AA
AA
AA


Example 114
A
AA
AA
AA


Example 115
A
AA
AA
AA


Example 116
A
AA
AA
AA


Example 117
A
AA
AA
AA


Example 118
A
AA
AA
AA


Example 119
A
AA
AA
AA


Example 120
A
AA
AA
AA


Example 121
A
AA
AA
AA


Example 122
A
AA
AA
AA


Example 123
A
AA
AA
AA


Example 124
A
AA
AA
AA


Example 125
A
AA
AA
AA


Example 126
A
AA
AA
AA


Example 127
A
AA
AA
AA


Example 128
A
AA
AA
AA


Example 129
A
AA
AA
AA


Example 130
A
AA
AA
AA


Example 131
A
AA
AA
AA


Example 132
A
AA
AA
AA


Example 133
A
AA
AA
AA


Example 124
A
AA
AA
AA


Example 135
A
AA
AA
AA


Example 136
A
AA
AA
AA


Example 137
A
AA
AA
AA


Example 138
A
AA
AA
AA


Example 139
A
AA
AA
AA


Example 140
A
AA
AA
AA





















TABLE 23








Retention ratio
Resistance to




Transmit-
of transmittance
yellowing by



tance in
by heat
heat



initial
resistance
resistance



stage
testing at
testing at
Adhesion



400 nm
150° C.
150° C.
testing




















Example 141
A
AA
AA
AA


Example 142
A
AA
AA
AA


Example 143
A
AA
AA
AA


Example 144
A
AA
AA
AA


Example 145
A
AA
AA
AA


Example 146
A
AA
AA
AA


Example 147
A
AA
AA
AA


Example 148
A
AA
AA
AA


Example 149
A
AA
AA
AA


Example 150
A
AA
AA
AA


Example 151
A
AA
AA
AA


Example 152
A
AA
AA
AA


Example 153
A
AA
AA
AA


Example 154
A
AA
AA
AA


Example 155
A
AA
AA
AA


Example 156
A
AA
AA
AA


Example 157
A
AA
AA
AA


Example 158
A
AA
AA
AA


Example 159
A
AA
AA
AA


Example 160
A
AA
AA
AA


Example 161
A
AA
AA
AA


Example 162
A
AA
AA
AA


Example 163
A
AA
AA
AA


Example 164
A
AA
AA
AA






















TABLE 24








Retention ratio
Resistance to





Transmit-
of transmittance
yellowing



tance in
by heat
by heat



initial
resistance
resistance



stage
testing at
testing at
Adhesion



400 nm
150° C.
150° C.
testing
Remarks





















Comparative
—
—
—
—
Not


Example 1




hardened


Comparative
A
C
C
C
Wrinkled


Example 2


Comparative
—
—
—
—
Not


Example 3




dissolved


Comparative
—
—
—
—
Not


Example 4




hardened


Comparative
A
C
C
C
Wrinkled


Example 5


Comparative
—
—
—
—
Not


Example 6




dissolved


Comparative
A
B
B
B
Wrinkled


Example 7






















TABLE 25








Retention ratio
Resistance to





Transmit-
of transmittance
yellowing by



tance in
by heat
heat



initial
resistance
resistance



stage
testing at
testing at
Adhesion
Hardening



400 nm
150° C.
150° C.
testing
properties





















Example 165
A
A
A
A
A


Example 166
A
A
A
A
A


Example 167
A
A
A
A
A


Example 168
A
A
A
A
A


Example 169
A
AA
AA
AA
A


Example 170
A
AA
AA
AA
A


Example 171
A
AA
AA
AA
A


Example 172
A
AA
AA
AA
A


Example 173
A
AA
AA
AA
A


Example 174
A
AA
AA
AA
A


Example 175
A
AA
AA
AA
A


Example 176
A
AA
AA
AA
A


Example 177
A
AA
AA
AA
A


Example 178
A
AA
AA
AA
A


Example 179
A
AA
AA
AA
A


Example 180
A
AA
AA
AA
A


Example 181
A
AA
AA
AA
A


Example 182
A
AA
AA
AA
A


Example 183
A
AA
AA
AA
A


Example 184
A
AA
AA
AA
A


Example 185
A
AA
AA
AA
A


Example 186
A
AA
AA
AA
A


Example 187
A
AA
AA
AA
A


Example 188
A
AA
AA
AA
A


Example 189
A
AA
AA
AA
A


Example 190
A
AA
AA
AA
A


Example 191
A
AA
AA
AA
A


Example 192
A
AA
AA
AA
