# Patent

## Title
Optical element and manufacturing method of the optical element

## Abstract

An optical element having an optical axis, comprises an element body having the maximum first length of 4 mm or less in the optical axis direction and the second maximum length of 6 mm or less in the direction perpendicular to the optical axis direction; wherein the element body is made of a resin containing a polymer having an alicyclic structure and is treated by one of heat treatment and wet-heat treatment for 16 hours or longer at a temperature lower by 35° C. to 45° C. than the glass transition temperature of the resin after the element body has been formed by injecting the resin in a mold, where the glass transition temperature of the resin is measured by differential-scanning-calorimetry method at heating rate 10° C./min on the basis of JIS K7121.

## Background
BACKGROUND OF THE INVENTION
This invention relates to a small-sized optical element and its manufacturing method, which is used for a light pickup lens of light pickup device and so on.
Lately, there are manufactured and on sale, various kinds of optical element of various sizes, such as large-sized optical elements used for telescope lenses and microscope lenses and small-sized optical elements used for light pickup lenses of CD (Compact Disc) and DVD (Digital Video Disc). These optical elements are usually manufactured through so called “injection molding” process in which specific resin corresponding to the application is injected into a prescribed die for molding, however on the surface layer of the mold, there occurs birefringence to some extent, created by a residual stress, and therefore, a light scattering phenomenon occurs on the surface layer to make it difficult to maintain the focal distance to be the wanted design value.
In Patent Document 1, it is described that the residual stress generated in a molded product can be relieved and birefringence generated in the mold can be minimized by means of annealing the product at a temperature below the glass transition-temperature after cooling (leaving as it is) at the room temperature.
[Patent Document 1] U.S. Pat. No. 3,055,443
However, the objective of the technique disclosed in Patent Document 1 is to apply annealing process to relatively large-sized optical elements when they are molded to add some preferable performance to the molds, and though the conditions for the annealing process are specified in detail, the conditions are not available to every optical element made of resin manufactured through an injection molding process. For example, regarding a small-sized optical element of a several millimeter scale used as the aforementioned light pickup lens, only if the conditions for the annealing process slightly differ in each manufacturing lot, the difference of the conditions affects performance of forming a spot of condensed light greatly. Therefore, the annealing process of the technique disclosed in the Patent Document 1, can not relieve the residual stress sufficiently and can not maintain the thermal balance condition stably during the annealing process so that sufficient performance can not be obtained for a optical element of light pickup lens.
SUMMARY OF THE INVENTION
An objective of this invention regards a optical element which can be used favorably as a small-sized optical element of light pickup lens and its manufacturing method, and is to provide a optical element with optical characteristics such as astigmatism, which are tremendously improved after the residual stress is sufficiently relieved, and its manufacturing method.
The invention described in Item 1 to solve the above-mentioned problems is related to an optical element having an optical axis, comprises:
an element body having the maximum first length of 4 mm or less in the optical axis direction and the second maximum length of 6 mm or less in the direction perpendicular to the optical axis direction;
wherein the element body is made of a resin containing a polymer having an alicyclic structure and is treated by one of heat treatment and wet-heat treatment for 16 hours or longer at a temperature lower by 35° C. to 45° C. than the glass transition temperature of the resin after the element body has been formed by injecting the resin in a mold, where the glass transition temperature of the resin is measured by differential-scanning-calorimetry method at heating rate 10° C./min on the basis of JIS K7121.
In the optical element described in Item 1, the optical element described in Item 2 is characterized in that the treating time is 150 hours or longer.
In the optical element described in Item 1, the optical element described in Item 3 is characterized in that a relative humidity at each temperature of the wet-heat treatment is 40% to 80%.
In the optical element described in Item 1, the optical element described in Item 4 is characterized in that a relative humidity at each temperature of the wet-heat treatment is 55% to 65%.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view showing a schematic structure of a light pickup device.
FIG. 2(a) is a perspective view and FIG. 2(b) is a cross-sectional view showing a schematic structure of a light pickup lens.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Firstly, preferable structures to attain the above object are explained.
The invention described in Item 2-1 to solve the above-mentioned problems is related to an optical element having the maximum length in the optical axis direction is less than 3 mm and the maximum length in the direction perpendicular to the optical axis direction is less than 5 mm, wherein the optical element is annealed at a temperature lower than the glass transition temperature of the resin by 35° C. through 45° C. for more than 16 hours after resin which contains a polymer having an alicyclic structure is injected into a die for molding.
In the optical element described in Item 2-1, an optical element described in Item 2-2 is characterized in that the resin containing polymers having an alicyclic structure contains repeating unit (a) having an alicyclic structure represented by following general formula (1) and repeating unit (b) comprising a chain structure represented by following general formula (2) and/or (3) so as to make the sum content of repeating unit not less than 90 weight %, and, further, make the content of repeating unit (b) not less than 1 weight % and less than 10 weight % among whole repeating units of a polymer having a weight average molecular weight (Mw) of 1,000 to 1,000,000, and the chain of the repeating unit (a) satisfies the following formula (Z):

A≦0.3×B  (Z)

(in the formula (Z), A=(a weight average molecular weight of a repeating unit chain having an alicyclic type structure), and B=(a weight average molecular weight of a hydrocarbon copolymer having an alicyclic type structure(Mw)×(the number of repeating units having an alicyclic type structure/the number of whole repeating units constructing the hydrocarbon copolymer having the alicyclic type structure).





(X in general formula (1) represents an alicyclic hydrocarbon group, R1–R13 in formulas (1), (2) and (3) each independently represent a hydrogen atom, a chain hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ether group, an ester group, a cyano group, an amido group, an imido group, a silyl group and a chain hydrocarbon group substituted by a polar group (a halogen atom, an alkoxy group, a hydroxyl group, an ether group, an ester group, a cyano group, an amido group, an imido group or a silyl group). In general formula (3) “ . . . ” represents a carbon-carbon saturated bond or a carbon-carbon unsaturated bond.) In the optical element described in Item 2-2, an optical element described in Item 2-3 is characterized in that the resin containing polymers having an alicyclic structure includes block copolymers having polymer block [A] containing a repeating unit [1] represented by a formula (11) and poloymer block [B] containing a repeating unit [1] and a repeating unit [2] represented by a formula (12) and/or a repeating unit [3] represented by a formula (13) and the block copolymers satisfy the relationship of a>b, where a is a mol fraction (mol %) of the repeating unit [1] in the polymer block [A] and b is a mol fraction (mol %) of the repeating unit [1] in the polymer block [B].





(In the formula (11), R1 represents a hydrogen atom or an alkyl group having a carbon number of 1–20, R2–R12 each independently represent a hydrogen atom, an alkyl group having a carbon number of 1–20, a hydroxyl group, an alkoxy group having a carbon number of 1–20 or a halogen group.)





(In the formula (12), R13 represents a hydrogen atom or an alkyl group having a carbon number of 1–20.)





(In the formula (13), R14 and R15 each independently represent a hydrogen atom or an alkyl group having a carbon number of 1–20.)

The invention described in claim 4 is characterized by using the optical element described in any one of claims 1 through 3 as a light pickup lens of light pickup device.
The invention is related to a manufacturing method for an optical element having the maximum length in the optical axis direction is less than 4 mm and the maximum length in the direction perpendicular to the optical axis direction is less than 6 mm, wherein the molded resin is annealed at a temperature lower than the glass transition temperature of the resin by 35° C. through 45° C. for more than 16 hours after resin which contains a polymer having an alicyclic structure is injected into a die for molding.
In the optical element of Items 2-1 through 2-4, the residual stress is relieved sufficiently and optical characteristics such as astigmatism are tremendously improved because it is annealed at a temperature lower than the glass transition temperature of the resin by 35° C. through 45° C. for more than 16 hours after resin which contains a polymer having an alicyclic structure is injected into a die for molding.
In the optical element described in claims 5, it is possible to manufacture an optical element wherein the residual stress is relieved sufficiently and the optical characteristics such as astigmatism are tremendously improved, because the molded resin is annealed at a temperature lower than the glass transition temperature of the resin by 35° C. through 45° C. for more than 16 hours after resin which contains a polymer having an alicyclic structure is injected into a die for molding.
Preferred embodiments of the invention will be explained referring to diagrams, however the scope of the invention is not limited to the examples illustrated in the diagrams.
FIG. 1 is a cross-sectional view showing a schematic structure of light pickup device 1.
As shown in FIG. 1, the light pickup device 1 has light source unit 2. The light source unit 2 has box-shaped casing 3 composed of a translucent base board shown in the upper portion of the casing 3 in FIG. 1. CD light source 4 which emits a light (laser beam) with a specific wavelength for CD and DVD light source 5 which emits a light (laser beam) with a specific wavelength for DVD are arranged in casing 3. Light emitted from CD light source 4 permeates through the translucent base plate of casing 3 and continues to travel in the permeation direction as a light beam indicated by dotted lines in FIG. 1, and light emitted from DVD light source 5 permeates through the translucent base plate of casing 3 and continues to travel in the permeation direction as a light beam indicated by solid lines in FIG. 1.
In the optical axis direction of each light beam emitted from CD light source 4 and DVD light source 5, collimator 11, splitter 12, 1⁄4 wavelength plate 13, aperture plate 14 and light pickup lens 15 are arranged in order of the position from the lower side toward the upper side in FIG. 1, and CD 20 and DVD 30 representing information recording media are arranged at the position facing light pickup lens 15. In the right side of splitter 12 in FIG. 1, cylindrical lens 16, concave lens 17 and sensor 18 are arranged in order of the position from the left side toward the right side in FIG. 1.
Light pickup lens 15 used as an optical element related to this invention is an aspherical objective lens for optical discs and arranged at the position facing CD 20 and DVD30 representing information recording media. The light pickup lens 15 is arranged movable in the vertical direction in FIG. 1 and is located at the position shown by dotted lines when information in CD 20 is read, and it is located at the position shown by solid lines when information in DVD 30 is read.
A brief explanation of the movement and operation of light pickup device 1 will be given as follows.
When information in CD 20 is read, light pickup lens 15 is located at the position shown by dotted lines in FIG. 1 and CD light source 4 emits light on this condition. The light emitted from CD light source 4 firstly permeates through collimator 12 to become a parallel light flux, and then permeates through splitter 12 and 1⁄4 wavelength plate 13 to be narrowed by an aperture plate 14, and further it permeates light pickup lens 15 to form a spot of condensed light on the recording surface of CD 20.
The light which forms a spot of condensed light is modulated by an information pit on the recording surface of CD 20, and reflected on the recording surface, and then, the reflected light permeates through light pickup lens 15, apertures plate 14 and 1⁄4 wavelength plate 13 to be split by splitter 12, and further it permeates through cylindrical lens 16 and concave lens 17 to be received by sensor 18. Thereby, information recorded in CD 20 is read.
When information in DVD 30 is read, light pickup lens 15 is located at the position shown by solid lines in FIG. 1 and DVD light source 5 emits light on this condition, and thereafter, information recorded in DVD 30 is read by the same movement and operation as the case in which information in CD2 is read.
FIG. 2 is a diagram showing a schematic structure of light pickup lens 15, and FIG. 2(a) is a perspective view of light pickup lens 15, and then, FIG. 2(b) is a cross-sectional view of light pickup lens 15.
As shown in FIGS. 2(a), and (b), light pickup lens 15 has a dome-shaped lens part 15a and a ring-shaped flange part 15b supporting the periphery of the lens part 15a so that lens part 15a and flange part 15b are structured integrally, and the maximum length D of light pickup lens 15 in the optical axis direction (maximum thickness of the lens part 15a) is less than 3 mm and the maximum length L in the direction perpendicular to the optical axis direction (the maximum length between both ends of the flange part 15b) is less than 5 mm.
Light pickup lens 15 is composed of resin which contains a polymer having an alicyclic structure and specifically, the above-mentioned resin is injected into the inside of a die, cooled at the room temperature to be molded, and after molding, it is annealed at a temperature lower than the glass transition temperature of the resin by 30° C. through 65° C., and preferably at a temperature lower than the glass transition temperature of the resin by 35° C. through 45° C. for more than 16 hours.
Here, “resin containing a polymer having an alicyclic structure” is explained in detail.
It may be preferable that “Resin containing polymers having an alicyclic structure” contains repeating unit (a) having an alicyclic structure represented by following general formula (1) and repeating unit (b) comprising a chain structure represented by following general formula (2) and/or (3) so as to make the sum content of repeating unit not less than 90 weight %, and, further, make the content of repeating unit (b) not less than 1 weight % and less than 10 weight % among whole repeating units of a polymer having a weight average molecular weight (Mw) of 1,000 to 1,000,000, and the chain of the repeating unit (a) satisfies the following formula:

