CN110895381A - Photosensitive solder resist ink composition, application thereof and circuit board containing same - Google Patents
Photosensitive solder resist ink composition, application thereof and circuit board containing same Download PDFInfo
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- CN110895381A CN110895381A CN201911141015.9A CN201911141015A CN110895381A CN 110895381 A CN110895381 A CN 110895381A CN 201911141015 A CN201911141015 A CN 201911141015A CN 110895381 A CN110895381 A CN 110895381A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
Abstract
The present invention relates to a photosensitive solder resist ink composition comprising: (A) a photosensitive resin containing both a carboxyl group and at least two ethylenically unsaturated bonds in a molecule, and the following components based on 100 parts by weight of the photosensitive resin: (B)1-40 parts by weight of photoinitiator, (C)0.1-20 parts by weight of organic surface auxiliary agent, (D)2-200 parts by weight of diluent, (E)3-100 parts by weight of thermosetting component, (F)1-50 parts by weight of photopolymerization monomer, and (G)20-150 parts by weight of inorganic filler; wherein the inorganic filler (G) comprises 20 to 150 parts by weight of an inorganic filler having a reactive functional group on the surface, based on 100 parts by weight of the photosensitive resin. In addition, the invention also provides a circuit board comprising a cured film formed by the photosensitive solder resist ink composition.
Description
Technical Field
The invention relates to a novel photosensitive solder resist ink composition, application thereof in preparing a printed circuit board, and a circuit board containing the photosensitive solder resist ink composition.
Background
In a Printed Circuit Board (PCB), a solder resist curing film as a permanent protective film needs to have good resistance to different external environments (temperature, humidity, light, etc.) to improve the aging resistance of the PCB, thereby greatly prolonging the service life thereof. For a high-reliability circuit board, PCT (Pressure Cooker Test) and TCT (Temperature Cycle Test) are important Test methods for accelerated aging life tests, and are widely used in the high-performance circuit board industry.
However, the photosensitive solder resist ink in the market generally has poor performance in the aspects of PCT and TCT tests, and cannot basically meet the test requirements of high-performance PCBs in the aspects of PCT and TCT. In particular, during PCT testing, solder resist peeling, blistering, and even peeling often occur, and eventually lead to failure of the circuit board. Similarly, solder masks are more prone to cracking between the traces of a PCB during TCT testing, particularly if cycled over a larger temperature range.
To solve the above problems, Japanese patent laid-open No. 2000-109541 discloses that PCT and TCT resistance are improved by increasing the proportion of inorganic filler, but too high a proportion of filler generally results in deterioration of leveling property of the ink and also in deterioration of scratch resistance of the ink. Based on this, CN103034054A discloses a method of adding a naphthalene derivative and/or naphthoquinone and derivatives thereof to a solder resist ink to solve the problem of poor leveling property of the ink and to improve PCT resistance, but the naphthalene derivative or naphthoquinone and derivatives thereof are expensive and have a deep color, which affects the photosensitivity of the ink.
Generally, a certain amount of inorganic filler is added to photosensitive solder resist ink to make it have hardness, chemical resistance and higher electrical properties. The inventor finds that in the process of carrying out the PCT test, the bonding force of the interface between the resin and the inorganic filler is weaker than that of the resin, so that high-pressure water vapor slowly permeates into the solder mask from the interface with weaker bonding force and enters between the solder mask and a copper surface to accelerate the oxidation process of the copper surface, further the adhesion force between the solder mask and the copper surface is reduced, the phenomena of solder mask peeling, bubbling, even falling and the like occur, and finally the circuit board fails. Similarly, during the TCT test, cracking is most likely to occur at the interface of the weaker-binding resin and inorganic filler during cycling over a greater temperature range due to the difference in the Coefficient of Thermal Expansion (CTE) of the resin and inorganic filler.
Accordingly, there is a need to provide photosensitive solder resist inks that overcome the disadvantages of the prior art and that, when applied to printed wiring boards, can greatly improve PCT and TCT resistance without degrading other properties of the ink.
Disclosure of Invention
To solve the above problems, in one aspect, the present invention provides a photosensitive solder resist ink composition comprising:
(A) a photosensitive resin containing both a carboxyl group and at least two ethylenically unsaturated bonds in a molecule, and the following components based on 100 parts by weight of the photosensitive resin:
(B)1 to 40 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight of a photoinitiator,
(C)0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight of an organic surface auxiliary,
(D)2 to 200 parts by weight, preferably 5 to 100 parts by weight, more preferably 8 to 60 parts by weight of a diluent,
(E)3 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 10 to 50 parts by weight of a thermosetting component,
(F)1 to 50 parts by weight, preferably 2 to 40 parts by weight, more preferably 5 to 20 parts by weight of a photopolymerizable monomer, and
(G)20 to 150 parts by weight, preferably 50 to 120 parts by weight, more preferably 60 to 110 parts by weight of an inorganic filler;
wherein the inorganic filler (G) comprises an inorganic filler having a reactive functional group on the surface thereof in an amount of 20 to 150 parts by weight, preferably 50 to 120 parts by weight, more preferably 60 to 110 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (A).
Furthermore, the invention relates to the use of the photosensitive solder resist ink composition for the preparation of printed circuit boards.
In another aspect, the present invention also provides a wiring board comprising a cured film formed from the above photosensitive solder resist ink composition.
Unexpectedly, a cured film formed on a circuit board by the photosensitive solder resist ink composition has the characteristics of good heat resistance, adhesion, solvent resistance, acid resistance, hardness and the like, and can remarkably improve the PCT and TCT resistance.
Detailed Description
In the present invention, all operations were carried out at room temperature (25 ℃ C.) and normal pressure (101KPa), unless otherwise specified.