A


Example 193
A
AA
AA
AA
A


Example 194
A
AA
AA
AA
A


Example 195
A
AA
AA
AA
A


Example 196
A
AA
AA
AA
A


Example 197
A
AA
AA
AA
A






















TABLE 26








Retention ratio
Resistance to





Transmit-
of transmittance
yellowing by



tance in
by heat
heat



initial
resistance
resistance



stage
testing at
testing at
Adhesion
Hardening



400 nm
150° C.
150° C.
testing
properties





















Example 198
A
AA
AA
AA
A


Example 199
A
AA
AA
AA
A


Example 200
A
AA
AA
AA
A


Example 201
A
AA
AA
AA
A


Example 202
A
AA
AA
AA
A


Example 203
A
AA
AA
AA
A


Example 204
A
AA
AA
AA
A


Example 205
A
AA
AA
AA
A


Example 206
A
AA
AA
AA
A


Example 207
A
AA
AA
AA
A


Example 208
A
AA
AA
AA
A


Example 209
A
AA
AA
AA
A


Example 210
A
AA
AA
AA
A


Example 211
A
AA
AA
AA
A


Example 212
A
AA
AA
AA
A


Example 213
A
AA
AA
AA
A


Example 214
A
AA
AA
AA
A


Example 215
A
AA
AA
AA
A


Example 216
A
AA
AA
AA
A


Example 217
A
AA
AA
AA
A


Example 218
A
AA
AA
AA
A


Example 219
A
AA
AA
AA
A


Example 220
A
AA
AA
AA
A


Example 221
A
AA
AA
AA
A


Example 222
A
AA
AA
AA
A


Example 223
A
AA
AA
AA
A


Example 224
A
AA
AA
AA
A


Example 225
A
AA
AA
AA
A


Example 226
A
AA
AA
AA
A


Example 227
A
AA
AA
AA
A


Example 228
A
AA
AA
AA
A


Example 229
A
AA
AA
AA
A


Example 230
A
AA
AA
AA
A






















TABLE 27








Retention ratio
Resistance to





Transmit-
of transmittance
yellowing by



tance in
by heat
heat



initial
resistance
resistance



stage
testing at
testing at
Adhesion
Hardening



400 nm
150° C.
150° C.
testing
properties





















Example 231
A
AA
AA
AA
A


Example 232
A
AA
AA
AA
A


Example 233
A
AA
AA
AA
A


Example 234
A
AA
AA
AA
A


Example 235
A
AA
AA
AA
A


Example 236
A
AA
AA
AA
A


Example 237
A
AA
AA
AA
A


Example 238
A
AA
AA
AA
A


Example 239
A
AA
AA
AA
A


Example 240
A
AA
AA
AA
A


Example 241
A
AA
AA
AA
A


Example 242
A
AA
AA
AA
A


Example 243
A
AA
AA
AA
A


Example 244
A
AA
AA
AA
A


Example 245
A
AA
AA
AA
A


Example 246
A
AA
AA
AA
A


Example 247
A
AA
AA
AA
A


Example 248
A
AA
AA
AA
A


Example 249
A
AA
AA
AA
A


Example 250
A
AA
AA
AA
A


Example 251
A
AA
AA
AA
A


Example 252
A
AA
AA
AA
A


Example 253
A
AA
AA
AA
A


Example 254
A
AA
AA
AA
A


Example 255
A
AA
AA
AA
A


Example 256
A
AA
AA
AA
A


Example 257
A
AA
AA
AA
A


Example 258
A
AA
AA
AA
A


Example 259
A
AA
AA
AA
A


Example 260
A
AA
AA
AA
A


Example 261
A
AA
AA
AA
A


Example 262
A
AA
AA
AA
A


Example 263
A
AA
AA
AA
A






















TABLE 28








Retention ratio
Resistance to





Transmit-
of transmittance
yellowing by



tance in
by heat
heat



initial
resistance
resistance



stage
testing at
testing at
Adhesion
Hardening



400 nm
150° C.
150° C.
testing
properties





















Example 264
A
AA
AA
AA
A


Example 265
A
AA
AA
AA
A


Example 266
A
AA
AA
AA
A


Example 267
A
AA
AA
AA
A


Example 268
A
AA
AA
AA
A


Example 269
A
AA
AA
AA
A


Example 270
A
AA
AA
AA
A


Example 271
A
AA
AA
AA
A


Example 272
A
AA
AA
AA
A


Example 273
A
AA
AA
AA
A


Example 274
A
AA
AA
AA
A


Example 275
A
AA
AA
AA
A


Example 276
A
AA
AA
AA
A


Example 277
A
AA
AA
AA
A


Example 278
A
AA
AA
AA
A