A≦0.3×B  (Z)

(In the formula (Z), A=(a weight average molecular weight of a repeating unit chain having an alicyclic type structure), and B=(a weight average molecular weight of a hydrocarbon copolymer having an alicyclic type structure(Mw)×(the number of repeating units having an alicyclic type structure/the number of whole repeating units constructing the hydrocarbon copolymer having the alicyclic type structure).





In formula (1), X represents an alicyclic hydrocarbon group, R1–R13 in formulas (1), (2) and (3) each independently represent a hydrogen atom, a chain hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ether group, an ester group, a cyano group, an amido group, an imido group, a silyl group and a chain hydrocarbon group substituted by a polar group (a halogen atom, an alkoxy group, a hydroxyl group, an ether group, an ester group, a cyano group, an amido group, an imido group or a silyl group). Among them, a hydrogen atom or a chain hydrocarbon group having a carbon number of 1–6 is preferred because of excellent heat resistance and a low water absorbing property. Halogen atoms include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Chain hydrocarbon groups substituted by a polar group include, for example, a halogenated alkyl group having a carbon number of 1–20, preferably of 1–10 and more preferably of 1–6. Chain hydrocarbon groups include, for example, an alkyl group having a carbon number of 1–20, preferably of 1–10 and more preferably of 1–6; and alkenyl group having a carbon number of 2–20, preferably of 2–10 and more preferably of 2–6.
In general formula (1), X represents an alicyclic hydrocarbon group, and the carbon number constituting which is generally 4–20, preferably 4–10 and more preferably 5–7. By setting the carbon number constituting an alicyclic structure into this range, double refraction can be reduced. Further, an alicyclic structure may include not only a monocyclic structure but also polycyclic structures such as a norbornane ring and a dicyclohexane ring.
The alicyclic hydrocarbon group may be provided with a carbon-carbon unsaturated bond, however, the content is not more than 10%, preferably not more than 5% and more preferably not more than 3%, based on the total carbon-carbon bonds. By setting the content of carbon-carbon unsaturated bonds of an alicyclic hydrocarbon group into this range, transparency and heat resistance are improved. Further, to carbon atoms constituting an alicyclic hydrocarbon group, bonded may be such as a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ether group, an ester group, a cyano group, an amido group, an imido group, a silyl group and a chain hydrocarbon group substituted by a polar group (a halogen atom, an alkoxy group, a hydroxyl group, an ether group, an ester group, a cyano group, an amido group, an imino group or a silyl group). Among them, a hydrogen atom or a chain hydrocarbon group having a carbon number of 1–6 is preferred because of excellent heat resistance and a low water absorbing property.
Further, . . . in general formula (3) represents a carbon-carbon saturated bond or a carbon-carbon unsaturated bond, and the content of an unsaturated bond is generally not more than 10%, preferably not more than 5% and more preferably not more than 3%, based on the total carbon-carbon bonds constituting the main chain, when transparency and heat resistance are strongly required.
Among repeating units represented by general formula (1), the repeating units represented by general formula (4) is excellent with respect to heat resistance and a low water absorbing property.




Among repeating units represented by general formula (2), the repeating units represented by general formula (5) is excellent with respect to heat resistance and a low water absorbing property.




Among repeating units represented by general formula (3), the repeating units-represented by general formula (6) is excellent with respect to heat resistance and a low water absorbing property.




Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Rl, Rm and Rn in general formula (4), (5) and (6) each independently represent a hydrogen atom or a lower chain hydrocarbon group, and hydrogen atom or a lower alkyl group having a carbon number of 1–6 is preferred due to excellent with respect to heat resistance and low water absorbability.
Among repeating units of a chain structure represented by general formula (2) and (3), the repeating units of a chain structure represented by general formula (3) exhibits a more excellent strength property of obtained hydrocarbon type polymer.
In this invention, the sum content of repeating unit (a) provided with an alicyclic structure represented by general formula (1) and repeating unit (b) provided with a chain structure represented by general formula (2) and/or general formula (3), in hydrocarbon copolymer, is generally not less than 90%, preferably not less than 95% and more preferably not less than 97%, based on weight. By setting the sum content into the aforesaid range, low double refraction, heat resistance, low water absorbability and mechanical strength are highly suitably balanced.
The content of repeating unit (b) provided with a chain structure in an alicyclic hydrocarbon type copolymer is appropriately selected depending on the objective of application, however, is generally in a range of 1–10%, preferably of 1–8% and more preferably of 2–6%, based on weight. When the content of repeating unit (b) is in the aforesaid range, low double refraction, heat resistance and low water absorbability are highly suitably balanced.
Further, a chain length of repeating unit (a) is sufficiently short compared to a molecular chain length of an alicyclic hydrocarbon type copolymer, and specifically A is in a range of not more than 30% of B, preferably not more than 20%, more preferably not more than 15% and most preferably not more than 10%, when A=(a weight average molecular weight of a repeating unit chain provided with an alicyclic structure) and B=(a weight average molecular weight of an alicyclic hydrocarbon type copolymer (Mw)×(a number of repeating units provided with an alicyclic structure/a number of the whole repeating unit constituting an alicyclic hydrocarbon type copolymer)). Low double refraction is inferior when A is out of this range.
Further, a chain length of repeating unit (a) preferably has a specific distribution. Specifically, A/C is preferably in a range of not less than 1.3, more preferably 1.3–8 and most preferably 1.7–6, when A=(a weight average molecular weight of a repeating unit chain provided with an alicyclic structure) and C=(a number average molecular weight of a repeating unit chain provided with an alicyclic structure). A blocking degree increases when A/C is excessively small while a random degree increases when A/C is excessively large and low double refraction is inferior in the both cases.
The molecular weight of an alicyclic hydrocarbon type copolymer is in a range of 1,000–1,000,000, preferably 5,000–500,000, more preferably 10,000–300,000 and most preferably 50,000–250,000 as a polystyrene (or polyisoprene) equivalent weight average molecular weight which is measured by means of gel permeation chromatography (hereinafter, referred to as GPC). A strength property of the molded material is inferior when the weight average molecular weight of an alicyclic hydrocarbon type copolymer is excessively small, while the double refraction of the molded material become large when it is excessively too large.
The molecular weight distribution of such copolymers can be appropriately selected depending on the objective of the application, however, it is generally in a range of not more than 2.5, preferably not more than 2.3 and more preferably not more than 2, as a ratio (Mw/Mn) of a polystyrene (or polyisoprene) equivalent weight average molecular weight which is measured by means of GPC (Mw) to a number average molecular weight (Mn). Mechanical strength and heat resistance can be highly suitably balanced when Mw/Mn is in this range.
The glass transition temperature (Tg) of the copolymer may be suitably selected depending on the objective of the application, however, is generally 50–250° C., preferably 70–200° C. and more preferably 90–180° C.
Next, a manufacturing method of “Alicyclic Hydrocarbon Type Copolymer” is explained.
Manufacturing method of alicyclic hydrocarbon type copolymer of this invention includes (1) a method in which aromatic vinyl type compound and another copolymerizable monomer are copolymerized and carbon-carbon unsaturated bonds of the main chain and of aromatic ring are hydrogenated; and (2) a method in which alicyclic vinyl type compound and another copolymerizable monomer are copolymerized and the resulting product is appropriately hydrogenated.
In the case of manufacturing an alicyclic hydrocarbon type copolymer of this invention according to the aforesaid method, it can be efficiently prepared by hydrogenating carbon-carbon unsaturated bonds in the main chain and unsaturated rings such as an aromatic or a cycloalkene ring of a copolymer, which is a copolymer of an aromatic vinyl type compound and/or an alicyclic vinyl type compound (a′) and copolymerizable another monomer (b′) and a repeating unit arising from compound (a′) in the copolymer is provided with a chain structure in which D is not more than 30% of E, preferably not more than 20%, more preferably not more than 15% and most preferably not more than 10%, when D=(the weight average molecular weight of a repeating unit chain arising from an aromatic vinyl type compound and/or an alicyclic vinyl type compound) and E=(the weight average molecular weight of hydrocarbon type copolymer (Mw)×(the number of a repeating unit chain arising from an aromatic vinyl type compound and/or an alicyclic vinyl type compound/the total number of repeating unit constituting a hydrocarbon type copolymer)). The low double refraction property of the obtained alicyclic hydrocarbon type copolymer is inferior when D is out of the aforesaid range.
In this invention, method (1) is preferred to prepare an alicyclic hydrocarbon type copolymer more efficiently.
Copolymers before the above-described hydrogenation is further preferably have D/F in a definite range when F=(a number average molecular weight of a repeating unit chain arising from an aromatic vinyl type compound and/or an alicyclic vinyl type compound). Specifically, D/F is preferably in a range of not less than 1.3, more preferably 1.3–8 and most preferably 1.7–6. The low double refraction property of the obtained alicyclic hydrocarbon type copolymer is inferior when D/F is out of this range.
The weight average molecular weight and number average molecular weight of a repeating unit arising from the aforesaid compound (a′) can be determined, for example, by a method, described in Macromolecules, vol. 16, pp. 1925–1928 (1983), in which unsaturated double bonds in an aromatic vinyl type copolymer are reductive cleaved after having been subjected to ozone addition and the molecular weight of obtained aromatic vinyl chain is measured.
The molecular weight of a copolymer before hydrogenation is in a range of 1,000–1,000,000, preferably 5,000–500,000 and more preferably 10,000–300,000, as a polystyrene (or polyisoprene) equivalent weight average molecular weight which is measured by means of GCP. A strength property of the obtained alicyclic hydrocarbon type copolymer is inferior when the weight average molecular weight (Mw) of the copolymer is excessively small, while the hydrogenation reactivity is inferior when it is excessively large.
Specific examples of aromatic vinyl type compounds utilized in above-described method (1) include, for example, styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-isopropylstyrene, α-t-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, monochlorostyrene, dichlorostyrene, monofluorostyrene and 4-phenylstyrene, and such as styrene, 2-methylstyrene, 3-methylstyrene and 4-methylstyrene are preferable.
Specific examples of alicyclic vinyl type compounds utilized in above-described method (2) include, for example, cyclobutylethylene, cyclopentylethylene, cyclohexylethylene, dicycloheptylethylene, cyclooctylethylene, nolbonylethylene, dicyclohexylethylene, α-methylcyclohexylethylene, α-t-butylcyclohexylethylene, cyclopentenylethylene, cyclohexenylethylene, cyclobutenylethylene, cyclooctenylethylene, cyclodecenylethylene, nolbonenylethylene, α-methylcyclohexenylethylene and α-t-butylcyclohexenylethylene, and cyclohexylethylene and α-methylcyclohexylethylene are preferable among them.
These aromatic vinyl type compounds and alicyclic vinyl type compounds can be utilized alone or in combination of two or more types.
Copolymerizable another monomers are not specifically limited, and utilized are such as chain vinyl compounds and chain conjugated diene compounds. In the case of utilizing chain conjugated diene compounds, the operating properties in the manufacturing process is superior, as well as the strength property of obtained alicyclic hydrocarbon type copolymer is excellent.
Specific examples of chain vinyl compounds include, for example, chain olefin monomers such as ethylene, propylene, 1-butene, 1-pentene and 4-methyl-1-pentene; nitrile type monomers such as 1-cyanoethylene (acrylonitrile), 1-cyano-1-methylethylene (methacrylonitrile) and 1-cyano-1-chloroethylene (α-chloroacrylonitrile), (meth)acrylic acid ester type monomers such as 1-(methoxycarbonyl)-1-methylethylene (methacrylic acid methyl ester), 1-(ethoxycarbonyl)-1-methylethylene (methacrylic acid ethyl ester), 1-(propoxycarbonyl)-1-methylethylene (methacrylic acid propyl ester), 1-(butoxycarbonyl)-1-methylethylene (methacrylic acid butyl ester), 1-methoxycarbonylethylene (acrylic acid methyl ester), 1-ethoxycarbonylethylene (acrylic acid ethyl ester), 1-propoxycarbonylethylene (acrylic acid propyl ester) and 1-butoxycarbonylethylene (acrylic acid butyl ester); unsaturated fatty acid type monomers such as 1-carboxyethylene (acrylic acid), 1-carboxy-1-methylethylene.(methacrylic acid) and maleic anhydride, preferable are chain olefin monomers and most preferable are ethylene, propylene and 1-butene.
Conjugated dienes include, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene. Among these chain vinyl compounds and chain conjugated dienes, preferable are chain conjugated dienes and specifically preferable are butadiene and isoprene.
These chain vinyl compounds and chain conjugated dienes each can be utilized alone or in combination of two or more types.
A method to polymerize compounds (a′) is not specifically limited and includes such as a one-step polymerization method (a batch method) and a monomer successive addition method (a method in which, after starting polymerization by using a part of the whole using amount of the monomer, polymerization is proceeded by successively adding the residual monomer). In particular, a hydrocarbon type copolymer provided with a preferable chain structure can be prepared by employing a monomer successive addition method. A copolymer before hydrogenation has the more random structure, the smaller is the aforesaid D, and/or the larger is the D/F. How much degree of random structure a copolymer has, is determined by a rate ratio of a polymerization rate of aromatic vinyl compound to that of copolymerizable another monomer, and the smaller is this rate ratio, the chain structure of more random structure has the copolymer.
According to the aforesaid monomer successive addition method, since uniformly mixed monomers are successively added into the polymerization system, it is possible to more decrease the polymerization selectivity of monomer in a polymer growth process by polymerization, different from a batch method, resulting in more random chain structure of the obtained copolymer. Further, the polymerization temperature can be stably maintained low because accumulation of polymerization reaction heat in the polymerization system is small.
In the case of a monomer successive addition method, polymerization is started by addition of an initiator in the state that generally 0.01–60 weight %, preferably 0.02–20 weight % and more preferably 0.05–10 weight % among the total using amount of the monomer presents as an initial monomer in a polymerization reaction vessel in advance. By setting the amount of the initial monomer in such a range, easily removed can be reaction heat generated in the initial reaction after starting polymerization resulting in preparation of a copolymer having a more random chain structure.
By continuing the reaction until a polymerization conversion ratio of the aforesaid monomer reaches to not less than 70%, preferably not less than 80% and more preferably not less than 90%, preparation of a copolymer having a more random chain structure results. Thereafter, the residual portion of the aforesaid monomer is discontinuously added to the reaction system, and the addition rate is determined in view of consumption rate of the monomer in the polymerization system.
The addition of the residual monomer is adjusted to finish in a range of 0.5–3.times, preferably 0.8–2 times and more preferably 1–1.5 times, of a time duration given by a relation [(100-I)×T/I], when a required time until the polymerization conversion ratio of the initial monomer reaches to 90% is T, and the ratio (%) of the initial monomer to the total monomer utilized is I. Specifically, the addition rates of the initial monomer and of the residual monomer are determined so that the addition time duration of the residual monomer is in a range of generally 0.1–30 hours, preferably 0.5–5 hours and more preferably 1–3 hours. Further, a polymerization conversion ratio of the total monomer immediately after the finish of the monomer addition is generally not less than 80%, preferably not less than 85% and more preferably not less than 90%. By setting a polymerization conversion ratio of the total monomer immediately after the finish of the monomer addition to the aforesaid range, obtained copolymer have a more random chain structure.
The polymerization method includes such as radical polymerization, anion polymerization and cation polymerization, and is not specifically limited. However, anion polymerization is preferred in view of polymerization operation, easiness of a hydrogenation reaction in the post process and mechanical strength of a finally obtained hydrocarbon type copolymer.
In the case of radical polymerization, block polymerization, solution polymerization, suspension polymerization and emulsion polymerization in the presence of an initiator, in a temperature range of generally 0–200° C. and preferably 20–150° C. can be employed, and in particular, in the case of prevention of impurity mixing in resin is required, block polymerization and suspension polymerization are preferred. As a radical initiator, utilized can be organic peroxides such as benzoyl peroxide, lauroyl peroxide and t-butyl-peroxy-2-ethylhexaate, azo compounds such as azobisbutyronitrile, 4,4-azobis-4-cyanopenoic acid and azodibenzoyl, water-soluble catalysts exemplified by potassium persulfate and ammonium persulfate and redox initiators.
In the case of anion polymerization, block polymerization, solution polymerization and slurry polymerization in the presence of an initiator, in a temperature range of generally 0–200° C., preferably 20–100° C. preferably and specifically preferably 20–80° C. can be employed, however, solution polymerization is preferred in view of removal of reaction heat. In this case, an inert solvent which can dissolve the polymer and the hydrogenation product thereof is utilized. Inert solvents utilized in solution reaction include, for example, aliphatic hydrocarbons such as n-butane, n-pentane, iso-pentane, n-hexane, n-heptane and iso-octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane and decalin; and aromatic hydrocarbons such as benzene and toluene, and aliphatic hydrocarbons and alicyclic hydrocarbons among them can be utilized as it is as an inert solvent also for the hydrogenation reaction. These solvents can be utilized alone or in combination of two or more types, and are utilized at a ratio of 200–10,000 weight parts against 100 weight parts of the total using monomers.
As an initiator for the anion polymerization described above, usable are, for example, mono organolithium compounds such as n-butyl lithium, sec-butyl lithium, t-butyl lithium, hexyl lithium and phenyl lithum; and multi-functional organolithium compounds of such as dilithiomethane, 1,4-dilithiobutane and 1,4-dilithio-2-ethylcyclohexane.
In polymerization reaction, a polymerization accelerator and a randomizer (an additive to prevent a chain of certain one component from becoming long) can also be utilized. In the case of anion polymerization, for example, a Lewis base compound can be utilized as a randomizer. Specific examples of a Lewis base compound include, for example, ether compounds such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, diphenyl ether, ethylene glycol diethyl ether and ethylene glycol methylphenyl ether; tertiary amine compounds such as tetramethylethylenediamine, trimethylamine, triethylamine and pyridine; alkali metal alkoxide compounds such as potassium-t-amyloxide and potassium-t-butyloxide; and phosphine compounds such as triphenylphsphine. These Lewis base compounds can be utilized each alone or in combination of two or more types.
Polymers obtained according to the above radical polymerization or anion polymerization can be recovered by means of commonly known methods such as a steam stripping method, a direct desolvation method and an alcohol coagulation method. Further, at the time of polymerization, in the case of utilizing an inert solvent in hydrogenation reaction, the polymer is not recovered from polymerization solution but can be supplied into hydrogenation process as it is.
Hydrogenation Method of Unsaturated Bond
In the case of performing hydrogenation of carbon-carbon double bonds in an unsaturated ring such as an aromatic ring and a cycloalkene ring or unsaturated bonds in a main chain of in copolymers before hydrogenation, the reaction method and reaction form are not specifically limited, and can be performed according to commonly known method. However, preferred is a hydrogenation method which can increase a hydrogenation degree as well as decrease a polymer chain cleaving reaction caused simultaneously with the hydrogenation, and listed is a method employing a catalyst containing at least one metal selected from nickel, cobalt, iron, titanium, rhodium, palladium, platinum, ruthenium and rhenium, in an organic solvent. As a hydrogenation catalyst, either a heterogeneous catalyst or a homogeneous catalyst can be utilized.
A heterogeneous catalyst can be utilized as a metal or a metal compound as it is, or by being carried in an appropriate carrier. Carriers include, for example, active carbon, silica, alumina, calcium carbonate, titania, magnesia, zirconia, diatomaceous earth and silicon carbide, and the carring amount of the catalyst is generally in a range of 0.01–80 weight % and preferably 0.05–60 weight %. As a homogeneous catalyst, utilized can be catalyst combining nickel, cobalt, titanium or iron compounds and organometallic compounds (such as organoaluminum compounds and organolithium compounds); or organometallic complex catalysts of such as rhodium, palladium, platinum, ruthenium and rhenium. As nickel, cobalt, titanium or iron compounds, utilized are, for example, acetylacetone salts, naphthenate salts, cyclopentadienyl compounds and cyclopentadienyl dichloro compounds of various types of metals. As organoaluminum compounds, suitably utilized are alkylaluminums such as triethylaluminum and triisobutylaluminum; halogenated aluminums such as diethylaluminum chloride and ethylaluminum dichloride; and alkylaluminum hydrides such as diisobutylaluminum hydride.
