CN112940560B - Photosensitive solder resist ink composition, use thereof and circuit board containing same - Google Patents
Photosensitive solder resist ink composition, use thereof and circuit board containing same Download PDFInfo
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- CN112940560B CN112940560B CN202110138344.9A CN202110138344A CN112940560B CN 112940560 B CN112940560 B CN 112940560B CN 202110138344 A CN202110138344 A CN 202110138344A CN 112940560 B CN112940560 B CN 112940560B
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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
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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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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- 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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- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention relates to a photosensitive solder resist ink composition, which comprises the following components: (A) A photosensitive resin having 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 of photoinitiator, (C) 0.1 to 20 parts by weight of surface auxiliary agent, (D) 2 to 200 parts by weight of diluent, (E) 1 to 50 parts by weight of photopolymerizable monomer, (F) 3 to 100 parts by weight of thermosetting component, and (G) 20 to 150 parts by weight of inorganic filler; wherein the photopolymerizable monomer (E) comprises a polyfunctional unsaturated monomer modified with a flexible group C 1‑8 Alkoxy or epsilon-caprolactone; the thermosetting component (F) contains a polyfunctional epoxy compound having a core of a rigid compound, which is a polycyclic aromatic compound. The invention also relates to the use of the ink composition for preparing printed circuit boards and to circuit boards comprising the same.
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
With the development of automobile electronization and the upgrade of new energy automobile electronic control systems, printed Circuit Boards (PCBs) must have high reliability as carriers for electronic component integration, so as to ensure that quality problems cannot occur in the use process for decades. Therefore, the solder resist curing film is required to have better tolerance to different external environments (temperature, humidity, illumination and the like) as a permanent protective coating of the circuit board, so as to improve the aging resistance of the circuit board, thereby greatly prolonging the service life of the circuit board. For a circuit board applied to automobile electronics, high reliability is the most critical performance requirement, a TCT (Temperature Cycle Test) is taken as an important Test method (IPC-TM-650.6.6) of an accelerated aging life Test and is widely applied to the high-performance circuit board industry, and environmental changes which may occur in the use process of 20 years in the future are simulated through the high-low Temperature Cycle Test under extreme environmental conditions.
However, the photosensitive solder resist ink in the market generally has poor performance in high and low temperature cycle resistance, and can not meet the performance requirements of safety components in automotive electronics on high-performance PCBs. Specifically, in the high and low temperature resistance cycle test process, the solder mask often cracks, peels off, even falls off and the like after a certain number of cycles, and finally the circuit board fails.
In general, a certain amount of polyfunctional unsaturated monomer and polyfunctional epoxy resin are added to photosensitive solder resist ink as a crosslinking curing component for photo-curing and thermal curing to improve all aspects of photosensitivity, adhesion, hardness, chemical resistance and electrical properties of the photosensitive solder resist ink. After research, the inventor finds that the solder mask is easy to crack, peel and even fall off after rapid thermal expansion and cold contraction in the process of high-low temperature circulation in a large temperature difference range of the common solder mask ink.
In order to solve the above problems, patent application CN104380197A suppresses the generation of cracks during TCT by adding a thermoplastic. Patent application CN104392950A discloses a method for improving the resistance to high and low temperature cycles by adding block copolymers.
The inventors have conducted extensive experiments to verify that the addition of thermoplastic resins, such as rubber-modified bisphenol a epoxy resins (see, for example, patent application CN 104380197A) or block copolymers (see, for example, patent application CN 104392950A) only improves the high and low temperature cycle resistance in a relatively low temperature range (e.g., -40 ℃ to 85 ℃, or-40 ℃ to 125 ℃), and when the high temperature requirements are further increased (e.g., -40 ℃ to 140 ℃), these new methods still have difficulty in meeting the cracking resistance requirements in a larger temperature range. The increase of the high and low temperature range endured by the curing film formed by the photosensitive solder resist ink can not only obviously improve the service life of the curing film, but also increase the application range of the curing film, such as the application in the field of automobile transmission system control and power system control.
Therefore, it is desirable to provide a photosensitive solder resist ink that overcomes the disadvantages of the prior art, and can greatly improve the high and low temperature cycle resistance without reducing other properties of the ink when applied to printed circuit boards with higher temperature requirements.