In the context of the present invention, acid number means the value obtained by measuring GB/T2895-2008 by means of acid-base titration of KOH standard solutions. The viscosity is measured according to the test method of GB/T7193-2008 (VT-4, No. 2 rotor, 60 r/min) unsaturated polyester resin, and the solid content is measured according to the test method of GB/T7193-2008 unsaturated polyester resin. The number-average molecular weight is determined by Gel Permeation Chromatography (GPC) according to GB/T21863-2008 Gel Permeation Chromatography (GPC) using tetrahydrofuran as eluent (German standard DIN 55672-1: 2007 Gel Permeation Chromatography (GPC) part 1 using Tetrahydrofuran (THF) as eluting solvent).
According to a first aspect of the present invention, there is provided a photosensitive solder resist ink composition comprising:
(A) a photosensitive resin containing both a carboxyl group and at least two ethylenically unsaturated bonds in a molecule, and the following components based on 100 parts by weight of the photosensitive resin:
(B)1 to 40 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight of a photoinitiator,
(C)0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight of an organic surface auxiliary,
(D)2 to 200 parts by weight, preferably 5 to 100 parts by weight, more preferably 8 to 60 parts by weight of a diluent,
(E)3 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 10 to 50 parts by weight of a thermosetting component,
(F)1 to 50 parts by weight, preferably 2 to 40 parts by weight, more preferably 5 to 20 parts by weight of a photopolymerizable monomer, and
(G)20 to 150 parts by weight, preferably 50 to 120 parts by weight, more preferably 60 to 110 parts by weight of an inorganic filler;
wherein the inorganic filler (G) comprises an inorganic filler having a reactive functional group on the surface thereof in an amount of 20 to 150 parts by weight, preferably 50 to 120 parts by weight, more preferably 60 to 110 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (A).
In a preferred embodiment of the present invention, the solid content of the photosensitive resin (A) has an acid value of 40 to 160mgKOH/g, preferably 50 to 120mgKOH/g, more preferably 60 to 100mgKOH/g, which can be prepared by any one of the following methods:
(1) subjecting a polyfunctional epoxy compound (a) having two or more epoxy groups in the molecule to an esterification reaction with an unsaturated monocarboxylic acid (b), and then reacting the resultant esterified product with a saturated or unsaturated polybasic acid anhydride (c);
(2) reacting (meth) acrylic acid with other comonomer (d) having an ethylenically unsaturated bond to form a copolymer, and then reacting a part of the resulting copolymer with glycidyl (meth) acrylate;
(3) reacting a copolymer of glycidyl (meth) acrylate and other comonomer (d) having an ethylenically unsaturated bond with an unsaturated monocarboxylic acid (b), and then reacting the resulting reaction product with a saturated or unsaturated polybasic acid anhydride (c);
(4) reacting a polyfunctional epoxy compound (a) having two or more epoxy groups in the molecule, an unsaturated monocarboxylic acid (b), and a compound (e) having at least two hydroxyl groups in the molecule and having one other group reactive with an epoxy group to obtain an intermediate (I), and then reacting the intermediate (I) with a saturated or unsaturated polybasic acid anhydride (c);
(5) reacting an unsaturated polybasic acid anhydride and an aromatic hydrocarbon having a vinyl group to form a copolymer, and then reacting the resulting copolymer with a hydroxyalkyl (meth) acrylate; or
(6) Reacting the intermediate (I) obtained in the method (4) with a saturated or unsaturated polybasic acid anhydride (c) and an unsaturated group-containing monoisocyanate (f).
In a preferred embodiment of the present invention, the polyfunctional epoxy compound (a) having two or more epoxy groups in the molecule in the methods (1) and (4) may be bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol a type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, novolak type epoxy resin, biphenol type epoxy resin, bixylenol type epoxy resin, triphenol methane type epoxy resin, and N-glycidyl type epoxy resin. When a novolak epoxy resin, a cresol novolak epoxy resin and a bisphenol a novolak epoxy resin are used, a solder resist cured film having excellent solder heat resistance, chemical resistance and the like can be obtained, and therefore, novolak epoxy resins, cresol novolak epoxy resins and bisphenol a novolak epoxy resins are preferably used. The polyfunctional epoxy compound having two or more epoxy groups in the molecule may be used alone or in the form of a mixture thereof.
In a preferred embodiment of the present invention, the unsaturated monocarboxylic acid (b) in the methods (1), (3) and (4) may be acrylic acid, acrylic acid dimer, methacrylic acid, β -styrylacrylic acid, β -furfurylacrylic acid, crotonic acid, α -cyanocinnamic acid, cinnamic acid, and a reaction product of a saturated or unsaturated dibasic acid anhydride and a (meth) acrylate containing one hydroxyl group in the molecule or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated monoglycidyl compound.
In a preferred embodiment of the present invention, the saturated or unsaturated polybasic acid anhydride (c) in the processes (1), (3), (4) and (6) may be: dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like; polybasic aromatic carboxylic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, and the like; and 5- (2, 5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexenyl-1, 2-dicarboxylic anhydride, and polybasic acid anhydride derivatives thereof. In view of the characteristics of the cured film, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and succinic anhydride are preferable. The saturated or unsaturated polybasic acid anhydrides may be used alone or in the form of a mixture thereof.
In a preferred embodiment of the present invention, the amount of the saturated or unsaturated polybasic acid anhydride (c) is such that the solid component of the reaction product has an acid value of 40 to 160mgKOH/g, preferably 50 to 120mgKOH/g, more preferably 60 to 100 mgKOH/g. When the acid value of the solid component of the reaction product is less than 40mgKOH/g, the photosensitive solder resist ink composition is poor in alkali solubility, and the resulting cured film is difficult to develop in a subsequent dilute aqueous alkali solution. However, when the acid value of the solid component of the reaction product is more than 160mgKOH/g, the resulting cured film is poor in development resistance, and sometimes even an effective cured film cannot be formed because the solubility in an aqueous alkali solution is too good.