As examples of an organometallic complex catalyst, utilized are metal complexes such as γ-dichloro-π-benzene complexes, dichloro-tris(triphenylphosphine) complexes and hydride-chloro-triphenylphosphine complexes of the aforesaid each metal. These hydrogenated catalysts can be utilized each alone or in combination of two or more types, and the using amount is generally 0.01–100 parts preferably 0.05–50 parts and more preferably 0.1–30 parts, based on weight against the polymer.
The hydrogenation reaction is generally performed at a temperature of 10–250° C., however, is preferably performed at a temperature of 50–200° C. and more preferably 80–180° C., for the reason of an increasing hydrogenation degree as well as decreasing a polymer chain cleaving reaction which is caused simultaneous with a hydrogenation reaction. Further, hydrogen pressure is generally 0.1–30 MPa, however, it is preferably 1–20 MPa and more preferably 2–10 MPa, with respect to easy operation in addition to the above reasons.
The hydrogenation rate of thus obtained hydrogenated compounds is generally not less than 90%, preferably not less than 95% and more preferably not less than 97%, based on 1H-NMR measurement, with respect to any of carbon-carbon unsaturated bonds of a main chain, carbon-carbon double bonds of an aromatic ring and carbon-carbon double bonds of an unsaturated ring. Such as a low double refraction property and thermal stability are deteriorated when the hydrogenation rate is low.
A method to recover a hydrogenated compound after finishing the hydrogenation reaction is not specifically limited. Generally, utilized can be a method in which the solvent is removed from the hydrogenated compound solution by means of direct drying after elimination of the residue of a hydrogenation catalyst by means of such as filtration and centrifugal separation, and a method in which the hydrogenated compound solution is poured into a poor solvent for the hydrogenated compound to coagulate the hydrogenated
(Resin Composition)
In the invention, a resin composition comprising the polymer having the alicyclic structure containing an antioxidant is provided.
For the antioxidant, a phenol type antioxidant, a phosphor type antioxidant and a sulfur type antioxidant are usable, and among them the phenol type antioxidant, particularly an alkyl-substituted phenol type antioxidant, is preferable. By addition of these antioxidants, coloring and lowering of the strength of the molded material caused by the degradation by oxidation on the occasion of the molding can be prevented without lowering in the transparency and the low moisture absorption.
For the phenol type antioxidant, usually known ones ca be employed. For example, acrylate compounds described in Japanese Patent Tokkai Nos. 63-179953 and 1-168643 such as 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate and 2,4-di-t-amyl-6-(1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl)phenyl acrylate; an alkyl-substituted phenol compound such as octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylene-bis(4-methyl-6-t-butylphenol), 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′-hydroxyphenylpropionate)methane, namely pentaerythrimethyl-tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenylpropionate) and triethylene glycol bis-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionate; and a triazine group-containing phenol compound such as 6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bisoctyl-1,3,5-triazine, 4-bisoctylthio-1,3,5-triazine and 2-octylthio-4,6-bis-(3,5-di-t-butyl-4-oxyanilino)-1,3,5-triazine are cited.
For the phosphor type antioxidant, ones usually employed in the field of resin industry can be employed without any limitation. For example, monophosphite compounds such as triphenyl phosphate, diphenylisodecyl phosphate, phenylisodecyl phosphate, tris(nonylphenyl) phosphate, tris(dinonylphenyl) phosphate, tris(dinonylphenyl) phosphate, tris(2,4-di-t-butylphenyl) phosphate, and 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-Phosphaphenanthrene-10-oxide; and diphosphite compounds such as 4,4′-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecyl phosphate and 4,4′-isopropyridene-bis(phenyl-di-alkyl(C12 to C15) phosphate) are cited. Among them, the monophosphite compounds are preferable and tris(nonylphenyl) phosphate, tris(dinonylphenyl) phosphate and tris(2,4,-di-t-butylphenyl) phosphate are particularly preferable.
As the sulfur type antioxidant, for example, dilauryl 3,3-thiodipropionate, dimyrystyl 3,3′-thiodipropionate, distearyl 3,3-thiodipropionate, laurystearyl 3,3-dithiopropionate, pentaerythrytol-tetrakis-(β-laurylstearyl-thio-propionate and 3,9-bis-(2-dodecylthioethyl)-2,4,8,10-tetrakispiro[5,5]undecane are cited.
These antioxidants may be employed singly or in combination of two or more kinds. The adding amount of the antioxidant is optionally decided within the range in which the object of the invention is not vitiated; it is usually from 0.001 to 5 parts by weight and preferably from 0.01 to 1 part by weight to 100 parts by weight of the polymer having the alicyclic structure.
In the invention, a resin composition containing the polymer having the alicyclic structure and at least one selected from the group consisting of (1) a soft polymer, (2) an alcoholic compound and (3) an organic or inorganic filler is employed. By adding such the additives, occurrence of white turbid caused by standing for a long period under a high temperature and high humidity condition can be prevented without degradation in properties such as the transparency, low moisture absorption and mechanical strength.
Among the above-mentioned, (1) the soft polymer and (2) the alcoholic compound are excellent in the white turbid preventing effect and the transparency of the resin composition.
(1) Soft Polymer
The soft polymer to be employed in the invention is usually a polymer having a Tg of not more than 30° C. When the polymer shows plural Tgs, it is allowed that the lowest Tg is not more than 30° C.
The concrete examples of the soft polymer include an olefin type copolymer such as liquid polyethylene, polypropylene, poly-1-butene, ethylene.α-olefin copolymer, propylene.α-olefin copolymer, ethylene.propylene.diene copolymer (EPDM) and ethylene.propylene.styrene copolymer; an isobutylene type soft polymer such as polyisobutylene, isobutylene.isoprene rubber and isobutylene.styrene copolymer; a diene type soft polymer such as polybutadiene, polyisoprene, butadiene.styrene random copolymer, isoprene.styrene random copolymer, acrylonitrile.butadiene copolymer, acrylonitrile.butadiene.styrene copolymer, butadiene.styrene block copolymer, isoprene.styrene block copolymer, styrene.butadiene.styrene block copolymer, isoprene.styrene block copolymer and styrene.isoprene.styrene block copolymer; a silicon-containing soft polymer such as dimethylpolysilbxane, diphenylpolysiloxane and dihydroxypolysiloxane; a soft polymer composed of α,β-unsaturated acid such as poly(butyl acrylate), poly(butyl methacrylate), poly(hydroxyethyl methacrylate), polyacrylamide, polyacrylonitrile and butyl acrylate.styrene copolymer; a soft polymer composed of a unsaturated alcohol and amine, an acyl derivative thereof or acetal such as poly(vinyl alcohol), poly(vinyl acetate), poly(vinyl stearate) and cetate.styrene copolymer; an epoxy type soft polymer such as poly(ethylene oxide), poly(propylene oxide) and epichlorohydrine rubber; a fluorine-containing soft polymer such as vinylidene fluoride type rubber and ethylene tetrafluoride-propylene rubber; and another soft polymer such as natural rubber, polypeptide, protein, a polyester type thermoplastic estramer, a vinyl chloride type thermoplastic estramer and a polyamide type thermoplastic estramer. The soft polymers may be one having a crosslinking structure and one introduced with a functional group by a modification reaction.
In the above soft polymers, the diene type soft polymer is preferable, particularly a hydride compound in which carbon-carbon unsaturated bond is hydride, is superior in the rubber elasticity, mechanical strength, softness and dispersing ability.
(2) Alcoholic Compound
The alcoholic compound is a compound having at least one non-phenolic hydroxyl group, and preferably at least one hydroxyl group and at least one ether bond or ester bond. Concrete examples of such the compound include an alcoholic ether and ester compounds such as a poly-valent alcohol for example di or more-valent alcohol, preferably tri or more-valent alcohol, and more preferably poly-valent alcohol having 3 to 8 hydroxyl groups, in which one of the hydroxyl group is etherized or esterized.
As the di- or more-valent alcohol, for example, poly(ethylene glycol), glycerol, trimethylolpropane, pentaerythrytol, diglycerol, triglycerol, dipentaerythrytol, 1,6,7-trihydroxy-2,2-di(hydroxymethyl)-4-oxo-heptane, sorbitol, 2-methyl-1,6,7-trihydroxy-2-hydroxymethyl-4-oxo-heptane, 1,5,6-trihydroxy-3-oxo-hexanepentaerythrytol and tris(2-hydroxyethyl)isocyanurate are cited, and the tri- or more-valent alcohol, particularly having 3 to 8 hydroxyl groups, are preferable. To obtain the alcoholic ester compound, glycerol, diglycerol and triglycerol are preferable, by which alcoholic ester compound containing α,β-diol can be synthesized.
Examples of such the alcoholic compound include a poly-valent alcoholic esterized compound such as glycerol monostearate, glycerol monolaurate, glycerol monobehenate, glycerol monostearate, glycerol distearate, glycerol dilaurate, pentaerythrytol monostearate, pentaerythrytol monolaurate, pentaerythrytol monobehenate, pentaerythrytol distearate, pentaerythrytol dilaurate, pentaerythrytol tristearate and dipentaerythrytol distearate; 3-(octyloxy)-1,2-propanediol, 3-(decyloxy)-1,2-propanediol, 3-(lauryloxy)-1,2-propanediol, 3-(4-nonylphenyloxy)-1,2-propanediol, 1,6-dihydroxy-2,2-di(hydroxymethyl)-7-(4-nonylphenyloxy)-4-oxo-eptane, an alcoholic ether compound obtained by reaction of a condensate of p-nonylphenyl ether with formaldehyde and glycidol, an alcoholic ether compound obtained by reaction of a condensate of p-octylphenyl ether with formaldehyde and crycidol, and an alcoholic ether compound obtained by reaction of a condensate of p-octylphenyl ether with dicyclopentadiene and crycidol are employable. These poly-valent alcoholic compounds are employed singly or in combination of two or more kinds thereof. The molecular weight of these poly-valent alcoholic compounds is usually from 500 to 2,000, preferably from 800 to 1,500 even though the molecular weight is not specifically limited.
(3) Organic or Inorganic Filler
As the organic filler, a usual organic polymer particle or a crosslinked organic polymer particle can be employed. For example, a particle or a crosslinked particle of a polyolefin such as polyethylene and polypropylene; a halogen-containing vinyl polymer such as poly(vinyl chloride) and poly(vinylidene chloride); a polymer derived from a α,β-unsaturated acid such as polyallylate and polymethacrylate; a polymer derived from a unsaturated alcohol such as poly(vinyl alcohol) and poly(vinyl acetate); a polymer derived from poly(ethylene oxide) or bisglycidol ether; an aromatic condensate polymer such as poly(phenylene oxide), polycarbonate and polysulfone; polyurethane; polyamide; polyester; aldehyde; aldehyde.phenol type resin; and natural polymer compound are employable.
As the inorganic filler, for example, a powder of a compound of an element of Group 1 of periodic table such as lithium fluoride and borax (sodium borate hydrate); a compound of an element of Group 2 such as magnesium carbonate, magnesium phosphate, calcium carbonate, strontium titanate and barium carbonate; a compound of an element of Group 4 such as titanium dioxide (titania) and titanium monoxide; a compound of an element Group 6 such as molybdenum dioxide and molybdenum trioxide; a compound of an element of Group 7 such as manganese chloride and manganese acetate; a compound of an element of Groups 8 to 10 such as cobalt chloride and cobalt acetate; a compound of an element of Group 11 such as cuprous iodide; a compound of an element of Group 12 such as zinc oxide and zinc acetate; a compound of an element of Group 13 such as aluminum oxide (alumina), aluminum fluoride and aluminosilicate (alumina silicate, kaolin and kaolinite): a compound of an element of Group 14 such as silicon oxide (silica and silicagel); and a natural mineral such as graphite, carbon and glass; carnallite, kinite, mica (mica and golden mica) and bairose mineral are employable.
Tough the adding amount of the compounds of (1) to (3) is decided by the combination of the polymer having the alicyclic structure and the compound to be added, the glass transition point and the transparency of the composition is largely lowered when the adding amount is too large in general. When the adding amount is too small, white turbid tends to occur under the high temperature and high humid condition so that the composition becomes unsuitable to use for the optical material. The adding amount is usually from 0.01 to 10, preferably from 0.02 to 5, particularly preferably from 0.05 to 2, parts by weight to 100 parts by weight of the polymer having the alicyclic structure. When the adding amount is too small, the effect for preventing occurrence of the white turbid under the high temperature and high humidity condition cannot be obtained, and when the adding amount is too large, the heat resistivity and the transparency of the molded product are lowered.
Another additive such as a UV absorbent, a light stabilizer, a near infrared absorbent, a colorant such as a dye and a pigment, a slipping agent, a plasticizer, an antistatic agent and a fluorescent whitening agent may be added to the resin composition of the invention according to necessity. These additives may be employed singly or in a combination of two or more kinds thereof, and the adding amount is optionally decided within the range in which the object of the invention is not vitiated.
UV absorbents include benzophenone type UV absorbents such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-methoxy-2′-benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone and bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane; and benzotriazole type UV absorbents such as 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(2H-benzotriazole-2-il)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidylmethyl)phenol, 2-(2H-benzotriazole-2-il)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2′-hydroxy-3′5′-di-tertiary-butylphenyl)benzotriazole, 2-(2′-hydroxy-3′-tertiary-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-5′-tertiary-octylphenyl)benzotriazole, 2-(2′-hydroxy-3′5′-di-tertiary-amylphenyl)benzotriazole, 2-[2′-hydroxy-3′-(3′′,4′′,5′′6′′-tetrahydrophthalimidomethyl)-5′-methylphenyl]benzotriazole and 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazle-2-il)phenol]. Among them, preferable are 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(2H-benzotriazole-2-il)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidylmethyl)phenol and 2-(2H-benzotriazole-2-il)-4,6-bis(1-methyl-1-phenylethyl)phenol, with respect to such as heat resistance and low volatility.
Light fastness stabilizers include benzophenone type light fastness stabilizers, benzotriazole type light fastness stabilizers and hindered amine type light fastness stabilizers, and, in this invention, preferably utilized are hindered amine type light fastness stabilizers, with respect to transparency and an anti-coloring property of a lens. Among hindered amine type light fastness stabilizers (hereinafter, abbreviated as a HALS), those having a polystyrene equivalent Mn, measured by means of GPC employing THF as a solvent, of preferably 1000–10000, more preferably 2000–5000 and most preferably 2800–3800. When Mn is excessively small, a predetermined amount may not be blended due to evaporation at the time of blending said HALS in a polymer by thermal fusion kneading, or foams and silver streaks may generate at the time of thermal fusion molding in the ejection molding, resulting in decrease of manufacturing stability. Further, volatile gases may be generated from a lens when the lens is used for a long period keeping an on-state of a lamp. On the contrary, when Mn is excessively large, the dispersibility of HALS in a block copolymer is decreased to decrease transparency of a lens which results in deterioration of the improvement effect of light fastness. Therefore, in this invention, obtained can be lenses exhibiting excellent manufacturing stability, low gas generation and transparency by setting Mn of HALS in the above range.
Specific examples of such a HALS include high molecular weight HALS in which a plural number of piperidine rings are bonded via a triazine skeleton such as N,N′,N′′,N′′′-tetrakis-[4,6-bis-{butyl-(N-methyl-2,2,6,6-tetramethylpiperidine-4-il)amino}-triazine-2-il]-4,7-diazadecane-1,10-diamine, a polycondensation compound of dibutylamine, 1,3,5-triazine and N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)butylamine, poly[{(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diil}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], a polycondensation compound of 1,6-hexadiamine-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl) and morphorine-2,4,6-trichloro-1,3,5-triazine and poly[(6-morphorino-s-triazine-2,4-diil)(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene[((2,2,6,6-tetramethyl-4-piperidyl)imino); high molecular weight HALS in which a piperidine rings are bonded via a ester bonding such as a polymerization compound of dimethylsuccinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, a mixed esterified compound of 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethyl)-2,4,8,10-tetraoxasupiro[5,5]undecane.
Among them, preferred are polymers having Mn of 2000–5000, such as a polycondensation compound of dibutylamine, 1,3,5-triazine and N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)butylamine; poly[{(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazie-2,4-diil}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], a polymerization compound of dimethylsuccinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol.
The blending amount of UV absorbent and HALS described above in a block copolymer according to this invention is preferably 0.01–20 weight parts, more preferably 0.02–15 weight parts and most preferably 0.05–10 weight perts based on 100 weight parts of the polymer compound. The improvement effect of light fastness may not be obtained sufficiently resulting in coloring in such as the case of long period outdoor use, when the addition amount is excessively small. While, when the blending amount of HALS is excessively large, a part of the HALS may be converted to a gas to be generated, or dispersibility of the HALS may be decreased, resulting in decrease of transparency of a lens.
Further, a composition of the above “−Resin containing polymers having an alicyclic structure” can be obtained by mixing above components appropriately. As a mixing method, for example, a method in which the block copolymer in a molten state is kneaded with the additives by a mixer, double-axial kneader, rollers, brabender or extruder and a method in which the materials are dissolved in a suitable solvent and dispersed and solidified may be employed. When the double-axial kneader is employed, the molten mixture is usually extruded in a form of stick and cut into a suitable length by a pelettizer to form pellets for employing as the molding material.
An optical element described in Item 2-5 is the optical element described in Item 2-1, wherein the resin containing polymers having an alicyclic structure includes block copolymers having polymer block [A] containing a repeating unit [1] represented by a formula (11) and polymer block [B] containing a repeating unit [1] and a repeating unit [2] represented by a formula (12) and/or a repeating unit [3] represented by a formula (13) and the block copolymers satisfy the relationship of a>b, where a is a mol fraction (mol %) of the repeating unit [1] in the polymer block [A] and b is a mol fraction (mol %) of the repeating unit [1] in the polymer block [B].