Example 279
A
AA
AA
AA
A


Example 280
A
AA
AA
AA
A


Example 281
A
AA
AA
AA
A


Example 282
A
AA
AA
AA
A


Example 283
A
AA
AA
AA
A


Example 284
A
AA
AA
AA
A


Example 285
A
AA
AA
AA
A


Example 286
A
AA
AA
AA
A


Example 287
A
AA
AA
AA
A


Example 288
A
AA
AA
AA
A


Example 289
A
AA
AA
AA
A


Example 290
A
AA
AA
AA
A


Example 291
A
AA
AA
AA
A


Example 292
A
AA
AA
AA
A


Example 293
A
AA
AA
AA
A


Example 294
A
AA
AA
AA
A


Example 295
A
AA
AA
AA
A


Example 296
A
AA
AA
AA
A






















TABLE 29








Retention ratio
Resistance to





Transmit-
of transmittance
yellowing by



tance in
by heat
heat



initial
resistance
resistance



stage
testing at
testing at
Adhesion
Hardening



400 nm
150° C.
150° C.
testing
properties





















Example 297
A
AA
AA
AA
A


Example 298
A
AA
AA
AA
A


Example 299
A
AA
AA
AA
A


Example 300
A
AA
AA
AA
A


Example 301
A
AA
AA
AA
A


Example 302
A
AA
AA
AA
A


Example 303
A
AA
AA
AA
A


Example 304
A
AA
AA
AA
A


Example 305
A
AA
AA
AA
A


Example 306
A
AA
AA
AA
A


Example 307
A
AA
AA
AA
A


Example 308
A
AA
AA
AA
A


Example 309
A
AA
AA
AA
A


Example 310
A
AA
AA
AA
A


Example 311
A
AA
AA
AA
A


Example 312
A
AA
AA
AA
A


Example 313
A
AA
AA
AA
A


Example 314
A
AA
AA
AA
A


Example 315
A
AA
AA
AA
A


Example 316
A
AA
AA
AA
A


Example 317
A
AA
AA
AA
A


Example 318
A
AA
AA
AA
A


Example 319
A
AA
AA
AA
A


Example 320
A
AA
AA
AA
A


Example 321
A
AA
AA
AA
A


Example 322
A
AA
AA
AA
A


Example 323
A
AA
AA
AA
A


Example 324
A
AA
AA
AA
A


Example 325
A
AA
AA
AA
A


Example 326
A
AA
AA
AA
A


Example 327
A
AA
AA
AA
A


Example 328
A
AA
AA
AA
A























TABLE 30









Resistance








to





yellowing




Retention ratio of
by heat



Transmittance
transmittance by
resistance



in initial stage
heat resistance
testing at
Adhesion
Hardening



400 nm
testing at 150° C.
150° C.
testing
properties
Remarks






















Comparative
—
—
—
—
—
Not


Example 8





hardened


Comparative
A
C
C
C
C
Wrinkled


Example 9


Comparative
—
—
—
—
—
Not


Example 10





dissolved


Comparative
—
—
—
—
—
Not


Example 11





hardened


Comparative
A
C
C
C
C
Wrinkled


Example 12


Comparative
—
—
—
—
—
Not


Example 13





dissolved


Comparative
A
B
B
B
B
A small


Example 14





amount of








blisters








Uneven








film









Examples 329 to 656
To each varnish prepared in preparation steps of the hardened materials 1 to 328, the phosphor (YAG) subjected to surface treatment with the silane coupling agent was mixed for a concentration of particles of the phosphor to be 20% by mass. Then, 100 μm-thick films were prepared in a manner similar to the operations in Examples 1 to 328 except for addition of YAG. A film obtained was cut using a cutter knife, and a sample for measurement was prepared. The samples for measurement obtained from kinds of varnishes prepared in the preparation steps of the hardened materials 1 to 328 were used are described in Examples 329 to 656, respectively.
Comparative Examples 1 to 14 