In a preferred embodiment of the present invention, the other comonomer (d) having an ethylenically unsaturated bond in the methods (2) and (3) may be styrene, chlorostyrene, α -methylstyrene, acrylate or methacrylate substituted with methyl, ethyl, propyl, isopropyl, N-butyl, isobutyl, tert-butyl, amino, 2-ethylhexyl, octyl, decanoyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isobornyl, methoxyethyl, butoxyethyl, 2-hydroxyethyl, 2-hydroxypropyl or 3-chloro-2-hydroxypropyl, monoacrylate or monomethacrylate of polyethylene glycol, or monoacrylate or monomethacrylate of polypropylene glycol, vinyl acetate, vinyl butyrate or vinyl benzoate, acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-methoxymmethacrylamide, N-ethoxymethacrylamide, N-butoxymethacrylamide, acrylonitrile or maleic anhydride, etc.
In a preferred embodiment of the present invention, the compound (e) having at least two hydroxyl groups in the molecule and having one other group reactive with an epoxy group in the methods (4) and (6) may be a monocarboxylic acid having a polyhydroxy group, such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, dimethylolhexanoic acid, etc.; and dialkanolamines such as diethanolamine, diisopropanolamine and the like. The compounds having at least two hydroxyl groups in the molecule and having one other group reactive with an epoxy group may be used alone or in a mixture thereof.
In a preferred embodiment of the present invention, the monoisocyanate (f) having an unsaturated group may be a product obtained by reacting methacryloyloxyethyl isocyanate or an organic diisocyanate with (meth) acrylic acid having one hydroxyl group in the molecule in an approximately equimolar ratio. The unsaturated monoisocyanates may be used alone or in the form of mixtures thereof.
The photosensitive resin (a) of the present invention is not limited to the photosensitive resin obtained by the above-described method, and it may be used alone or in the form of a mixture thereof.
According to an embodiment of the present invention, the number average molecular weight of the photosensitive resin (a) is 200 to 1000000, preferably 500 to 100000, further preferably 1000 to 50000
According to an embodiment of the present invention, in the photosensitive solder resist ink composition, the photoinitiator (B) may be: benzine and benzine alkyl ethers such as benzine, benzine methyl ether, benzine ethyl ether, benzine isopropyl ether, and the like; acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone and the like; aminophenylacetophenones such as 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, N-dimethylaminoacetophenone and the like; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, etc.; thioxanthones such as 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, 2, 4-diisopropylthioxanthone, etc.; ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal, and the like; organic peroxides such as benzoyl peroxide, dicumyl peroxide, and the like; ketoxime esters such as OXE-1, OXE-2, etc.; thiol compounds such as 2,4, 5-triarylimidazole dimer, riboflavin tetrabutyl ester, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, etc.; organic halides such as 2,4, 6-tris-s-triazine, 2,2, 2-tribromoethanol, tribromomethylphenylketone, and the like; benzophenones such as benzophenone, 4' -bisdiethylaminobenzophenone and the like; and 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, etc.; benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and the like; or thioxanthones, such as 2-isopropyl thioxanthone; phosphine oxides such as (2, 6-dimethoxybenzoyl) -2,4, 4-pentylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, and ethyl-2, 4, 6-trimethylbenzoyl phenylphosphine oxide; various peroxides, titanocene initiators, and the like. In addition, these photoinitiators may be used together with tertiary amine photosensitizers such as ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, amyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine.
In a preferred embodiment of the present invention, the photoinitiator (B) may be contained in an amount of 1 to 40 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight, and most preferably 10 to 15 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (A).
According to an embodiment of the present invention, in the photosensitive solder resist ink composition, the organic surface assistant (C) may be a thixotropic agent, an antifoaming agent and a leveling agent, which are those conventionally used in the art. The amount thereof may be 0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (A).
In one embodiment of the present invention, the thixotropic agent may be a thixotropic agent conventionally used in the art, including, but not limited to, fumed silica, organobentonite, castor oil, and polyamides, such as BYK-411. The content of the thixotropic agent may be 0.05 to 40 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (a).
In one embodiment of the present invention, the defoaming agent may be silicone type, or acrylate type, or a mixture of both types of defoaming agent. Including but not limited to KS-66, commonly available from shin-Etsu corporation of Japan; german TEGO Digao antifoam: foamex N, Foamex 815N, Foamex 825, Foamex 840, Foamex 842; modemus antifoam agent: DEUCHEM 3200, DEUCHEM 3500, DEUCHEM 5300, DEUCHEM 5400, DEUCHEM 5600, DEUCHEM6500, DEUCHEM 6800; DEUCHEM 6600, and the like; acrylic defoamers from BYK, germany: BYK-051, BYK-052, BYK-053, BYK-057 and the like. The content of the defoaming agent may be 0.05 to 40 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (a).
In one embodiment of the present invention, the leveling agent may be a leveling agent conventionally used in the art, including, but not limited to, for example, BYK-354, BYK-306, BYK-399, etc., of BYK chemistry, or a mixture thereof, and other leveling agents may also be used, without particular limitation. The content of the leveling agent may be 0.05 to 40 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (a).
According to an embodiment of the present invention, in the photosensitive solder resist ink composition, the diluent (D) may be an organic solvent, for example, ethers such as ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, and the like; esters such as ethyl acetate, butyl acetate, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, dipropylene glycol butyl ether acetate, and the like; ketones, such as butanone, cyclohexanone, isophorone; aromatic solvents such as toluene, xylene, tetramethylbenzene; and petroleum solvents such as naphtha, oxidized naphtha, solvent naphtha, and the like. These diluents may be used alone or in the form of a mixture thereof.