(In the formula (11), R1 represents a hydrogen atom or an alkyl group having a carbon number of 1–20, R2–R12 each independently represent a hydrogen atom, an alkyl group having a carbon number of 1–20, a hydroxyl group, an alkoxy group having a carbon number of 1–20 or a halogen group.)





(In the formula, R13 represents a hydrogen atom or an alkyl group having a carbon number of 1–20.)





(In the formula (13), R14 and R15 each independently represent a hydrogen atom or an alkyl group having a carbon number of 1–20.)

A preferable structure of repeating unit [1] represented by above formula (11) is one in which R1 is a hydrogen atom or a methyl group and all of R2–R12 are hydrogen atoms. The transparency and mechanical strength are superior when the content of repeating unit [1] in polymer block [A] is in the above range. In polymer block [A], the residual parts except aforesaid repeating unit [1] are repeating units arising from chain conjugated dienes or chain vinyl compounds which have been hydrogenated.
Polymer block [B] contains aforesaid repeating unit [1] and repeating unit [2] represented by following formula (12) and/or [3] represented by following formula (13). The content of repeating unit [1] in polymer block [B] is preferably 40–95 mol % and more preferably 50–90 mol %. The transparency and mechanical strength are superior when the content of repeating unit [1] is in the above range. When a mol fraction of repeating unit [2] in polymer block [B] is m2 (mol %) and a mol fraction of repeating unit [3] is m3 (mol %), 2×m3+m2 is preferably not less than 2 mol %, more preferably 5–60 mol % and most preferably 10–50 mol %.
A preferable structure of repeating unit [2] represented by above formula (12) is one in which R13 is a hydrogen atom or a methyl group.
A preferable structure of repeating unit [3] represented by above formula (13) is one in which R14 is a hydrogen atom and R15 is a methyl group or an ethyl group.
The mechanical strength is decreased when the content of aforesaid repeating unit [2] or repeating unit [3] in polymer block [B] is excessively small. Therefore, transparency and mechanical strength are superior when the content of repeating unit [2] and repeating unit [3] is in the above range. Polymer block [B] may contain repeating unit [X] represented by following formula (X). The content of repeating unit [X] is in a range not to damage the characteristics of a block copolymer of this invention, and is preferably not more than 30 mol % and more preferably not more than 20 mol %, based on the total block copolymer.