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 having 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 a surface auxiliary,
(D) 2 to 200 parts by weight, preferably 5 to 100 parts by weight, more preferably 6 to 60 parts by weight of a diluent,
(E) 1 to 50 parts by weight, preferably 2 to 45 parts by weight, more preferably 5 to 40 parts by weight of a photopolymerizable monomer,
(F) 3 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 8 to 60 parts by weight of a thermosetting component, 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 photopolymerizable monomer (E) comprises a polyfunctional unsaturated monomer modified with a flexible group C 1-8 Alkoxy, preferably C 2-6 Alkoxy, more preferably C 2-4 Alkoxy, such as methoxy, ethoxy, propoxy, or epsilon-caprolactone;the thermosetting component (F) contains a polyfunctional epoxy compound having a core of a rigid compound which is a polycyclic aromatic compound, preferably a trisphenolmethane, an anthracene, a tetraphenolethane or a naphthalene.
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 screen printing property, photosensitivity, heat resistance, adhesion, solvent resistance, acid resistance, hardness and the like, and can remarkably improve the high and low temperature cycle resistance.
Detailed Description
In the present invention, all operations were carried out at room temperature (25 ℃ C.) and normal pressure (101 KPa), 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) with tetrahydrofuran as eluent (German standard DIN 55672-1, 2007 Gel Permeation Chromatography (GPC) part 1: tetrahydrofuran (THF) as elution solvent). The epoxy equivalent is determined according to the national standard GB/T46122008. The softening point of the solid epoxy resin was determined according to GB/T12007.6-1989.
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 a surface auxiliary,
(D) 2 to 200 parts by weight, preferably 5 to 100 parts by weight, more preferably 6 to 60 parts by weight of a diluent,
(E) 1 to 50 parts by weight, preferably 2 to 45 parts by weight, more preferably 5 to 40 parts by weight of a photopolymerizable monomer,
(F) 3 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 8 to 60 parts by weight of a thermosetting component, 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 photopolymerizable monomer (E) comprises a polyfunctional unsaturated monomer modified with a flexible group C 1-8 Alkoxy, preferably C 2-6 Alkoxy, more preferably C 2-4 Alkoxy, such as methoxy, ethoxy, propoxy, or epsilon-caprolactone; the thermosetting component (F) contains a polyfunctional epoxy compound having a core of a rigid compound, which is a polycyclic aromatic compound, preferably trisphenolmethane, anthracene, tetraphenolethane or naphthalene.
In a preferred embodiment, the polyfunctional unsaturated monomer is understood to be a monomer comprising a plurality of unsaturated functional groups, for example from 2 to 10, preferably from 2 to 8, more preferably from 2 to 6 unsaturated functional groups per molecule, for example unsaturated double bonds. Thus, in a preferred embodiment, the polyfunctional unsaturated monomer is an unsaturated monomer comprising 2, 3, 4,5 or 6 double bonds in one molecule. In a preferred embodiment, the multifunctional unsaturated monomer is a (meth) acrylate monomer.
In a preferred embodiment, in the molecular structure of the polyfunctional unsaturated monomer modified with a flexible group, particularly (meth) acrylates, the flexible group is preferably introduced in an equivalent amount of 1 to 20, more preferably 2 to 10, and in view of properties in terms of viscosity, reactivity, and the like, the flexible group is preferably introduced in an equivalent amount of 2 to 8, preferably 3 to 6.
In a preferred embodiment, the viscosity of the flexible group-modified polyfunctional unsaturated monomer is from 100 to 5000mpa.s, preferably from 200 to 4000mpa.s, still preferably from 300 to 3000mpa.s, still more preferably from 500 to 2500mpa.s, most preferably from 900 to 2000mpa.s.
In a preferred embodiment, in the photosensitive solder resist ink composition, the polyfunctional unsaturated monomer modified with a flexibilizing group may be an ethoxylated polyfunctional (meth) acrylate selected from the group consisting of ethoxylated pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate ethoxylated bisphenol a bis (meth) acrylate, commercially available as exemplified by: xingxing EM2380, EM2411, japanese chemical PEG400DA, R-551, R-712, GPO-303, THE-330, dismann AgiSyn 2844, agiSyn 2844; propoxylated multifunctional acrylates selected from glycerol propoxylate tri (meth) acrylate and propoxylated trimethylolpropane tri (meth) acrylate, commercially available as exemplified by: TPA-330 of Japan chemical drugs, SR-9020NS of Saedoma USA; commercially available epsilon-caprolactone-modified (meth) acrylates include: r-167, HX-220, HX-620, DPCA-20, DPCA-30, DPCA-60, DPCA-120 of Japanese chemilla. The above photopolymerizable monomers may be used alone or in the form of a mixture thereof.