In a preferred embodiment of the present invention, the content of the diluent (D) may be 2 to 200 parts by weight, preferably 5 to 100 parts by weight, more preferably 8 to 60 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (a).
According to an embodiment of the present invention, in the photosensitive solder resist ink composition, the thermosetting component (E) is an epoxy compound having two or more epoxy groups in the molecule. The epoxy compound is usually bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol a type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol a novolak type epoxy resin, biphenol type epoxy resin, bixylenol type epoxy resin, triphenolmethane type epoxy resin, N-glycidyl type epoxy resin, triglycidyl isocyanurate, 2, 6-xylenol dimer diglycidyl ether, aliphatic epoxy resin, xylene type epoxy resin. The above epoxy compounds may be used alone or in the form of a mixture thereof.
In a preferred embodiment of the present invention, the content of the thermosetting component (E) may be 3 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 8 to 80 parts by weight, still more preferably 10 to 50 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (a).
According to an embodiment of the present invention, in the photosensitive solder resist ink composition, examples of the photopolymerizable monomer (F) may be: hydroxyl group-containing acrylates such as hydroxyethyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc.; hydroxyl group-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate; monofunctional (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and lauryl (meth) acrylate; bifunctional (meth) acrylates such as 1, 6-hexanediol bis (meth) acrylate, dipropylene glycol bis (meth) acrylate, diethylene glycol bis (meth) acrylate, ethoxylated bisphenol a bis (meth) acrylate, and neopentyl glycol diethoxy/propoxy bis (meth) acrylate; polyfunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; and ethoxylated multifunctional acrylates and propoxylated multifunctional acrylates and the like. These photopolymerizable monomers may be used alone or in the form of a mixture thereof.
In a preferred embodiment of the present invention, the photopolymerizable monomer (F) may be contained in an amount of 1 to 50 parts by weight, preferably 2 to 40 parts by weight, more preferably 3 to 30 parts by weight, still more preferably 4 to 20 parts by weight, most preferably 5 to 10 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (a).
According to an embodiment of the present invention, in the photosensitive solder resist ink composition, the inorganic filler (G) may be an inorganic filler commonly used in the art, such as barium sulfate, barium titanate, calcium dioxide, talc, fumed silica, clay, magnesium carbonate, calcium carbonate, alumina, titanium oxide, mica powder, kaolin, and the like. The content of the inorganic filler (G) may be 20 to 150 parts by weight, preferably 50 to 120 parts by weight, more preferably 60 to 110 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (a).
According to an embodiment of the present invention, in the photosensitive solder resist ink composition, the inorganic filler (G) includes an inorganic filler having a reactive functional group on the surface thereof, and the inorganic filler (G) and a precursor of the inorganic filler having a reactive functional group on the surface thereof (i.e., an inorganic filler having an untreated surface without a reactive functional group) may be barium sulfate, barium titanate, calcium dioxide, talc, fumed silica, clay, magnesium carbonate, calcium carbonate, alumina, titanium oxide, mica powder, kaolin, or the like, preferably barium sulfate, silica, alumina, calcium carbonate, or a mixture thereof; the reactive functional group in the inorganic filler having a reactive functional group on the surface thereof may be a functional group that reacts with a group in the photosensitive resin (a), including, but not limited to, an epoxy group, an ethylenically unsaturated bond, an amino group, a carboxyl group, a hydroxyl group, a thiol group, etc., preferably an epoxy group, an ethylenically unsaturated bond, a hydroxyl group. Among these, the reactive functional groups are vinyl groups, and there may be mentioned: barium sulfate, barium titanate, calcium dioxide, talcum powder, fumed silica, clay, magnesium carbonate, calcium carbonate, alumina, titanium oxide, mica powder, kaolin or a mixture thereof with vinyl on the surface after surface treatment; the inorganic filler precursor having a reactive functional group on the surface is exemplified by silica, and can be exemplified by: silicon dioxide with one or more reactive functional groups such as olefinic unsaturated bond, epoxy group, amino group, carboxyl group or hydroxyl group on the surface after surface treatment. These inorganic fillers having a reactive functional group on the surface may be used alone or in the form of a mixture thereof.
In the present invention, the term "reactive functional group" is understood by those skilled in the art to mean that the surface of the inorganic filler contains a reactive functional group that can chemically react with a functional group (including, but not limited to, carboxyl group, ethylenic unsaturated bond) in the photosensitive resin to form a chemical bond that increases the bonding force between the inorganic filler and the resin.
In a preferred embodiment of the present invention, wherein, in the photosensitive solder resist ink composition, the content of the inorganic filler having a reactive functional group on the surface is 20 to 150 parts by weight, preferably 30 to 100 parts by weight, more preferably 40 to 100 parts by weight, still more preferably 50 to 90 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (a).
In a preferred embodiment of the present invention, the inorganic filler (G) having no reactive functional group on the surface and the inorganic filler precursor in the inorganic filler having a reactive functional group on the surface may be the same or different, preferably the same.
In a preferred embodiment of the present invention, the content of the inorganic filler having a reactive functional group on the surface is 20 to 100% by weight, preferably 30 to 100% by weight, more preferably 50 to 100% by weight, still more preferably 50 to 90% by weight, based on the total weight of the inorganic filler (G).