(In the formula (X), R25 represents a hydrogen atom or an alkyl group having a carbon number of 1–20, R26 represents a nitrile group, an alkoxycarbonyl group, a formyl group, a hydroxycarbonyl group or a halogen group, and R27 represents a hydrogen atom. R25 and R27 may represent an acid anhydride group or an imido group by bonding to each other.)

Further, polymer block [B] utilized in this invention preferably satisfy the relationship of a>b, when the mol fraction of repeating unit [1] in polymer block [A] is a, and the mol fraction of repeating unit [1] in polymer block [B] is b. Thereby, transparency and mechanical strength are superior.
Further, with respect to block copolymer utilized in this invention, the ratio ma/mb is preferably 5/95–95/5, more preferably 30/70–70/30 and most preferably 40/60–60/40, when a mol number of total repeating units constituting block [A] is ma and a mole number of total repeating units constituting block [B] is mb. Mechanical strength and heat resistance are superior when ma/mb is in the above range.
The molecular weight of an block copolymer utilized in this invention is preferably in a range of 10,000–300,000, more preferably 15,000–250,000 and most preferably 20,000–200,000 as a polystyrene (or polyisoprene) equivalent weight average molecular weight (hereinafter, described as Mw) which is measured by means of gel permeation chromatography employing tetrahydrofuran (THF) as a solvent. The balance of mechanical strength, heat resistance and a molding property is superior when Mw of a block copolymer is in the above range.
The molecular weight distribution of a block copolymer can be appropriately selected depending on the objective of the application, however, it is preferably not more than 5, more preferably not more than 4 and most preferably not more than 3, as a ratio (Mw/Mn) of a polystyrene (or polyisoprene) equivalent weight average molecular weight which is measured by means of GCP (hereinafter referred to as Mw) to a number average molecular weight (Mn). Mechanical strength and heat resistance are superior when Mw/Mn is in this range.
The glass transition temperature (Tg) of the copolymer may be suitably selected depending on the objective of the application, however, is preferably 70–200° C., more preferably 80–180° C. and most preferably 90–160° C., as a high temperature side value measured by a differential scanning type thermal analyzer (hereinafter, described as DSC).
The above-described block copolymer utilized in this invention is provided with polymer block [A] and polymer block [B], and may be any of a di-block copolymer of ([A]-[B]) form, a tri-block copolymer of ([A]-[B]-[A]) or ([B]-[A]-[B]) and a block copolymer in which at least 4 blocks of polymer block [A] and polymer block [B] are bonded alternately. Further, it mey be a block copolymer in which these blocks are bonded in a radial form.
Block copolymers utilized in this invention can be obtained by the following methods. Listed is a method in which a polymer block having a repeating unit arising from an aromatic vinyl compound and/or an alicyclic vinyl compound, and a polymer block having a repeating unit arising from a vinyl type monomer are prepared by polymerizing a mixture of a monomer mixture containing an aromatic vinyl compound and/or an alicyclic vinyl compound, and a monomer mixture containing a vinyl type monomer (except aromatic vinyl compounds and alicyclic vinyl compounds), followed by hydrogenation of aromatic rings and/or aliphatic rings in said block copolymers. Further, listed is a method in which a monomer mixture containing a saturated alicyclic vinyl compound and a vinyl type monomer (except aromatic vinyl compounds and alicyclic vinyl compounds) are polymerized to prepare block copolymer having a repeating unit arising from an alicyclic vinyl compound and a repeating unit arising from a vinyl type compound. Among them, more preferable to obtain a block copolymer of this invention is, for example, the following method.

    (1) In the first method, first, polymer block [A′] containing a repeating unit arising from an aromatic vinyl compound and/or an alicyclic vinyl compound which has unsaturated bonds in the ring is prepared by polymerizing a monomer mixture [a′] containing not less than 50 mol % of an aromatic vinyl compound and/or an alicyclic vinyl compound which has unsaturated bonds in the ring. Polymer block [B′] is prepared by polymerizing a monomer mixture [b′] which contains not less than 2 mol % of a vinyl type monomer (except aromatic vinyl compounds and alicyclic vinyl compounds), and containing an aromatic vinyl compound and/or an alicyclic vinyl compound which has unsaturated bonds in the ring at a ratio less than that in monomer mixture [a′]. After preparing a block copolymer provided with aforesaid polymer block [A′] and polymer block [B′] via at least these process, aromatic rings and/or alicyclic rings in said block copolymer are hydrogenated.
    (2) In the second method, first, polymer block [A] containing a repeating unit arising from an saturated alicyclic vinyl compound by polymerizing a monomer mixture containing not less than 50 mol % of an saturated alicyclic vinyl compound. Polymer block [B] containing a repeating unit arising from a saturated alicyclic vinyl compound and a repeating unit arising from a vinyl monomer is prepared by polymerizing a monomer mixture [b] which contains not less than 2 mol % of a vinyl type monomer (except aromatic vinyl compounds and alicyclic vinyl compounds), and containing a saturated alicyclic vinyl at a ratio less than that in monomer mixture [a]. A block copolymer provided with aforesaid polymer block [A] and polymer block [B] via at least these process.


Among the above methods, above-described method (1) is more preferred, with respect to easy availability of monomers, polymerization yield, easiness of introducing a repeating unit [1] into polymer block [B′].
Specific examples of aromatic vinyl compounds in above method (1) include such as styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-isopropylstyrene, α-t-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, monochlorostyrene, dichlorostyrene, monofluorostyrene and 4-phenylstyrene, as well as those having substituents such as a hydroxyl group and an alkoxy group therein. Among them, preferable are such as 2-methylstyrene, 3-methylstyrene and 4-methylstyrene.
Specific examples of unsaturated alicyclic vinyl compounds in above method (1) include such as cyclohexenyl ethylene, α-methylcyclohexenyl ethylene and α-t-butylcyclohexenyl ethylene, as well as those having substituents such as a halogen group, an alkoxy group or a hydroxyl group therein.
These aromatic vinyl compounds and alicyclic vinyl compounds can be utilized each alone or in combination of two or more types. However, it is more preferable, in this invention, to utilize an aromatic vinyl compound in either of monomer mixtures of [a′] and [b′], and, in particular, more preferable to utilize α-methylstyrene.
Vinyl monomers utilized in the above method include chain vinyl compounds and chain conjugated diene compounds.
Specific examples of chain vinyl compounds include chain olefin monomers such as ethylene, propylene, 1-butene, 1-pentene and 4-mthyl-1-pentene, and, among them, most preferable are ethylene, propylene and 1-butene.
Chain conjugated diene compounds include, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene. Chain conjugated dienes, among these chain vinyl compounds and chain conjugated dienes, are preferred, and butadiene and isoprene are most preferred. These chain vinyl compounds and chain conjugated dienes can be utilized each alone or in combination of two or more types.
In the case of utilizing a monomer mixture containing the above-described monomers, a polymerization reaction may be performed by means of any polymerization method such as radial polymerization, anion polymerization or cation polymerization, and preferably by means of anion polymerization and most preferably by means of living anion polymerization in the presence of an inert solvent.
Anion polymerization is performed in the presence of a polymerization initiator in a temperature range of generally 0–200° C., preferably 20–100° C. and most preferably 20–80° C. As initiators, utilized can be, for example, mono-organolithium compounds such as n-butyl lithium, sec-butyl lithium, t-butyl lithium, hexyl lithium and phenyl lithium; and multifunctional organolithium compounds such as dilithiomethane, 1,4-dilithiobutane and 1,4-dilithio-2-ethylcyclohexane.
Inert solvents utilized include, for example, aliphatic hydrocarbons such as n-butane, n-pentane, iso-pentane, n-hexane, n-heptane and iso-octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane and decalin; and aromatic hydrocarbons such as benzene and toluene, and aliphatic hydrocarbons and alicyclic hydrocarbons among them can be utilized as it is as an inert solvent also for the hydrogenation reaction. These solvents can be utilized each alone or in combination of two or more types, and are utilized at a ratio of 200–10,000 weight parts against 100 weight parts of the total using monomers.
At the time of polymerizing each polymer block, a polymerization accelerator or a randomizer can be utilized to prevent a certain one component chain from growing long. In particular, in the case of performing a polymerization reaction by means of anion polymerization, such as a Lewis base compound can be utilized as a randomizer. Specific examples of a Lewis base compound include, ether compounds such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, diphenyl ether, ethylene glycol diethyl ether and ethylene glycol methylphenyl ether; tertiary amine compounds such as tetramethylethylenediamine, trimethylamine, triethylamine and pyridine; alkali metal alkoxide compounds such as potassium-t-amyloxide and potassium-t-butyloxide; and phosphine compounds such as triphenylphsphine. These Lewis base compounds can be utilized each alone or in combination of two or more types.
A method to preparation a block copolymer by means of living anion polymerization includes commonly known methods such as a consecutive addition polymerization reaction method and a coupling method, and in this invention, a consecutive addition polymerization reaction method is preferably employed.
In the case of preparing the above block copolymer provided with polymer block [A′] and polymer block [B′] by means of a consecutive addition polymerization method, a process to obtain polymer block [A′] and a process to obtain polymer block [B′] are performed successively in order. Specifically, in an inert solvent, polymer block [A′] is prepared by polymerizing monomer mixture [a′] in the presence of the above-described living anion polymerization catalyst, and polymer block [B′] connected to polymer block [A′] is prepared by continuing polymerization by successively adding monomer mixture [b′] into the reaction system. Further, if desired, monomer mixture [a′] is added to perform polymerization resulting in preparation of a tri-block substance by connecting polymer block [A′], then monomer mixture [b′] is further added to perform polymerize resulting in preparation of a tetra-block substance.
The obtained block copolymer is recovered by means of commonly known methods such as a steam stripping method, a direct desolvation method and an alcohol coagulation method. Further, at the time of polymerization, in the case of utilizing an inert solvent in a hydrogenation reaction, it is not necessary to recover the polymer from polymerization solution because the polymerization solution can be utilized in the hydrogenation process as it is.
Block copolymers provided with polymer block [A] and polymer block [B′], which is prepared by aforesaid method (1), are preferably those having a repeating unit of the following structure.
Preferable polymer block [A′] constituting block copolymer of before hydrogenation is a polymer block containing not less than 50% of repeating unit [4] represented by the following formula (4).