In a preferred embodiment, the polyfunctional unsaturated monomer modified with a flexible group is epsilon-caprolactone-modified (meth) acrylate, particularly epsilon-caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the commercially available products are, for example, DPCA-20, DPCA-30, DPCA-40, DPCA-60, DPCA-120 of japanese chemists, which are different in the introduced equivalent of epsilon-caprolactone of the DPHA molecule. Most preferred is DPCA-60 in which the introduced equivalent weight of epsilon-caprolactone in a molecule of dipentaerythritol hexaacrylate (DPHA) is 6, corresponding to 6 molecules of epsilon-caprolactone introduced in 1 molecule of DPHA. The specific preparation method is known, for example, from "improvement of synthesis process of epsilon-caprolactone modified dipentaerythritol hexaacrylate" of wangjiao Jiaojiao.
In the context of the present invention, the polyfunctional epoxide compounds with a core of a rigid compound can be difunctional to hexafunctional epoxides, preferably difunctional to tetrafunctional epoxides, such as difunctional, trifunctional and tetrafunctional epoxides.
In a preferred embodiment of the invention, the relative molecular weight of the polyfunctional epoxy compound with the rigid compound as core may be in the range from 100 to 3000g/mol, preferably in the range from 150 to 2000g/mol, more preferably in the range from 200 to 1500g/mol, most preferably in the range from 250 to 1000g/mol.
In a preferred embodiment of the present invention, the softening point of the polyfunctional epoxy compound having a core of a rigid compound may be 50 to 200 ℃, preferably 50 to 170 ℃, more preferably 55 to 150 ℃, and most preferably 55 to 120 ℃.
In a preferred embodiment of the present invention, the epoxy equivalent of the rigid compound-cored polyfunctional epoxy compound may be 10 to 600 g/equivalent, preferably 30 to 500 g/equivalent, more preferably 50 to 400 g/equivalent, still more preferably 60 to 300 g/equivalent, and most preferably 80 to 200 g/equivalent.
In the context of the present invention, polyfunctional epoxides which are based on rigid compounds, such as trisphenolmethane, anthracene, tetraphenolethane or naphthalene, are understood to mean epoxides which are derived from rigid compounds which are commercially available or are prepared in a manner known to the person skilled in the art.
In a preferred embodiment, the polyfunctional epoxy compound with the rigid compound as core is selected from: triphenoylmethane-type structures (examples are triphenolmethanetriglycidyl ethers such as TPNE-5501, EPPN-501H, EPPN-501HY, EPPN-502H, SQTN-331 of Shandong holy, EPPN-5501L, and EPPN-5501, which are commercially available), anthracene-type structures (examples are anthracene-type bifunctional epoxy resins such as YX-8800, which are commercially available), tetraphenolethane-type structures (examples are tetraphenolethane tetraglycidyl ethers), naphthalene-type structures (examples are naphthalene-type tetrafunctional epoxy resins such as HP-4700, HP-4710, NC-00L, NC-737000L, alloda TACTIX-742, MY-720, which are commercially available from Japanese DIC),
the above epoxy compounds may be used alone or in the form of a mixture thereof.
In a preferred embodiment, the weight ratio of the flexible group-modified polyfunctional unsaturated monomer to the rigid compound-cored polyfunctional epoxy compound may be from 0.01 to 4.
In a most preferred embodiment, the polyfunctional unsaturated monomer modified with a flexible group is an epsilon-caprolactone-modified (meth) acrylate, the polyfunctional epoxide with a core of a rigid compound is a polyfunctional epoxide compound having a core of triphenolylmethane, and the weight ratio of the polyfunctional unsaturated monomer modified with a flexible group to the polyfunctional epoxide with a core of a rigid compound may be from 0.01 to 4, preferably from 0.05 to 3, more preferably from 0.1 to 2, most preferably from 0.15 to 1.5.
In another preferred embodiment of the invention, the epsilon caprolactone-modified (meth) acrylate is epsilon caprolactone-modified dipentaerythritol hexa (meth) acrylate and the polyfunctional epoxy compound having a triphenolmethane core is a triphenolmethane triglycidyl ether, preferably they are used in a weight ratio of from 0.01 to 4, preferably from 0.05 to 3, more preferably from 0.1 to 2, most preferably from 0.15 to 1.5, especially preferably from 0.15 to 1.