In a preferred embodiment of the present invention, the reactive functional group in the inorganic filler having a reactive functional group on the surface thereof may be one or more different reactive functional groups, preferably one reactive functional group, and the reactive functional group may be an epoxy group, an ethylenically unsaturated bond, an amino group, a carboxyl group, a hydroxyl group, a thiol group, preferably an epoxy group, an ethylenically unsaturated bond, a hydroxyl group, more preferably an ethylenically unsaturated bond, and particularly a vinyl group.
In a preferred embodiment of the present invention, the content of the reactive functional group in the inorganic filler having a reactive functional group on the surface thereof may be 0.001 to 0.5% by weight, preferably 0.005 to 0.3% by weight, more preferably 0.008 to 0.1% by weight, based on the total weight of the inorganic filler having a reactive functional group on the surface thereof.
In a preferred embodiment of the present invention, the reactive functional group in the inorganic filler having a reactive functional group on the surface thereof is a vinyl group, and the content of the vinyl group may be 0.001 to 0.5% by weight, preferably 0.005 to 0.3% by weight, more preferably 0.008 to 0.1% by weight, based on the total weight of the inorganic filler having a reactive functional group on the surface thereof.
In a preferred embodiment of the present invention, the weight ratio of the reactive functional group in the inorganic filler having a reactive functional group on the surface thereof to the photosensitive resin (a) may be 1:130-50000, preferably 1:300-40000, more preferably 1:1000-30000, still more preferably 1:10000-25000, most preferably 1: 11000-23000.
In the present invention, the particle diameter of the inorganic filler may be 0.001 to 100. mu.m, preferably 0.05 to 50 μm, more preferably 0.1 to 20 μm, still more preferably 0.1 to 5 μm. In particular, in the case where the composition is subsequently ground, the particle size of the inorganic filler may also be in other ranges, which is not particularly limited.
In the present invention, the content of the reactive functional group in the inorganic filler having a reactive functional group on the surface thereof can be obtained according to the instructions of commercially available products or determined according to a method known to those skilled in the art. For example, in the case where the reactive functional group is a carboxyl group, the acid value can be measured by a method of measuring the acid value in GB/T2895-2008. In the case of epoxy groups, the determination can be carried out using GB/T4612-2008. Similarly, in the case of hydroxyl groups, it is determined using the method described in GB/T12008.3-2009; in the case of vinyl groups, the determination is carried out using the method described in GB/T28610-. In the case of amino groups, this can be determined by reference to the method described in HG/T4260-2011. In the case of preparing the above inorganic filler having a reactive functional group on the surface by a physical adsorption method, the content of the reactive functional group can be indirectly calculated by combining the weight difference before and after adsorption with the chemical structure of the adsorbed compound.
In the present invention, the inorganic filler having a reactive functional group on the surface is commercially available or can be prepared by a method known in the art, for example, by physical adsorption or according to the method disclosed in japanese patent application laid-open publication No. 2011-225381.
In a particularly preferred embodiment of the present invention, the photosensitive solder resist ink composition may further comprise one or more additives selected from the group consisting of: epoxy curing accelerators, pigments, adhesion promoters, and the like, which may use all compounds conventional in the art. The content of the additive may be 0 to 40 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (a).
In a preferred embodiment of the present invention, the epoxy resin curing accelerator may be those conventionally used in the art. Common examples are: imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, guanamine, methylguanamine, benzoguanamine, and melamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphine compounds such as triphenylphosphine; and s-triazine derivatives such as 2, 4-diamino-6-methacryloyloxyethyl-s-triazine, 2-vinyl-2, 4-diamino-s-triazine, 2-vinyl-4, 6-diamino-s-triazine-isocyanuric acid adduct, and 2, 4-diamino-6-methacryloyloxyethyl-s-triazine-isocyanuric acid adduct. Further, blocked isocyanate compounds of dimethylamine produced by four chemical industries, such as 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ and 2P4 MHZ; U-CAT3503N and U-CAT3502T manufactured by SAN-APRO company, bicyclic amidine compounds and salts thereof DBU, DBN, U-CATA SA102, U-CAT5002 and the like. The content of the epoxy resin curing accelerator may be 0.05 to 40 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (a).
In a preferred embodiment of the present invention, the pigments are those conventionally used in the art, having an average particle diameter D50May be less than 1 micron, preferably less than 0.5 micron. Including, but not limited to, phthalocyanine green, phthalocyanine blue, carbon black, ultramarine, lithopone, permanent violet, permanent yellow, titanium dioxide, and the like. Common commercial products may be listed as: titanium dioxide R-706, R-900, R-902, R-931, R-960, R-102, R-103, R-104, R-105, R-350 from DuPont, USA; nippon stonewite pigment R-930, CR-60-2, R-200, R-600, R-980, CR-50-2, CR-58-2, CR-93, CR-80, CR-95, CR-97, etc.; basf L6480 Blue, basf L3980 red, Green Green L8730, Blue K7014LW, Blue K7090, Blue K6907, Blue D7079, Blue K6912, Blue L7080, Green Green D9360/6G, Blue L7085, Blue L6960F/BSNF, Blue K7072, Blue L7087/PG, Blue K6902, Blue L6700F, Blue K6911D, Blue L6875F, Green K8740, Blue L6900, Green K9360, Blue L6901F, Blue K7096/GBP, Blue L6920, Green L9361, Blue L6930, Blue L7101F, Blue L89 69 6989F, Green L8690 P.G7. The content of the pigment may be 0.05 to 40 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (a).
In the present invention, the adhesion promoters include, but are not limited to, for example, phosphate (meth) acrylates, and common commercial products are: CD9051 by sartomer, usa, PM2 by japan chemical company, and the like. The content of the adhesion promoter may be 0.05 to 40 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (a).
It should be noted that, in the present invention, the candidate substances of certain components may coincide, and in the case where the selected substances coincide, the substances having different functions are each metered to satisfy the respective content requirements.
