Source: http://www.google.com/patents/US4943516?dq=Frischling
Timestamp: 2017-11-18 05:28:03
Document Index: 572007015

Matched Legal Cases: ['arts2', 'arts2', 'arts2', 'arts2', 'arts2', 'arts2', 'arts75', 'arts2', 'arts2', 'arts1', 'arts2', 'arts75', 'arts75']

Patent US4943516 - Photosensitive thermosetting resin composition and method of forming solder ... - Google Patents
A photosensitive thermosetting resin composition, comprising (A) a photosensitive prepolymer containing at least two ethylenically unsaturated bonds in the molecular unit thereof, (B) a photoinitiator, (C) a photopolymerizable vinyl monomer and/or an organic solvent as a diluent, (D) a finely powdered...http://www.google.com/patents/US4943516?utm_source=gb-gplus-sharePatent US4943516 - Photosensitive thermosetting resin composition and method of forming solder resist pattern by use thereof
Publication number US4943516 A
Application number US 07/274,966
Also published as CA1331711C, CN1028535C, CN1033389A, CN1036693C, CN1081557A, DE3885260D1, DE3885260T2, EP0323563A2, EP0323563A3, EP0323563B1
Publication number 07274966, 274966, US 4943516 A, US 4943516A, US-A-4943516, US4943516 A, US4943516A
Inventors Yuichi Kamayachi, Kenji Sawazaki, Morio Suzuki, Shoji Inagaki
Patent Citations (15), Referenced by (85), Classifications (33), Legal Events (6)
Photosensitive thermosetting resin composition and method of forming solder resist pattern by use thereof
US 4943516 A
A photosensitive thermosetting resin composition, comprising (A) a photosensitive prepolymer containing at least two ethylenically unsaturated bonds in the molecular unit thereof, (B) a photoinitiator, (C) a photopolymerizable vinyl monomer and/or an organic solvent as a diluent, (D) a finely powdered epoxy compound containing at least two epoxy groups in the molecular unit thereof and exhibiting sparing solubility in the diluent to be used, and optionally (E) a curing agent for epoxy resin, excels in developing property and sensitivity and enjoys a long shelf life.
1. A photosensitive thermosetting-resin composition, comprising (A) a potosensitive prepolymer containing at least two ethylenically unsaturated bonds in the molecular unit thereof, (B) a photoinitiator, (C) a photopolymerizable vinyl monomer and/or an organic solvent as a diluent, and (D) a finely powdered epoxy compound containing at least two epoxy groups in the molecular unit thereof and exhibiting sparing solubility in the diluent to be used.
An object of this invention is to provide a photosensitive thermosetting resin composition which suffers from none of the various drawbacks mentioned above, excels in both developing property and sensitivity, enables an exposed pert thereof to withstand the developing solution, and enjoys a long pot life.
In the case of solder resist quality photosensitive thermosetting resin compositions using an epoxy resin as a thermosetting component in combination with a photosensitive prepolymer, it has been customary to employ an epoxy resin of the kind solution in an organic solvent. When a photosensitive thermosetting resin composition is prepared by using an epoxy resin of this kind, it is presumed that the epoxy resin is dissolved therein as intertwined with the photosensitive prepolymer (with the chain-length portions of the resins held in intertwined state). When a composition using a photosensitive prepolymer soluble in an aqueous alkali solution is developed with an aqueous alkali solution, for example, since the epoxy resin is generally insoluble in an aqueous alkali solution and it is held as intertwined with the photosensitive prepolymer, the photosensitive prepolymer in the unexposed portion suffers from loss of solubility. Further, since the epoxy resin is dissolved in the composition, the epoxy resin reacts unduly rapidly with the curing agent which is liable to induce the socalled heat fogging, a phenomenon that incomplete development occurs during the courses of development. Therefore the composition acquires an inferior developing property. When a composition using a photosensitive prepolymer soluble in the organic solvent used for the development is developed with an organic solvent, the composition tends to induce the same heat fogging and suffers from a decline of developing property in spite of the solubility of the epoxy resin in the solvent. Further in the exposed portion, the coating tends to be corroded and suffers from impairment of sensitivity because the photosensitive prepolymer permits no enhancement of cross-linking density owing to the presence of the epoxy resin and dissolves into the developing solution (organic solvent). In said either case the shelf life of the composition becomes short, since the reaction of the epoxy resin with the curing agent is rapid as mentioned above.