(In the formula (14), R16 represents a hydrogen atom or an alkyl group having a carbon number of 1–20, R17–R11 each independently represent a hydrogen atom, an alkyl group having a carbon number of 1–20, a hydroxyl group, an alkoxy group having a carbon number of 1–20 or a halogen group. Herein, the aforesaid R17–R21 represent R17, R18, . . . and R21.)

Further, preferable polymer block [B′] necessarily contains the aforesaid repeating unit [4], and provided with at least either one of repeating unit [5] represented by following formula (5) or repeating unit [6] represented by following formula (6). Further, a′>b′, when mol fraction of repeating unit [4] in polymer block [A′] is a′ and mol fraction of repeating unit [4] in polymer block [B′] is b′.




(In the formula, R22 represents a hydrogen atom or an alkyl group having a carbon number of 1–20.)





(In the formula (16), R23 represents a hydrogen atom or an alkyl group having a carbon number of 1–20, and R24 represents a hydrogen atom or an alkyl group or an alkenyl group having a carbon number of 1–20)

Further block [B′] may contain repeating unit [Y] represented by following formula (Y).




(In the formula (Y), R28 represents a hydrogen atom or an alkyl group having a carbon number of 1–20, R29 represents a nitrile group, an alkoxycarbonyl group, a formyl group, hydroxycarbonyl group or a halogen group, or R29 and R30 may form an acid anhydride group or an imido group by bonding to each other.)

Further, a preferable block copolymer before hydrogenation is one having ratio ma/mb of preferably 5/95–95/5, more preferably 30/70–95/5 and most preferably 40/60–90/10, when a mol number of total repeating units constituting block [A′] is ma′ and a mole number of total repeating units constituting block [B′] is mb′. The mechanical strength and heat resistance are superior when ma/mb is in the above range.
The molecular weight of a block copolymer before hydrogenation is preferably in a range of 12,000–400,000, more preferably 19,000–350,000 and most preferably 25,000–300,000 as a polystyrene (or polyisoprene) equivalent Mw which is measured by means of GCP employing THF as a solvent. Mechanical strength is decreased when Mw of a block copolymer is excessively small while hydrogenation degree is decreased when Mw of a block copolymer is excessively large.
The molecular weight distribution of a block copolymer before hydrogenation can be appropriately selected depending on the objective of the application, however, it is preferably not more than 5, more preferably not more than 4 and most preferably not more than 3, as a ration (Mw/Mn) of a polystyrene (or polyisoprene) equivalent molecular weight Mw to Mn, which are measured by means of GCP. The hydrogenation degree is improved when Mw/Mn is in this range.
The Tg of a block copolymer before hydrogenation may be suitably selected depending on the objective of the application, however, is preferably 70–150° C., more preferably 80–140° C. and most preferably 90–130° C., as a high temperature side value measured by means of DSC.
The reaction method and reaction form of performing hydrogenation of carbon-carbon unsaturated bonds in an unsaturated ring of such as an aromatic ring and a cycloalkene ring and unsaturated bonds in a main chain or a side chain, in the aforesaid block copolymer before hydrogenation, are not specifically limited, and can be performed according to commonly known methods. However, preferred is a hydrogenation method which can increase a hydrogenation degree as well as decrease a polymer chain cleaving reaction, and listed is a method employing a catalyst containing at least one metal selected from nickel, cobalt, iron, titanium, rhodium, palladium, platinum, ruthenium and rhenium, in an organic solvent. As a hydrogenation catalyst, either a heterogeneous catalyst or a homogeneous catalyst can be utilized.
A heterogeneous catalyst can be utilized as a metal or a metal compound as it is, or by being carried in an appropriate carrier. Carriers include, for example, active carbon, silica, alumina, calcium carbonate, titania, magnesia, zirconia, diatomaceous earth and silicon carbide, and the carring amount of the catalyst is generally in a range of 0.01–80 weight % and preferably 0.05–60 weight %. As a homogeneous catalyst, utilized can be catalyst combining nickel, cobalt, titanium or iron compounds and organometallic compounds (such as organoaluminum compounds and organolithium compounds); or organometallic complex catalysts of such as rhodium, palladium, platinum, ruthenium and rhenium. As nickel, cobalt, titanium or iron compounds, utilized are, for example, acetylacetone salts, naphthenate salts, cyclopentadienyl compounds and cyclopentadienyl dichloro compounds of various types of metals. As organoaluminum compounds, suitably utilized are alkylaluminums such as triethylaluminum and triisobutylaluminum; halogenated aluminum such as diethylaluminum chloride and ethylaluminum dichloride; and hydrogenated alkylaluminum such as diisobutylaluminum hydride.
As examples of an organometallic complex catalyst, utilized are metal complexes such as γ-dichloro-π-benzene complexes, dichloro-tris(triphenylphosphine)-complexes and hydride-chloro-triphenylphosphine complexes of the aforesaid each metal. These hydrogenation catalysts can be utilized each alone or in combination of two or more types, and the using amount is generally 0.01–100 weight parts preferably 0.05–50 weight parts and more preferably 0.1–30 weight parts, per 100 weight parts of the polymer.
The hydrogenation reaction is generally performed at a temperature of 10–250° C., however, is preferably performed at a temperature of 50–200° C. and more preferably 80–180° C., for the reason of an increasing hydrogenation degree as well as decreasing a polymer chain cleaving reaction which is caused simultaneous with a hydrogenation reaction. Further, hydrogen pressure is generally 0.1–30 MPa, however, it is preferably 1–20 MPa and more preferably 2–10 MPa, with respect to easy operation in addition to the above reasons.
The hydrogenation degree of thus obtained hydrogenated compounds is preferably not less than 90%, more preferably not less than 95% and most preferably not less than 97%, based on 1H-NMR measurement, with respect to both of carbon-carbon unsaturated bonds of a main chain and a side chain, and carbon-carbon unsaturated bonds of an aromatic ring or a cycloalkene ring. Such as a low double refraction property and thermal stability of an obtained copolymer are deteriorated when the hydrogenation degree is low.
After finishing the hydrogenation reaction, the block copolymer can be recovered by such as a method in which the solvent is removed by means of direct drying after elimination of a hydrogenation catalyst from the reaction solution by means of such as filtration and centrifugal separation, and a method in which the hydrogenated compound solution is poured into a poor solvent for the hydrogenated compound to coagulate the hydrogenated compound.
Further, by blending a soft polymer having the lowest glass transition temperature of not higher than 30° C., it is possible to prevent turbidity under an environment of high temperature and high humidity for a long period without deteriorating such as transparency, heat resistance and mechanical strength.
Specific examples of the above soft polymers include olefin type soft polymer such as polyethylene, polypropyrene, ethylene-α-olefin copolymer and ethylene-propyrene-diene copolymer (EDPM); isobutylene type soft copolymers such as polyisobutylene, isobutylene-isoprene rubber and isobutylene-styrene copolymer; diene type soft copolymers such as polybutadiene, polyisoprene, butadiene-styrene random copolymer, isoprene-styrene random copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, butadiene-styrene.block copolymer, styrene-butadiene-styrene.block copolymer, isoprene-styrene.block copolymer and styrene-isoprene-styrene.block copolymer; silicon containing type soft polymers such as dimethyl polysiloxane and diphenyl polysiloxane; acryl type soft polymers such as polybutyl acrylate, polybutyl methacrylate and polyhydroxyethyl methacrylate; epoxy type soft polymers such as polyethyleneoxide, polypropyreneoxide and epichlorohydrine rubber; fluoride type soft polymers such as fluorovinyl type rubber and tetrafluoroethylene-propyrene rubber; other soft polymers such as natural rubber, polypeptide, protein, polyester type thermal plastic elastomers, vinylchloride type elastomers and polyamido type tnermoplastic elastomers. These soft elastomer may be provided with a cross-linking structure or introduced with a functional group by a modification reaction.
Diene type soft polymers are preferred among the soft polymers described above, and, in particular, hydrogenated compounds, in which carbon-carbon unsaturated bonds of said soft polymers are hydrogenated, are superior with respect to rubber elasticity, mechanical strength, flexibility and dispersibility. The blending amount of a soft polymer differs depending on types of the compound, however, generally, the glass transition temperature or transparency may be decreased remarkably resulting in being unusable as a lens when the blending amount is too large. While turbidity of a molded product may generates under high temperature and high humidity when the blending amount is excessively small. The blending amount is preferably 0.01–10 weight parts, more preferably 0.02–5 weight parts and specifically preferably 0.05–2 weight parts against 100 weight parts of the block copolymer.
As the method for forming the block copolymer composition by adding the additives to the block copolymer, for example, a method in which the block copolymer in a molten state is kneaded with the additives by a mixer, double-axial kneader, rollers, brabender or extruder and a method in which the materials are dissolved in a suitable solvent and dispersed and solidified. When the double-axial kneader is employed, the molten mixture is usually extruded in a form of stick and cut into a suitable length by a pelettizer to form pellets for employing as the molding material.
Other than the above resin, for example, a resin containing a norbonene type open ring (hydrogen) polymer described in Japanese Patent Tokkai No. 2003-73460 can be employed for the material of the optical element according to the invention.
The manufacturing method for light pickup lens 15 will be explained as follows.
First, the aforementioned “resin which contains a polymer having an alicyclic structure” is injected and fills a die which is heated at a prescribed temperature, and the filling resin is left in the die to cool down for solidification. After leaving during a prescribed time, the solidified resin (mold) is removed from the die and the mold is left to cool further at the room temperature. After a prescribed time has passed on this condition, the mold is transferred into a thermostatic chamber, and is annealed at a temperature lower than the glass transition temperature of the resin which composes the mold, by 35° C. through 45° C. for more than 16 hours to finish the manufacturing of the light pickup lens 15. Thereby, there can be manufactured light pickup lens 15 the optical characteristics of which such as astigmatism is tremendously improved because of sufficient relief of residual stress.
In the above stated embodiment, optical characteristics such as astigmatism and spherical aberration of light pickup lens 15 are tremendously improved and birefringence which occurs on the surface layer of the light pickup lens 15 is also tremendously reduced, because the mold is annealed at a temperature lower than the glass transition temperature of the resin which composes the mold, by 35° C. through 45° C., after injection molding and the residual stress is sufficiently relieved.
This invention is not limited to the aforementioned embodiments and various kinds of improvements and design changes can be applied without departing from the spirit of this invention.
For example, in the above-stated embodiment, an example in which optical element and the manufacturing method related to this invention are applied to light pickup lens 15, is described, however the optical element and the manufacturing method related to this invention can be applied to collimator 11, splitter 12, 1⁄4 wavelength plate 13, cylindrical lens 16 and concave lens 17 which compose light pickup device 1, and also can be applied to optical element used for other than light pickup device 1, and ultimately it can be applied to any small-sized optical molds wherein the maximum length in the optical axis direction is less than 3 mm and the maximum length in the direction perpendicular to the optical axis direction is less than 5 mm.
EXAMPLE
In this example, a light pickup lens was injection-molded as an optical element and a configuration of each molded sample was observed and spherical aberration and astigmatism were measured.
(1) Manufacturing of Samples
By using ZEONEX 340R produced by NIHONZEON Ltd. (Glass transition temperature is 122° C.; the value was measured by means of differential scanning calorimetry (DSC) in JIS K7121 employing temperature rising speed of 10° C./min), molds of CD/DVD compatible optical pickup lenses were obtained as “resin which contains a polymer having an alicyclic structure” explained in the aforementioned embodiment, by injecting and molding the resin in a prescribed die, and by leaving the molds for cooling in the room temperature. Each mold has diffraction structure on the whole optically functional surface of the mold, and the numerical aperture (NA) of CD was 0.45 and the numerical aperture (NA) of DVD was 0.65. Each mold had a lens part and a flange part surrounding the lens part as shown in FIG. 2, and the maximum length in the optical axis direction (maximum thickness of the lens part) was 2.00 mm and the maximum length in the direction perpendicular to the optical axis direction (the maximum length between both ends of the flange part) was 5.00 mm.
For theses molds, an oven or a thermo-humid chamber was used to conduct the heat treatment or the wet heat treatment shown in Table 1.
(2) Observation of the Configuration
A difference between the target configuration at the designing stage and the actual one of each mold treated under the treatment condition indicated in Table 1 was observed visually with a microscope. As shown in Table. 1, regarding molds other than Comparison example 2, the configuration accorded to the designed one, however large deformation was observed on the molds of Comparison example 2.
(3) Measurement of the Spherical Aberration and the Astigmatism
Spherical aberration and astigmatism were measured for each mold treated under the treatment condition indicated in Table 1 with interferometer (the used wavelength was 650 nm) which can perform numerical analysis by using a known method. The result of the measurement of each sample is shown in Table 1. As shown in Table 1, when the temperature of heat treatment or wet heat treatment was higher than a temperature which is lower than the glass transition temperature of the resin by 35° C. (87° C. in this example), the deformation was too large to measure the aberration (Comparison example 2). When the temperature of heat treatment or wet heat treatment was lower than a temperature which is lower than the glass transition temperature of the resin by 45° C. (77° C. in this example) or when neither heat treatment nor wet heat treatment was carried out, large values of the aberration which were out of the practically usable range were obtained, probably because the residual stress was not sufficiently relieved (Comparison examples 3, 4 and 6).