In the present invention, the term "photosensitive resin" is used synonymously with "solid component of photosensitive resin (a)" unless otherwise specified. This is because in use, the "photosensitive resin" usually contains a solvent component (e.g., for reducing viscosity, easy handling), however, only a component containing no solvent is usually considered when, for example, calculation of material ratio, measurement of acid value, or the like is involved, which is well known to those skilled in the art.
When the photosensitive solder resist ink composition is prepared, all the components are uniformly mixed and ground to obtain the required particle size.
Without being bound by any theory, it is believed that the surface of the inorganic filler, after containing reactive functional groups that can react with the resin, on the one hand improves the binding force between the inorganic filler and the resin; on the other hand, the oil absorption of the inorganic filler is reduced, so that the leveling performance of the solder resist ink is improved, the screen printing performance of the solder resist ink is improved, and the PCT resistance and TCT resistance of the PCB prepared by the solder resist ink are obviously improved.
According to a second aspect of the present invention, the present invention also relates to a wiring board comprising a cured film formed from the above-mentioned photosensitive solder resist ink composition.
When the photosensitive solder resist ink composition of the present invention is used for the production of a wiring board, the ink composition is applied to a wiring board on which a wiring is formed in advance by a spraying method, a flow coating method, a roll coating method, a wire bar coating method, a screen printing method or the like. Thereafter, drying is carried out at a temperature of about 50 ℃ to 90 ℃. And then selectively exposing, developing in a dilute alkali aqueous solution, and further curing in an oven at 130-180 ℃ to form the circuit board.
Furthermore, the invention relates to the use of the photosensitive solder resist ink composition for the preparation of printed circuit boards.
Hereinafter, the present invention will be described in more detail with reference to the following examples. The examples disclosed below are for illustrative purposes only and are not intended to limit the present invention. Various modifications, additions and substitutions may be made to the embodiments of the invention by those skilled in the art without departing from the scope and spirit of the invention.
Examples
Synthesis of photosensitive resin
A photosensitive resin (A) was prepared according to the following synthetic example
210g of o-cresol novolac epoxy resin (SQPN-704M available from Shandong Shengquan New materials Co., Ltd., epoxy equivalent 210), 0.5g of hydroquinone and 200g of diethylene glycol ethyl ether acetate were charged into a kettle equipped with a stirrer, a thermometer, a dropping funnel, N2In a four-necked round bottom flask of the apparatus, all materials were dissolved by stirring and heating to 105 ℃ and holding at this temperature for 1 hour. Cooling to 90 deg.C after completely dissolving, adding 72g acrylic acid and 1g triphenyl phosphorus dropwise, controlling the temperature at 95 deg.C during the dropwise addition process, increasing the temperature to 105 deg.C after the dropwise addition process, reacting at the temperature for 12 hr, measuring the acid value of the reactant as 0.8mgKOH/g, cooling to 60 deg.C, adding 75g tetrahydro hydrogenPhthalic anhydride and incubation at 90 ℃ for 3 hours. Thus, a pale yellow photosensitive resin (A) having a solid content of 64%, a viscosity of 420dPa.s, a number average molecular weight of 3200, and a solid acid value of 74mgKOH/g was obtained.
Examples 1 to 5 and comparative example 1
A main agent: the photosensitive resin A obtained above was mixed with other components in accordance with the main agent formulation shown in Table 1, dispersed for 20 minutes by a high-speed disperser (Kirchen U400\80-220, the same applies hereinafter), and then ground by a three-roll grinder (Mill S-65, the same applies hereinafter) to a particle size of less than 10 μm (measured by a doctor blade refiner (Fulun QXP-100ISO, the same applies hereinafter)) to obtain an ink main agent.
Curing agent: according to the curing agent formula shown in the following table 1, the components are uniformly mixed, dispersed for 10 minutes at a high speed by a dispersion machine, and then ground by a three-roll grinder until the particle size is less than 10 μm (detected by a scraper fineness meter), so as to obtain the ink curing agent component.
Before use, the main agent and the curing agent are mixed and evenly stirred for reuse.
TABLE 1 ink composition ingredient Table (parts by weight)
Note 1: pigment, phthalocyanine green L9361 from Pasteur
Note 2: photoinitiator, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, available from Zhejiang Yangshan New materials Ltd
Note 3: photoinitiator, 2-isopropyl thioxanthone, available from Tianjin Jiu chemical Co., Ltd
Note 4: epoxy curing accelerators available from Nanjing Mei Kao science Co Ltd
Note 5: thixotropic agent, R972 from Degussa, Germany
Note 6: antifoam agent available from Nippon Denshi Kabushiki Kaisha
And 7, note: levelling agents from BYK Chemicals, Germany
Note 8: chemically untreated silica, available from Q060 of Suzhou brocade New Material science and technology Ltd
Note 9: chemically treated silica having vinyl groups on the surface (precursor Q060), available from Q063, New technology, Tech, Inc., wherein the vinyl content is 0.01% by weight, based on the weight of the silica having vinyl groups on the surface
Note 10: diluent, diethylene glycol Ether acetate, available from Dow chemical USA
Note 11: o-cresol novolac epoxy resin available from SQCN704, san Francisco group, Shandong
Note 12: photopolymerizable monomers, commercially available from Saedoma USA
Test examples
The photosensitive solder resist ink compositions prepared in examples 1 to 5 and comparative example 1 were prepared into wiring boards containing the respective photosensitive solder resist ink compositions by the following methods, and the respective characteristics thereof were measured in the following manners, and the results are shown in Table 2.