The reaction is accomplished, for example, dissolving a novolak type epoxy compound in an organic solvent such as cellosolve acetate, carbitol acetate, or ethylmethyl ketone and causing the resultant solution and an unsaturated monocarboxylic acid and/or an unsaturated phenol compound added thereto react with each other by being heated and stirred at a temperature in the range of 70° to 140° C. in the presence of a thermal polymerization inhibitor such as hydroquinone, catechol, or pyrogallol and a catalyst such as a tertiary amine like benzyl diethylamine or triethylamine or a quaternary ammonium salt like benzyltrimethyl ammonium chloride or benzyltriethyl ammonium bromide.
The product aimed at is obtained by selecting at least one species from the aforementioned resins (a-1) through (b-2) and at least one species from the aforementioned polybasic acid anhydrides, mixing the selected species, and heating and stirring them at a temperature in the range of 70° to 120° C. as generally practised.
The addition products (a-1-2), (a-2-2), (b-1-2), and (b-2-2) between the secondary hydroxyl group of the complete esterification products (a-1), complete etherification products (b-1), partial esterification producrs (a-2), and partial etherification products (b-2) of novolak type epoxy compounds mentioned above and (meth)-acrylates possessing one hydroxyl group in the molecular unit thereof through the medium of diisocyanates are obtained as follows. As the first step, the diisocyanate and the (meth)acrylate having one hydroxyl group in the molecular unit thereof are caused to react with each other in an equimolar ratio by being heated and stirred at a temperature in the range of 30° to 100° C. for a period in the range of 2 to 12 hours as generally practised, using or not using an organic solvent such as cellosolve acetate, carbitol acetate, or ethylmethyl ketone in the presence of a catalyst such as an organic tin compound like tributyl tin dilaurate or a tertiary amine like benzyldimethyl amine or triethyl amine, to effect synthesis of a half-urethane acrylate. In this case, the (meth)acrylate possessing one hydroxyl group in the molecular unit and the diisocyanate are desired to be used in amounts forming an equimolar ratio. Optionally, the (meth)acrylate may be used in an excess amount so that the excess thereof will be utilized per se as a reactive diluent. Then, the half-urethane (meth)acrylate obtained as described above is cooled to a temperature in the range of 25° to 35° C., mixed with at least one species selected from the aforementioned products (a-1) through (b-2) in relative amounts such that the ratio of number of equivalents of the isocyanate of the half-urethane (meth)acrylate to number of equivalents of the secondary hydroxyl group possessed by the selected species exceeds 0.1, desirably falls in the range of 0.1 to 1.0, preferably in the range of 0.2 to 0.9. Then, the resultant mixture is heated and stirred for reaction at a temperature in the range of 30° to 100° C. for a period in the range of 2 to 12 hours. If, in this case, the equivalent ratio is less than 0.1, the effect in heightening the setting property manifested on exposure to the actinic ray is not obtained.
Now, the present invention will be described more specifically below with reference to working examples and comparative experiments. It should be noted, however, that the present invention is not limited to these examples. Wherever "parts" and "%" are mentioned, they are invariably based on weight unless otherwise specified.
In a three-neck flask provided with a stirrer and a condenser, 1,090 parts of a cresol novolak type epoxy resin having an epoxy equivalent of 218 (product of Tohto Kasei Co., Ltd. under registered trademark designation of "Epo Tohto" YDCN-702) was melted and stirred at a temperature in the range of 90° C. to 100° C. Then, 396 parts of acrylic acid, 0.6 part of hydroquinone, and 7.0 parts of benzyl dimethyl amine were added to the stirred molten resin. The resultant mixture was heated to a temperature in the range of 110° C. to 115° C. and stirred for reaction for 12 hours. The reaction mixture was removed from the flask and left cooling to normal room temperature, to obtain a complete esterification product (a-1) of the novolak type epoxy compound with acrylic acid having an acid value of 4.5 mg KOH/g. The product was in a semisolid state.