It has been unexpectedly found that when the photopolymerizable monomer (E) of the present invention is used together with the thermosetting component (F), a printed wiring board having a higher temperature requirement can be satisfied, and the high and low temperature cycle resistance can be greatly improved without lowering other properties of the ink.
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 a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a hydrogenated bisphenol a type epoxy resin, a novolak type epoxy resin, a cresol novolak type epoxy resin, a novolak type epoxy resin, a diphenol type epoxy resin, a bixylenol type epoxy resin, a triphenol methane type epoxy resin, and an N-glycidyl type epoxy resin. When using a novolak epoxy resin, a cresol novolak epoxy resin and a novolak epoxy resin of bisphenol A, 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 novolak epoxy resins of bisphenol A are preferably used. The polyfunctional epoxy compounds 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) acrylic ester having one hydroxyl group in the molecule or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated monoglycidyl compound. Acrylic acid or methacrylic acid is preferable in view of photocurability.
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 saturated or unsaturated polybasic acid anhydride (c) is used in an amount 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 solid component of the reaction product has an acid value of less than 40mgKOH/g, the photosensitive solder resist ink composition has poor 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 processes (2) and (3) may be styrene, chlorostyrene, α -methylstyrene; acrylic or methacrylic esters substituted by 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; monoacrylates or monomethacrylates of polyethylene glycol, or monoacrylates or monomethacrylates of polypropylene glycol; vinyl acetate, vinyl butyrate or vinyl benzoate; acrylamide, methacrylamide, N-hydroxymethyl acrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, N-butoxymethyl acrylamide, acrylonitrile, maleic anhydride, or the like. The other comonomers having ethylenic unsaturation can be used alone or in mixtures thereof.
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.
Photoinitiator (B)
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 and the like; 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-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-pentylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, ethyl-2, 4, 6-trimethylbenzoyl phenylphosphine oxide and the like; 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).
Surface auxiliary agent (C)
According to an embodiment of the present invention, in the photosensitive solder resist ink composition, the 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, DEUCHEM 6500, 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).
Diluent (D)
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 6 to 60 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (a).
Photopolymerizable monomer (E)
According to one embodiment of the present invention, the ink composition of the present invention comprises the photopolymerizable monomer described above. The photopolymerizable monomer (E) may also comprise other photopolymerizable monomers conventionally used in the art, such as hydroxyl group-containing (meth) acrylates of hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like; monofunctional (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and lauryl (meth) acrylate; difunctional (meth) acrylates such as 1, 6-hexanediol bis (meth) acrylate, dipropylene glycol bis (meth) acrylate, diethylene glycol bis (meth) acrylate, neopentyl glycol diethoxy/propoxy bis (meth) acrylate, and the like; polyfunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These photopolymerizable monomers may be used alone or in the form of a mixture thereof.
In a preferred embodiment of the present invention, in the photosensitive solder resist ink composition of the present invention, no other photopolymerizable monomer is used, in other words, only the photopolymerizable monomer of the present invention (i.e., polyfunctional unsaturated monomer modified with a flexible group) is used.
In a preferred embodiment of the present invention, the content of the photopolymerizable monomer (E) may be 1 to 50 parts by weight, preferably 2 to 45 parts by weight, more preferably 5 to 40 parts by weight, most preferably 8 to 25 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin (a).
Thermosetting component (F)
According to one embodiment of the present invention, the ink composition of the present invention comprises the thermosetting component described above. The thermosetting component (F) may also contain other thermosetting components commonly used in the art, such as epoxy compounds 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. A commercially available dicyclopentadiene type epoxy resin is described as JP chemical XD-1000.
In a preferred embodiment of the present invention, in the photosensitive solder resist ink composition of the present invention, no other thermosetting component is used, in other words, only the thermosetting component of the present invention (i.e., the polyfunctional epoxy compound having a core of a rigid compound) is used.
In a preferred embodiment of the present invention, the content of the thermosetting component (F) may be 3 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 6 to 60 parts by weight, still more preferably 8 to 60 parts by weight, most preferably 35 to 55 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 weight relationship among the photopolymerizable monomer (m), the photosensitive resin (n), and the thermosetting component (q) satisfies the following relationship:
0.10≤m/[nq/(n+q)]≤2.0；
preference is given to
0.15≤m/[nq/(n+q)]≤1.5；
More preferably
0.20≤m/[nq/(n+q)]≤1.0；
Most preferably
0.25≤m/[nq/(n+q)]≤0.8。
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).