Test example 1: silkscreen printing property
After an 8cm × 10 cm copper wiring substrate having a thickness of 35 μm was polished by an 800 mesh steel brush to remove an oxide layer, it was washed with water, dried, and then the photosensitive solder resist ink compositions prepared in examples 1 to 5 and comparative example 1 were printed on the cleaned and dried wiring substrate by means of 36T screen printing, and the screen printing effect of the board surface was visually checked. Silkscreen was evaluated according to the following criteria.
◎, no screen printing on the board, no orange peel, white spot, shrinkage cavity, etc.;
○, screen printing on the board surface without orange peel, white dots, shrinkage cavity, etc.;
◇, screen printing on the board surface, slight orange peel, white spot, or shrinkage cavity;
△, the screen printing on the board surface causes a lot of orange peel, white spots, or shrinkage cavities.
Test example 2: photosensitivity
A sample was prepared in the same manner as in test example 1 above, and was dried in a hot air circulation type drying oven at 75 ℃ for 50 minutes. After drying, a 7kW metal halide lamp (AMBA7000, the same applies to below) was loadedThe exposure apparatus exposes it to light through a 21-step exposure ruler (Stouffer Value exposure ruler, model T2115), and then 1% Na at 30 deg.C2CO3The aqueous solution (mass concentration) of (2) was developed (spray pressure was 0.1MPa) for 60 seconds. The Stouffer Value is recorded.
Test example 3: PCT resistance
A sample was prepared in the same manner as in test example 1 above, and was dried in a hot air circulation type drying oven at 75 ℃ for 50 minutes. After drying, the film was post-exposed with a self-designed special test film cover using an exposure apparatus loaded with a 7kW metal halide lamp, and then covered with 1% Na at 30 ℃2CO3After the aqueous solution (mass concentration) of (c) was developed (spraying pressure was 0.1MPa) for 60 seconds, the prepared sample was placed in a constant temperature oven at 150 ℃ and baked for 1 hour, and the test board was prepared. The test board was placed in a HAST test chamber (available from Japan, HIRAYAMA PC-R8) and tested for high temperature and high humidity resistance at 121 ℃ under an environment of 100% relative humidity for 96 hours under a pressure of 0.2 MPa. After the test was completed, the surface condition was visually inspected with a 10-fold mirror, and then the peel property was tested with 3M tape (purchased from 3M company, model 3M600, the same below). PCT resistance was evaluated according to the following criteria.
◎, no bubble, no peeling and no falling off in 10 times of microscopic examination, and no oil drop after 3M adhesive tape is pulled;
○ No blister, No peeling after 10 times of microscopic examination, but slight oil loss after 3M tape pulling;
◇, a small amount of bubbles, peeling or falling off is detected by 10 times of microscopic examination, and a large area of oil is removed after the 3M adhesive tape is pulled;
△ there was a large amount of blisters, peeling, or flaking after 10 times microscopic examination, and a large area of oil was lost after 3M tape was pulled.
Test example 4: TCT resistance
Test boards were prepared in the same manner as in test example 3 above, and the test boards were placed in a high and low temperature cycling test chamber (purchased from Weiss-Votch 7012S2, germany) to test TCT resistance. After the test was completed, the board surface was visually inspected with a 10-fold mirror. PCT resistance was evaluated according to the following criteria.
◎ No bubbling, peeling and falling after 1000 cycles;
○, little bubbling, peeling and no shedding appear after 1000 cycles;
◇, after 1000 cycles, a large amount of bubbling, peeling or a small amount of peeling occurs;
△ A lot of blistering, peeling, or flaking occurred after 1000 cycles.
Test example 5: heat resistance
A test board prepared in the same manner as in test example 2 above was coated with a rosin flux, and then immersed in a tin bath at 260 c for 10 seconds, taken out, washed with propylene glycol methyl ether acetate and dried, and then subjected to a peeling test with a 3M adhesive tape. The heat resistance was evaluated according to the following criteria.
◎, no bubbling, peeling or falling off after soaking tin for 4 times;
○ bubbling, peeling or falling off after soaking tin for 4 times;
◇ bubbling, peeling or falling off after 3 times of tin immersion;
△ blistering, peeling or shedding occurs after 2 times of tin immersion.
Test example 6: adhesion force
The test board prepared in the same manner as in test example 2 above was heated at 160 ℃ for 2 hours, and then the adhesion was tested by the cross-cut tape method (IPC-TM-6502.4.28.1). The adhesion was evaluated based on the number of cells from which the ink completely fell off in 100 cells, as follows.
◎: 100/100, namely all the lattices do not fall off;
○: 98/100, namely, the ink in 2 of 100 grids falls off;
◇: 95/100, namely 5 of 100 lattices in which the ink falls off;
△: 90/100, namely 10 or more cells in 100 cells are dropped off.
Test example 7: solvent resistance
The test panel prepared in the same manner as in test example 2 above was immersed in propylene glycol methyl ether acetate for 30 minutes, taken out, washed with water and dried. Peel tests were then performed using 3M tape. The solvent resistance was evaluated according to the following criteria.
◎, no bubbling, peeling, or flaking off of the ink at all;
○ little bubbling, no peeling off of the ink;
◇, the ink has little bubbling, stripping and even falling off;
△, the ink fell off in large quantities.
Test example 8: acid resistance
Test panels prepared in the same manner as in test example 2 above were immersed in 10 vol% H at room temperature2SO4After 30 minutes in aqueous solution, it was taken out, washed with water and dried. Peel tests were then performed with 3M tape. Acid resistance was evaluated according to the following criteria.
◎, no bubbling, peeling or even dropping of the ink occurs at all;
○ little bubbling, no peeling off of the ink;
◇, little bubbling, peeling and even falling off of the ink;
△, a large amount of ink drop occurred.