A partial esterification product (a-2) of a novolak type epoxy compound with acrylic acid having an acid value of 0.5 mg KOH/g was obtained by following the procedure of Preparation Example 1, excepting the amount of acrylic acid was changed to 250 parts and the length of reaction time to 7 hours. The product was in a solid state. Preparation Example 3:
In the same reaction vessel as used in Preparation Example 1, 450 parts of the complete esterification product (a-1) obtained in Preparation Example 1, 125 parts of cellosolve acetate, and 125 parts of a tetramethyl benzene-based petrolic solvent (produced by Idemitsu Petrochemical Co., Ltd. under registered trademark designation of "IPSOL" #150) were dissolved at a temperature in the range of 70° C. to 80° C. Then, the hot molten mixture and 120 parts of phthalic anhydride added thereto were heated to a temperature in the range of 95° C. to 100° C and stirred for reaction for 8 hours. The resultant reaction mixture was removed from the reaction vessel and left cooling to normal room temperature. Consequently, there was obtained an organic solvent solution of an acid anhydride adduct (a-1-1) of said complete esterification product of the novolak type epoxy compound with acrylic acid whose solid component possessed an acid value of 85 mg KOH/g.
In the same reaction vessel as used in Preparation Example 1, 87 parts of tolylene diisocyanate (a mixture of 65% of 2,4-position and 35% of 2,6-position), 50 parts of carbitol acetate, and 50 parts of Ipsol #150 were heated and stirred at 25° C. To the hot stirred mixture, a mixture consisting of 65 parts of 2-hydroxyethyl acrylate, 50 parts of cellosolve acetate, 50 parts of Ipsol #150, 0.05 part of phenothiazine, and 0.2 part of dibutyl tin dilaurate was added dropwise over a period of 2 hours, with the temperature thereof controlled below 35° C. Then, the resultant mixture was heated to 50° C. and stirred for reaction for 4 hours, to obtain a half urethane compound having a terminal acryl group. Then, the half urethane compound and 250 parts of the partial esterification product (a-2) obtained in Preparation Example 2 added thereto were heated to 80° C. and stirred for reaction for 6 hours and then left cooling to normal room temperature and removed from the reaction vessel. Consequently, there was obtained an organic solvent solution of a urethane acrylate adduct (a-2-2) of a partial esterification product of the novolak type epoxy compound with acrylic acid.
In the same reaction vessel as used in Preparation Example 1, 105 parts of a phenol novolak type epoxy resin having an epoxy equivalent of 210 (product of Dainippon Ink and Chemicals, Inc. under registered trademark designation of "EPICLON" N-865) and 130 parts of cellosolve acetate were dissolved at a temperature in the range of 70° C. to 80° C. and stirred. Then, 120 parts of 4'-hydroxychalcone and 3.5 parts of benzyltrimethyl ammonium bromide were added to the hot stirred mixture. The resultant mixture was heated to a temperature in the range of 125° C. to 130° C. and stirred for reaction for 15 hours. The reaction mixture was left cooling to 80° C. and, with 40 parts of hexahydrophthalic anhydride mixed therewith, heated to a temperature in the range of 90° C. to 95° C. and stirred for reaction for 10 hours, removed from the reaction vessel, and left cooling to normal room temperature. Consequently, there was obtained an organic solvent solution of an acid anhydride adducts (b-1-1) of the complete etherification product of the novolak tyep epoxy compound with an unsaturated phenol compound whose solid component possessed an acid value of 58 mg KOH/g.