TABLE 1









Diff.














Processing condition
from
Spheric
Astigmat-














Temp
Humidity
Time
design
aberr.
ism



(° C.)
(% RH)
(hours)
shape
(λrms)
(λrms)

















Exam. 1
85
60
155
No
0.001
0.001


Exam. 2
85
60
100
No
0.003
0.002


Exam. 3
85
60
18
No
0.008
0.006


Comp. 1
85
60
10
No
0.022
0.012


Comp. 2
90
60
2
Large
No
No







measured
measured


Exam. 4
80
60
155
No
0.002
0.003


Exam. 5
80
60
145
No
0.003
0.005


Comp. 3
75
60
155
No
0.020
0.030


Comp. 4
75
60
300
No
0.020
0.026


Exam. 6
85
45
155
No
0.002
0.003


Exam. 7
85
35
155
No
0.002
0.006


Exam. 8
85
75
155
No
0.002
0.003


Exam. 9
85
85
155
No
0.002
0.006


Exam. 10
80
below 1
155
No
0.005
0.008


Exam. 11
80
below 1
145
No
0.005
0.010


Exam. 12
80
below 1
18
No
0.010
0.018


Comp. 5
80
below 1
10
No
0.020
0.025











Comp. 6
No processing
No
0.030
0.040









Evaluation criteria for the result of aberration measurement
Greater than or equal to 0.02: Out of the practically usable range
Greater than or equal to 0.01 and less than 0.02: Within the usable range but not on a preferable level
Greater than or equal to 0.005 and less than 0.01: Usable
Less than 0.005: Sufficiently usable and on a preferable level
According to Table 1, even when the temperature of heat treatment or wet heat treatment was within the range from the temperature which was lower than the glass transition temperature of the resin by 45° C. to the temperature which was lower than the glass transition temperature of the resin by 35° C., sufficient stress relief could not be obtained and the aberration level was out of the practically usable range if the treatment time is shorter than 16 hours. (Comparison examples 1 and 5). It became clear that more preferable aberration level could be obtained when treatment was carried out for more than 150 hours (Examples 1, 2, 4 and 5).
When the temperature of the treatment was within the range from the temperature which was lower than the glass transition temperature of the resin by 45° C. to the temperature which was lower than the glass transition temperature of the resin by 35° C. and treatment time was longer than 16 hours, the values of aberration of molds treated under any humidity condition were not on problematic levels, however it was preferable for performance of the lens that the treatment was carried out with relative humidity of each temperature being 40% through 80% (Examples 6 through 9), and preferable result was obtained especially when the treatment was carried out with relative humidity of each temperature being 55% through 65% (Example 1).
As a result, it becomes clear that applying heat treatment or wet heat treatment to a mold after injection molding at a temperature lower than the glass transition temperature of the resin by 35° C. through 45° C. for more than 16 hours is effective to relieve sufficiently a residual stress on a small sized optical element, and preferably for more than 150 hours, and preferably with relative humidity of each temperature being 40% through 80%, and especially preferably with relative humidity of each temperature being 55% through 65%.

## Claims

1. An optical element having an optical axis, comprising:
an element body having the maximum first length of 4 mm or less in the optical axis direction and the second maximum length of 6 mm or less in the direction perpendicular to the optical axis direction;
wherein the element body is made of a resin containing a polymer having an alicyclic structure and is treated by one of heat treatment and wet-heat treatment for 16 hours or longer at a temperature lower by 35° C. to 45° C. than the glass transition temperature of the resin after the element body has been formed by injecting the resin in a mold, where the glass transition temperature of the resin is measured by differential-scanning-calorimetry method at heating rate 10° C./min on the basis of JIS K7121.

2. The optical element of claim 1, wherein the treating time is 150 hours or longer.

3. The optical element of claim 1, wherein a relative humidity at each temperature of the wet-heat treatment is 40% to 80%.

4. The optical element of claim 1, wherein a relative humidity at each temperature of the wet-heat treatment is 55% to 65%.

5. The optical element of claim 1, wherein the resin containing polymers having an alicyclic structure contains repeating unit (a) having an alicyclic structure represented by following general formula (1) and repeating unit (b) comprising a chain structure represented by following general formula (2) and/or (3) so as to make the sum content of repeating unit not less than 90 weight %, and, further, make the content of repeating unit (b) not less than 1 weight % and less than 10 weight % among whole repeating units of a polymer having a weight average molecular weight (Mw) of 1,000 to 1,000,000, and the chain of the repeating unit (a) satisfies the following formula: (That is, A≦0.3×B, where A=(a weight average molecular weight of a repeating unit chain having an alicyclic type structure), and B=(a weight average molecular weight of a hydrocarbon copolymer having an alicyclic type structure(Mw)×(the number of repeating units having an alicyclic type structure/the number of whole repeating units constructing the hydrocarbon copolymer having the alicyclic type structure),




where in formula (1), X represents an alicyclic hydrocarbon group, R1–R13 in formulas (1), (2) and (3) each independently represent a hydrogen atom, a chain hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ether group, an ester group, a cyano group, an amido group, an imido group, a silyl group and a chain hydrocarbon group substituted by a polar group (a halogen atom, an alkoxy group, a hydroxyl group, an ether group, an ester group, a cyano group, an amido group, an imido group or a silyl group), and in general formula (3), . . . represents a carbon-carbon saturated bond or a carbon-carbon unsaturated bond.

6. The optical element of claim 5, wherein the resin containing polymers having an alicyclic structure includes block copolymers having poloymer block [A] containing a repeating unit [1] represented by a formula (11) and poloymer block [B] containing a repeating unit [1] and a repeating unit [2] represented by a formula (12) and/or a repeating unit [3] represented by a formula (13) and the block copolymers satisfy the relationship of a>b, where a is a mol fraction (mol %) of the repeating unit [1] in the polymer block [A] and b is a mol fraction (mol %) of the repeating unit [1] in the polymer block [B].




where in the formula, R1 represents a hydrogen atom or an alkyl group having a carbon number of 1–20, R2–R12 each independently represent a hydrogen atom, an alkyl group having a carbon number of 1–20, a hydroxyl group, an alkoxy group having a carbon number of 1–20 or a halogen group,




where in the formula, R13 represents a hydrogen atom or an alkyl group having a carbon number of 1–20,




where in the formula, R14 and R15 each independently represent a hydrogen atom or an alkyl group having a carbon number of 1–20.

7. The optical element of claim 1, wherein the optical element is a optical pickup lens for use in an optical pickup apparatus.

8. A method of producing an optical element having an optical axis, comprising:
molding a resin containing a polymer having an alicyclic structure to form an element body having the maximum first length of 4 mm or less in the optical axis direction and the second maximum length of 6 mm or less in the direction perpendicular to the optical axis direction; and thereafter,
treating the element body by one of heat treatment and wet-heat treatment for 16 hours or longer at a temperature lower by 35° C. to 45° C. than the glass transition temperature of the resin, where the glass transition temperature of the resin is measured by differential-scanning-calorimetry method at heating rate 10° C./min on the basis of JIS K7121.

9. The method of claim 8, wherein the treating time is 150 hours or longer.

10. The method of claim 8, wherein a relative humidity at each temperature of the wet-heat treatment is 40% to 80%.

11. The method of claim 8, wherein a relative humidity at each temperature of the wet-heat treatment is 55% to 65%.