Test example 9: pencil hardness (refer to ASTM D3363 Pencil hardness test)
On a test specimen prepared in the same manner as in test example 2 described above, a 6H pencil ground flat with the tip of the refill was placed in a standard hardness test carriage and pushed flat at an angle of 45 ° to measure the pencil hardness of the coating film. The coating film hardness was evaluated according to the following criteria.
◎, no scratch;
○, heavy scratch;
◇, slight scratch;
△ exposing copper.
TABLE 2 test results
As can be seen from the results in table 2, the photosensitive solder resist ink composition of the present invention is used in the examples of the present invention, so that the screen printing property of the solder resist ink is improved and the PCT resistance and TCT resistance of the PCB prepared by the present invention are significantly improved without affecting other properties as compared to the comparative examples.
Claims (10)
1. A photosensitive solder resist ink composition comprising:
(A) a photosensitive resin containing both a carboxyl group and at least two ethylenically unsaturated bonds in a molecule, and the following components based on 100 parts by weight of the photosensitive resin:
(B)1 to 40 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight of a photoinitiator,
(C)0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight of an organic surface auxiliary,
(D)2 to 200 parts by weight, preferably 5 to 100 parts by weight, more preferably 8 to 60 parts by weight of a diluent,
(E)3 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 10 to 50 parts by weight of a thermosetting component,
(F)1 to 50 parts by weight, preferably 2 to 40 parts by weight, more preferably 5 to 20 parts by weight of a photopolymerizable monomer, and
(G)20 to 150 parts by weight, preferably 50 to 120 parts by weight, more preferably 60 to 110 parts by weight of an inorganic filler;
wherein the inorganic filler (G) comprises an inorganic filler having a reactive functional group on the surface thereof in an amount of 20 to 150 parts by weight, preferably 50 to 120 parts by weight, more preferably 60 to 110 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (A).
2. The photosensitive solder resist ink composition according to claim 1, wherein the photosensitive resin (a) is prepared by any one of the following methods:
(1) subjecting a polyfunctional epoxy compound (a) having two or more epoxy groups in the molecule to an esterification reaction with an unsaturated monocarboxylic acid (b), and then reacting the resultant esterified product with a saturated or unsaturated polybasic acid anhydride (c);
(2) reacting (meth) acrylic acid with other comonomer (d) having an ethylenically unsaturated bond to form a copolymer, and then reacting a part of the resulting copolymer with glycidyl (meth) acrylate;
(3) reacting a copolymer of glycidyl (meth) acrylate and other comonomer (d) having an ethylenically unsaturated bond with an unsaturated monocarboxylic acid (b), and then reacting the resulting reaction product with a saturated or unsaturated polybasic acid anhydride (c);
(4) reacting a polyfunctional epoxy compound (a) having two or more epoxy groups in the molecule, an unsaturated monocarboxylic acid (b), and a compound (e) having at least two hydroxyl groups in the molecule and having one other group reactive with an epoxy group to obtain an intermediate (I), and then reacting the intermediate (I) with a saturated or unsaturated polybasic acid anhydride (c);
(5) reacting an unsaturated polybasic acid anhydride and an aromatic hydrocarbon having a vinyl group to form a copolymer, and then reacting the resulting copolymer with a hydroxyalkyl (meth) acrylate; or
(6) Reacting the intermediate (I) obtained in the method (4) with a saturated or unsaturated polybasic acid anhydride (c) and an unsaturated group-containing monoisocyanate (f).
3. The photosensitive resist ink composition according to claim 1, wherein the solid content of the photosensitive resin (a) has an acid value of 40 to 160mgKOH/g, preferably 50 to 120mgKOH/g, more preferably 60 to 100 mgKOH/g.
4. The photosensitive solder resist ink composition according to claim 1, wherein the weight ratio of the reactive functional group in the inorganic filler having a reactive functional group on the surface to the photosensitive resin (a) is 1:130-50000, preferably 1:300-40000, more preferably 1:1000-30000, still more preferably 1:10000-25000, most preferably 1: 11000-23000.
5. The photosensitive solder resist ink composition according to any one of claims 1 to 4, wherein the inorganic filler (G) and the precursor of the inorganic filler having a reactive functional group on the surface are barium sulfate, barium titanate, calcium dioxide, talc, fumed silica, clay, magnesium carbonate, calcium carbonate, alumina, titanium oxide, mica powder, kaolin, preferably barium sulfate, silica, alumina, calcium carbonate or a mixture thereof.
6. The photosensitive solder resist ink composition of any one of claims 1 to 4, the reactive functional group being an epoxy group, an ethylenically unsaturated bond, an amino group, a carboxyl group, a hydroxyl group, a thiol group, or a combination of two or more thereof, preferably an epoxy group, an ethylenically unsaturated bond, a hydroxyl group.
7. The photosensitive solder resist ink composition according to any one of claims 1 to 4, the inorganic filler having a reactive functional group on the surface is silica having an ethylenically unsaturated bond (preferably vinyl) on the surface.
8. The photosensitive solder resist ink composition according to any one of claims 1 to 4, further comprising one or more additives selected from the group consisting of: epoxy resin curing accelerator, pigment and adhesion promoter.
9. Use of the photosensitive solder resist ink composition according to any one of claims 1 to 8 for the preparation of printed circuit boards.
10. A wiring board comprising a cured film formed from the photosensitive solder resist ink composition described in any one of claims 1 to 8.
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| CN112680018A (en) * | 2020-12-14 | 2021-04-20 | 江西沃格光电股份有限公司 | Diluent for printing minified backlight solder resist ink and application thereof |
| CN113527945A (en) * | 2020-04-22 | 2021-10-22 | 三星显示有限公司 | Light emitting element ink and method of manufacturing display device |
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