______________________________________Resin (a-1) obtained in Preparation Example 1                     30.0   partsDipentaerythritol hexaacrylate                     9.0    partsDiethylene glycol diacrylate                     22.0   partsBenzyl dimethyl ketal     4.0    parts2-(Dimethylamino)ethyl benzoate                     1.5    partsBarium sulfate            20.0   partsFinely powdered talc      5.0    partsPhthalocyanine green      0.5    partLeveling agent (product of Monsanto                     1.0    partChemical Co. under registered trademarkdesignation of "MODAFLOW")Finely powdered diglycidyl terephthalate                     4.0    parts(product of Nippon Oil and Fats Co., Ltd.under registered trademark designation of"BLEMMER")Particulate bisphenol S type epoxy resin                     3.0    parts(product of Nippon Kayaku Co., Ltd. underregistered trademark designation of"EBPS"-200)Total:                    100.0  parts______________________________________
The components indicated above were premixed in the proportions indicated correspondingly and the premix was kneaded three times with a three-roll mill to produce a photosensitive thermosetting resin composition. By a test with a grind meter (produced by Toyo Seiki Seisakusho Co., Ltd.), this composition was found to possess a particle size of not more than 25 μm. This photosensitive thermosetting resin composition was applied by the screen printing method on the entire surface of a copper throughhole printed circuit board. Then, a photomask having a predetermined pattern was set as opposed to the coated surface across a space of 0.7 mm. The coating of the composition was then exposed through the photomask to a light from a collimating ultra-high-pressure mercury-vapor lamp exposure device (product of ORC manufacturing Co., Ltd.). The exposed coating was developed with modified trichloroethane (product of Asahi Chemical Industry Co., Ltd. under registered trademark designation of "ETERNA" IR) applied as developing solution by spraying under a pressure of 2.0 kg/cm2. It was placed in a hot air circulation oven kept at a temperature of 200° C. and postcured for 50 minutes, to form a solder resist pattern.
______________________________________Resin (a-1) obtained in  25.0   partsPreparation Example 1Resin (a-2) obtained in  15.0   partsPreparation Example 2Cellosolve acetate       23.0   partsPentaerythritol tetraacrylate                    5.5    partsBenzyl dimethyl ketal    3.5    parts2-Chlorothioxanthone     2.5    partsBarium sulfate           11.0   partsFinely powdered silicon oxide (product                    1.0    partof Nippon Aerosil Co., Ltd. underregistered trademark designation of"AEROSIL" #200)Phthalocyanine green     0.5    partAnti-foaming agent (product of Kyoeisha                    1.0    partChemical Co., Ltd. under the trade nameof "FLOWLEN" AC-300)Finely powdered diglycidyl terephthalate                    10.0   parts(product of Nippon Oil and Fats Co., Ltd.under registered trademark designation of"BLEMMER"-DGT)Curing agent (product of Shikoku                    2.0    partsKasei Chemical Co., Ltd. marketed underregistered trademark designation of"CUREZOL" 2PHZTotal                    100.0  parts______________________________________
A photosensitive thermosetting resin composition was prepared by premixing the components indicated above in the proportions indicated correspondingly and kneading the premix twice with a three-roll mill. It was found to have a particle size of not more than 20 μm. This photosensitive thermosetting resin composition was applied to the entire surface of a copper through-hole printed circuit board with a roll coater (product of The Pilot Seiko Co., Ltd.). The board coated with the resin composition was placed in a hot air circulation oven, dried therein at 80° C. for 20 minutes, and then left cooling to room temperature, to produce a board with a dry coating.
A photomask having a predetermined pattern was placed contiguously on the coated surface of the board. The coating was exposed through the photomask to a light from a ultrahighpressure mercury-vapor lamp exposure device (product of ORC Manufacturing Co., Ltd.). The coated board was placed in a hot air circulation oven kept at a temperature of 150° C. and post-cured for 50 minutes. Consequently a solder resist pattern was formed by following the procedure of Example 1.