To each varnish prepared in preparation steps of the comparative hardened materials 1 to 14, the phosphor (YAG) subjected to surface treatment with the silane coupling agent was mixed for a concentration of particles of the phosphor to be 20% by mass. Then, 100 um-thick films were prepared in a manner similar to the operations in Examples 1 to 328, and samples for measurement were obtained. The samples for measurement obtained from kinds of varnishes prepared in the preparation steps of the comparative hardened materials 1 to 14 were used are described in Comparative Examples 15 to 28, respectively.
Color Change Testing
Color changes in films according to Examples 329 to 656 and Comparative Examples 15 to 28 were investigated by irradiating the resulting films with light from a blue LED chip, and the color changes were evaluated based on the following criteria:
Good: without a flare spot on a film; and
Bad: with a flare spot on a film.
Table 31 presents the results of evaluation of test specimens obtained in Examples 329 to 656 and Comparative Examples 15 to 28.










TABLE 31







Examples 329 to 656
Comparative Examples 5 to 28


















Flare spot
Good
Bad









The results in Table 31 clearly show that the hardened material obtained using the hardening resin composition according to the invention has a high transparency, and while the hardened material has adhesion strength comparable to the strength of a conventional epoxy resin, has an excellent resistance to thermal yellowing even under a high temperature environment over a long period of time.
Moreover, the hardened material obtained using the hardening resin composition according to the invention has a skeleton of double-decker silsesquioxane, and therefore is found to have an excellent compatibility with other compounds to allow the phosphor to be uniformly dispersed into the resin composition.
Furthermore, when the phosphor is subjected to surface modification with the silane coupling agent having the epoxy group upon preparing the hardened material, the phosphor is found to allow quick hardening with the epoxy group in the resin without sedimentation in the resin to allow obtaining of a wavelength conversion material, without a flare spot, into which the phosphor is uniformly dispersed.
Although the invention has been described in detail with reference to a specific embodiment, those skilled in the art will appreciate that various modifications and variations can be made without departing from the intention and the scope of the invention. In addition, the present application is based on Japan Patent Application (application for patent 2011-033970) applied on Feb. 18, 2011, which is herein incorporated by reference in its entirety.

## Claims

1. A hardening resin composition containing (A) to (E) below:
(A) a silicon compound that is obtained by performing a hydrosilylation reaction among compound (a), compound (b), and when necessary, compound (c) below, and has at least one of epoxy and oxetanyl, wherein
compound (a) is at least one of silicone and silsesquioxane having two or more of SiH in one molecule and is at least one kind selected from the group of compounds represented by formula (a-1) to formula (a-5) and formula (a-7) to formula (a-10) below,