______________________________________Resin (a-1-1) obtained in Preparation                     45.0   partsExample 3Propylene glycol monomethyl ether acetate                     5.0    partsDipentaerythritol hexaacrylate                     5.0    parts2-Hydroxyethyl acrylate   2.0    parts2-Amyl anthraquinone      3.5    partsBenzyl                    2.0    partsAluminum oxide powder     5.0    partsFinely powdered talc      5.0    partsBarium sulfate            11.0   partsPhthalocyanine green      0.5    part"MODAFLOW"                1.0    partsParticulate bisphenol S type epoxy resin                     15.0   parts(product of Dainippon Ink and ChemicalsIndustries, Ltd. under registered trademarkdesignation of "EPICLON" EXA-1514)Total:                    100.0  parts______________________________________
A photosensitive thermosetting resin composition was prepared by following the procedure of Example 2 using the components indicated above in the proportions indicated correspondingly. It was found to have a particle size of not more than 20 μm. This photosensitive thermosetting resin composition was applied to the entire surface of a copper through-hole printed circuit board with a roll coater (product of The Pilot Seiko Co., Ltd.). The coated board was placed in a hot air circulation oven, dried at 70° C. for 20 minutes, and left cooling to room temperature, to obtain a board with a dry coating. This coating was given an exposure in the same manner as in Example 2, developed with an aqueous 1% sodium carbonate solution used as a developing solution and applied by spraying under a pressure of 2.0 kg/cm2, washed with water, and then dried. The board with the dry coating was post-cured for 30 minutes in a hot air circulation oven kept at a temperature of 150 ° C., to form a solder resist pattern.
______________________________________Resin (a-1-1) obtained in Preparation                    45.0   partsExample 3Solid diallyl phthalate prepolymer                    5.0    parts(product of Daiso Co., Ltd. underregistered trademark designation of"DAISO DAP")Cellosolve acetate       5.0    partsTrimethylol propane triacrylate                    4.0    partsTriethylene glycol diacrylate                    3.0    parts2-Methyl-1-[4-(methylthio)phenyl]-2-                    3.0    partsmorpholinopropan-1-one2,4-Diisopropyl thioxanthone                    2.5    partsClay                     11.0   partsFinely powdered talc     5.0    partsPhthalocyanine green     0.5    part"MODAFLOW"               1.0    partParticulate bixylenol type epoxy resin                    12.0   parts(product of Yuka Shell Epoxy KabushikiKaisha under registered trademarkdesignation of "EPIKOTE" YX-4000)Dicyandiamide            2.0    partsCuring agent (product of Shikoku                    1.0    partChemicals, Co. under registeredtrademark designation of "CUREZOL"2E4MZ-CNS)Total:                   100.0  parts______________________________________
______________________________________Resin (a-2-2) obtained in Preparation                    30.0   partsExample 4Butyl cellosolve         12.0   partsPentaerythritol tetraacrylate                    5.0    partsHydroxycyclohexyl phenyl ketone                    3.0    partsN,N-dimethylaminoacetophenone                    1.0    partBarium sulfate           10.0   partsFinely powdered talc     4.0    partsPhthalocyanine green     0.5    part"AC-300"                 0.5    partPariticulate bisphenol S type epoxy                    15.0   partsresin (product of Asahi Denka KogyoCo., Ltd. under registered trademarkdesignation of "EPX-30")"2PHZ"                   1.0    partTotal:                   82.0   parts______________________________________
______________________________________Resin (b-1-1) obtained in                    25.0   partsPreparation Example 5Resin (a-1-1) obtained in                    10.0   partsPreparation Example 3Carbitol acetate         10.0   partsPentaerythritol tetraacrylate                    7.0    parts2-Ethylanthraquinone     3.0    parts"Aerosil #200"           1.5    partsFinely powdered talc     3.0    partsSilicon oxide powder     20.0   partsPhthalocyanine green     0.5    parts"MODAFLOW"               1.5    parts75% cellosolve acetate solution of                    5.0    partsbisphenol A type epoxy resin (productof Yuka Shell Epoxy Kabushiki Kaishaunder registered trademark designationof "EPIKOTE" 1009)Finely powdered heterocyclic epoxy resin                    10.0   parts"product of Nissan Chemical Industries,Ltd. under product code of "TEPIC")Polyvinyl phenol (product of Cosmo                    2.0    partsOil Company, Ltd. under product codeof "RESIN M")"2PHZ"                   1.5    partsTotal:                   100.0  parts______________________________________
______________________________________50% Butyl cellosolve solution                     53.0   partsof "DAISO DAP"Pentaerythritol tetraacrylate                     7.0    partsDimethylbenzyl ketal      3.5    parts2-(Dimethylamino)ethyl benzoate                     1.5    partsFinely powdered talc      9.5    partsBarium sulfate            10.0   parts"AC-300"                  1.0    partPhthalocyanine green      0.5    partFinely powdered biphenol type epoxy                     5.0    partsresin (product of Yuka Shell EpoxyKabushiki Kaisha under registeredtrademark designation of "EPIKOTE"YL-6056)Particulate bisphenol S type epoxy resin                     7.0    parts(product of Dainippon Ink and Chemicals,Inc. under registered trademark designationof "EPICLON"EXA-1514)2-Phenyl-4-benzyl-5-hydroxymethyl                     2.0    partsimidazoleTotal:                    100.0  parts______________________________________
______________________________________Resin (a-1) obtained in Preparation                    40.0   partsCellosolve acetate       22.0   partsPentaerythiritol tetraacrylate                    7.0    parts2-Ethyl anthraquinone    2.0    parts1-Chlorothioxanthone     2.5    partsFinely powdered talc     10.0   partsBarium sulfate           15.0   partsPhthalocyanine green     0.5    partAnti-foaming agent (product of Kyoeisha                    1.0    partChemical Co., Ltd. under the trade nameof "FLOWLEN"AC-300)Total:                   100.0  parts______________________________________
______________________________________Resin (a-1-1) obtained in                    42.0   partsPreparation Example 3Trimethylol propane triacrylate                    6.0    partsButyl cellosolve         4.0    partsBenzyl dimethyl ketal    3.5    parts2-Ethyl anthraquinone    1.5    partsBarium sulfate           12.0   partsFinely powdred talc      8.0    partsPhthalocyanine green     0.5    part"MODAFLOW"               1.5    parts75% butyl cellosolve solution of                    18.0   partsnovolac type epoxy resin (product.of Tohto Kasei Co., Ltd. underregistered trademark designation of"Epo Tohto"YDCN-702)Dicyandiamide            2.0    partsCuring agent (product of Shikoku                    1.0    partChemicals, Ltd. under registeredtrademark designation of "CUREZOL"2PZ-CNS)Total:                   100.0  parts______________________________________
______________________________________Resin (a-2-2) obtained in Preparation                    40.0   partsExample 4Cellosolve acetate       5.0    partsDipentaerythritol hexaacrylate                    4.0    partsDiethylene glycol diacrylate                    3.0    partsBenzyl dimethyl ketal    3.0    partsFinely powdered talc     11.0   partsClay                     12.0   partsPhthaloctanine green     0.5    part"MODAFLOW"               1.5    parts75% cellosolve acetate solution of                    15.0   partsbisphenol A type epoxy resin (product ofYuka Shell Epoxy Kabushiki Kaisha underregistered trademark designation of"EPIKOTE" 1007)Diaminodiphenyl sulfone  2.0    partsCuring agent (product of Shikoku                    1.0    partChemicals Co. under registered trademarkdesignation of "CUREZOL" 2MZ-AZIN)Total:                   100.0  parts______________________________________
(1) Test for photosensitivity
The photosensitivity was determined by exposing a sample to an ultraviolet light 365 nm in wavelength to a varying dosage of 500, 750, or 1,000 mJ/cm2 with the aid of an integral actinometer (product of Orc Manufacturing Co., Ltd.), developing the exposed sample for 60 seconds with a relevant developing solution applied by spraying under a pressure of 2 kg/cm2, and visually rating the condition of the coating consequently produced on the following four-point scale.