wherein, in formula (a-1) to formula (a-5) and formula (a-7) to formula (a-10),
R is a group independently selected from alkyl having 1 to 45 carbons, cycloalkyl having 4 to 8 carbons, aryl having 6 to 14 carbons and arylalkyl having 7 to 24 carbons; in the alkyl having 1 to 45 carbons, arbitrary hydrogen may be replaced by fluorine, and arbitral non-adjacent —CH2— may be replaced by —O— or —CH═CH—; in a benzene ring in the aryl and the arylalkyl, arbitrary hydrogen may be replaced by halogen or alkyl having 1 to 10 carbons, and in the alkyl having 1 to 10 carbons, arbitrary hydrogen may be replaced by fluorine, and arbitrary non-adjacent —CH2— may be replaced by —O— or —CH═CH—; the number of carbons of alkylene in the arylalkyl is 1 to 10, and arbitrary non-adjacent —CH2—may be replaced by —O—;
R1 and R2 are a group independently selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl;
R3 is a group independently selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl;
at least two of X, in one molecules of each compound, are hydrogen, and the rest of X is a group independently selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl; and
n is an integer from 0 to 100, and m is an integer from 3 to 10;
compound (b) is a compound having at least one of epoxy and oxetanyl, and alkenyl having 2 to 18 carbons in one molecule,
and compound (c) is at least one of silicone and silsesquioxane having two or more of alkenyl in one molecule;
(B) a phosphor;
(C) an epoxy resin;
(D) a hardening agent; and
(E) an antioxidant.

2. The hardening resin composition according to claim 1, wherein compound (b) is at least one kind selected from the group of compounds represented by formula (b-1) to formula (b-3) below, and compound (c) in a case where compound (c) is used when necessary is at least one kind selected from the group of compounds represented by formula (c-1) and (c-2):



wherein, in formula (b-1) to (b-3), at least one of R4 and R5 is alkenyl having 2 to 10carbons, and one of —CH2— in the alkenyl may be replaced by 1,4-phenylene, and the other is hydrogen or alkyl having 1 to 6 carbons:




wherein, in formula (c-1) and formula (c-2),
R and R3 are a group defined in a manner similar to the definitions of R and
R3 in formula (a-5) and formula (a-7) of claim 1,
R1 is a group independently selected from alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl and phenyl,
Y is a group independently selected from vinyl and allyl, and
n is an integer from 0 to 100.

3. The hardening resin composition according to claim 1, wherein compound (a) is a silsesquioxane derivative represented by formula (a-1-1) below:

4. The hardening resin composition according to claim 1, wherein compound (b) is one kind or two kinds selected from the group of compounds represented by formula (b-1-1), formula (b-2-1), formula (b-2-2), formula (b-3-1) and formula (b-3-2):

5. The hardening resin composition according to claim 2, wherein compound (c) is represented by formula (c-1-1) or formula (c-2-1) below:

6. The hardening resin composition according to claim 1, wherein the silicon compound represented by (A) and having the epoxy group is polysilsesquioxane represented by formula (α):



wherein, in formula (α), p is an integer from 1 to 100, q and r each are a value satisfying expressions: 0≦q≦1.95 and 0.1≦r≦4, s is a value satisfying an expression: 0 ≦s≦3, and q, r and s each are a value satisfying an expression: 2q+r+s≦4.

7. The hardening resin composition according to claim 1, wherein the silicon compound represented by (A) and having the epoxy is silsesquioxane represented by formula (β):

8. The hardening resin composition according to claim 1, wherein the phosphor represented by (B) is a phosphor for a white LED.

9. The hardening resin composition according to claim 1, wherein the epoxy resin represented by (C) is an epoxy resin represented by formula (γ1) or (γ2), and has at least one of the epoxy resins:

10. The hardening resin composition according to claim 1, wherein the hardening agent represented by (D) is a thermal cationic polymerization initiator or a photocationic polymerization initiator.

11. The hardening resin composition according to claim 1, wherein the antioxidant represented by (E) is a phenolic antioxidant or a phosphorus-based antioxidant, and a phenolic antioxidant.

12. A hardened material in a form of a film, a sheet or a coating film, obtained by applying onto a transparent base material the hardening resin composition according to claim 1, and hardening an applied product by heating or light irradiation.

13. A color conversion material containing the hardened material according to claim 12.

14. An optical semiconductor device including the color conversion material according to claim 13.