(2) Test for developing property
The developing property was determined by exposing a sample through a relevant photomask to an ultraviolet light 365 nm in wavelength to a dosage of 750 mJ/cm2 with the aid of an integral actinometer (product of ORC Manufacturing Co., Ltd.) thereby producing a test piece, developing the test piece for a varying duration of 20, 40, or 60 seconds with a relevant developing solution applied by spraying under apressure of 2 kg/cm2, and visually rating the condition of removal of the unexposed part of the coating on the following four-point scale.
(3) Test for adhesion
The adhesion was determiend by exposing a sample through a relevant photomask to an ultraviolet light 365 nm in wavelength to a dosage of 750 mJ/cm2 with the aid of an integral actinometer (product of ORC Manufacturing Co., Ltd.), developing the exposed smaple for 60 seconds with a relevant developing solution applied by spraying under a pressure of 2 kg/cm2, post-curing the developed sample under varying conditions thereby producing a test piece, incising cross cuts in the test piece after the pattern of a checkerboard as specified by Japanese Industrial standard (JIS) D 0202, and subjecting the incised test piece to a peeling test using an adhesive cellophane tape (Cello Tape®) and visually rating the condition of peeling on the following four-point scale.
(4) Test for pencil hardness
The pencil hardness was determined by measuring hardness of the same test piece as used in the test for adhesion in accordance with the method specified in JIS K 5400 under a fixed load of 1 kg.
(5) Test for resistance to acids
This property was determined by keeping the same test piece as used in the test for ahesion immersed in an aqueous 10 vol% sulfuric acid solution at 20° C. for 30 minutes, removing the test piece from the aqueous solution, and rating the test piece comprehensively with respect to film condition and adhesion on the following four-point scale.
(6) Test for resistance to alkalis
This property was determined by following the procedure of the test for resistance to acids, excepting an aqueous 10 wt% sodium hydroxide solution was used in the place of the aqueous 10 vol% sulfuric acid solution.
(7) Test for resistance to solvent
This property was determined by following the procedure of the test for resistance to acids, excepting acetone was used in the place of the aqueous 10 vol% sulfuric acid solution.
(8) Test for resistance to plating
This property was determined by plating the same test piece as used in the test for adhesion in a gold plating liquid (product of Electro Plating Engineers of Japan, Ltd. under registered trademark designation of "AUTRONEX" CI) at 30° C. for 9 minutes with a current density of 1 A/dm2 thereby depositing a gold plate 1.5 μm in thickness and examining the condition of produced coating in the same manner as in the test for resistance to acids.
(9) Test for resistance to soldering temperature
This property was determined by dipping the same test piece as used in the test for adhesion once, three times, or five times each for 10 seconds in a soldering bath at 260° C. in accordance with the method specified in JIS C 6481 and rating the condition of the coating consequently produced in the same manner as in the test for resistance to acids.
(10) Determination of insulation resistance
The test pieces were prepared under the same conditions as in the test for adhesion, using a comb-shaped test pattern of IPC-B-25. The insulation resistance of each test piece was measured under normal conditions and again after allowing the test piece to stand absorbing moisture for 7 days under temperature cycle between 25° C. and 65° C. at fixed relative humidity of 90%, under application of an electric current of D.C. 100 V.
(11) Determination of shelf life
This property was determined by allowing a sample to be stored at 20° C. and counting the days of standing until the viscosity of the sample immediately after manufacture rose to twice the original value.
TABLE 1__________________________________________________________________________                                      Comparative              Example                 Experiment              1  2  3  4  5  6  7  8  1  2  3__________________________________________________________________________Photosensitivity (1)        ml/cm.sup.2               o  o ⊚                       ⊚                          ⊚                              o Δ                                   o  o  Δ                                            x        500        750   ⊚                 ⊚                    ⊚                       ⊚                          ⊚                             ⊚                                o  ⊚                                      o  o  Δ        1000  ⊚                 ⊚                    ⊚                       ⊚                          ⊚                             ⊚                                ⊚                                   ⊚                                      ⊚                                         ⊚                                            ΔDeveloping property (2)        sec.  o  o  o  o  Δ                             Δ                                Δ                                   o  o  x  x        20        40    ⊚                 ⊚                    ⊚                       ⊚                          o  o  o  ⊚                                      o  x  Δ        60    ⊚                 ⊚                    ⊚                       ⊚                          ⊚                             ⊚                                ⊚                                   ⊚                                      ⊚                                         Δ                                            oAdhesion (3)       o  ⊚                    ⊚                       ⊚                          ⊚                             ⊚                                ⊚                                   ⊚                                      x  ⊚                                            oPencil hardness (4)              6H 8H 6H 6H 6H 9H 8H 5H H  4H 3HResistance to acids (5)              o  ⊚                    ⊚                       ⊚                          ⊚                             ⊚                                ⊚                                   ⊚                                      x  ⊚                                            oResistance to alkalis (6)              o  ⊚                    o  ⊚                          ⊚                             ⊚                                ⊚                                   ⊚                                      x  Δ                                            ΔResistance to solvents (7)              o  ⊚                    o  o  ⊚                             ⊚                                ⊚                                   o  Δ                                         o  ΔResistance to plating (8)              Δ                 o  o  ⊚                          o  ⊚                                ⊚                                   ⊚                                      x  Δ                                            ΔResistance to soldering        Once  ⊚                 ⊚                    ⊚                       ⊚                          ⊚                             ⊚                                ⊚                                   ⊚                                      x  ⊚                                            otemperature (9)        3 times              ⊚                 ⊚                    ⊚                       ⊚                          ⊚                             ⊚                                ⊚                                   ⊚                                      -- o  o        5 times              o  ⊚                    ⊚                       ⊚                          ⊚                             ⊚                                ⊚                                   ⊚                                      -- Δ                                            ΔInsulation   Normal              9.6                 3.2                    2.6                       2.5                          2.3                             3.6                                5.4                                   1.6                                      6.1                                         2.1                                            2.0resistance (10)        Conditions              ×                 ×                    ×                       ×                          ×                             ×                                ×                                   ×                                      ×                                         ×                                            ×              10.sup.12                 10.sup.13                    10.sup.13                       10.sup.13                          10.sup.13                             10.sup.13                                10.sup.13                                   10.sup.13                                      10.sup.12                                         10.sup.13                                            10.sup.13        After 4.5                 2.1                    1.9                       3.8                          6.2                             7.3                                3.8                                   2.6                                      8.6                                         5.4                                            3.8        moisture              ×                 ×                    ×                       ×                          ×                             ×                                ×                                   ×                                      ×                                         ×                                            ×              10.sup.11                 10.sup.12                    10.sup.12                       10.sup.12                          10.sup.12                             10.sup.12                                10.sup.12                                   10.sup.12                                      10.sup.8                                         10.sup.10                                            10.sup.10Shelf life (11)    90 40 25 25 45 40 20 70 120                                         7  15__________________________________________________________________________
GB2032939A * Title not available
JPS61272A * Title not available
JPS5114044A * Title not available
JPS5755914A * Title not available
JPS6148800A * Title not available
JPS49107333A * Title not available
JPS60208377A * Title not available
JPS61243869A * Title not available
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U.S. Classification 430/280.1, 430/330, 430/313, 528/113, 427/177, 522/26, 427/510, 430/271.1, 430/288.1, 522/103, 430/281.1, 430/286.1, 427/517, 430/325, 430/287.1
International Classification C08G59/17, C08F2/48, H05K3/28, C08F283/10, G03F7/032, C08F283/00, G03F7/027, G03C1/00, C08G59/68, C08G59/00, C08G65/40, C08G59/40
Cooperative Classification G03F7/032, G03F7/027, H05K3/287
European Classification H05K3/28G2, G03F7/032, G03F7/027
Owner name: TAIYO INK MANUFACTURING CO., LTD., MINAMI-TOKIWADA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:KAMAYACHI, YUICHI;SAWAZAKI, KENJI;SUZUKI, MORIO;AND OTHERS;REEL/FRAME:004980/0984
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KAMAYACHI, YUICHI;SAWAZAKI, KENJI;SUZUKI, MORIO;AND OTHERS;REEL/FRAME:004980/0984