In the present invention, the particle diameter of the inorganic filler may be 0.001 to 30 μm, preferably 0.05 to 20 μm, more preferably 0.1 to 10 μm, still more preferably 0.1 to 5 μm.
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 2P4MHZ; U-CAT3503N, U-CAT3502T, and bicyclic amidine compounds and salts thereof DBU, DBN, U-CATA SA102, U-CAT5002, and the like, which are manufactured by SAN-APRO. 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 D 50 May 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 rock titanium white powder 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 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 L6989F, green L8690 P.G7, etc. 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 lowering viscosity, ease of handling), however, only a component containing no solvent is usually considered when, for example, calculation of material ratio, measurement of acid value, and the like are 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, the inventors believe that the ink composition of the present invention may achieve the described benefits for the following reasons: the multifunctional epoxy compound with the rigid compound as the core can greatly improve the glass transition temperature of the solder resist ink, thereby reducing the CTE (coefficient of thermal expansion) of an ink curing film, namely greatly reducing the CTE difference between the ink curing film and an epoxy resin substrate and a copper circuit on a PCB (printed circuit board), further reducing stress concentration during shrinkage and improving the cracking resistance. Compared with the traditional multifunctional unsaturated monomer, the multifunctional unsaturated monomer modified by the flexible group can ensure photosensitivity and improve the tensile toughness of the ink curing film, namely the tensile strength of the ink curing film during shrinkage is greatly improved. The comprehensive use of the two can ensure that the final solder resist ink curing film can meet the high and low temperature cyclic cracking resistance under the condition of higher temperature.
Furthermore, the invention relates to the use of the photosensitive solder resist ink composition for the preparation of printed circuit boards.
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 ℃. Then selectively exposing, developing in dilute alkali solution, further curing in an oven at 130-180 deg.c to form the circuit board of the present invention.
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.
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, N 2 In 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. After complete dissolution, the temperature is reduced to 90 ℃, then 72g of acrylic acid and 1g of triphenyl phosphine are dripped, the temperature is controlled to be 95 ℃ in the dripping process, the temperature is increased to be 105 ℃ after the dripping is finished, the reaction is carried out for 12 hours at the temperature, the reactant is measured, the acid value is 0.8mgKOH/g, the temperature of the reactant is reduced to be 60 ℃, then 75g of tetrahydrophthalic anhydride is added, and the heat preservation is carried out for 3 hours at 90 ℃. 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 6 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 (Qikeu 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 Fine analyzer (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 gauge) 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 BASF
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: barium sulfate, B-30 from Sakai chemical
Note 9: diluent, diethylene glycol Ether acetate, available from Dow chemical USA
Note 10: thermosetting component, trisphenol-based methane epoxy resin, having softening point of 60-72 deg.C, obtained from SQTN-331 of Shandong-Shengquan group
Note 11: thermosetting component, bisphenol A epoxy resin, available from south Asia resin works E-51
Note 12: photopolymerizable monomer, ε -caprolactone-modified DPHA, viscosity 1250mPa.s, available from Nippon chemical Co., ltd, DPCA-60
Note 13: photopolymerizable monomer, viscosity 6500mPa.s, available from Hakken EM263
Test examples
The photosensitive solder resist ink compositions prepared in examples 1 to 6 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 x10 cm copper wiring substrate with a thickness of 35 μm was polished by an 800 mesh steel brush to remove an oxide layer, the substrate was washed with water and dried, and then the photosensitive solder resist ink compositions prepared in examples 1 to 6 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.
Very good: the plate surface has no screen printing, and has no adverse phenomena of orange peel, white dots, shrinkage cavity and the like;
o: the plate surface is printed with a screen, and the adverse phenomena of orange peel, white dots, shrinkage cavities and the like do not exist;
o: the plate surface is printed with a screen, and has the bad phenomena of slight orange peel, white spots, shrinkage cavity and the like;
and (delta): the plate surface is printed with a screen, and a large amount of orange peel, white spots, shrinkage cavities and other adverse phenomena appear.
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, an exposure apparatus loaded with a 7kW metal halide lamp (AMBA 7000, the same applies hereinafter) was used to expose the substrate at 300mJ/cm through a 21-step exposure ruler (Stouffer Value exposure ruler, model T2115) 2 Exposing it to energy, then 1% Na at 30 ℃ 2 CO 3 The aqueous solution (mass concentration) of (2) was developed (spray pressure was 0.1 MPa) for 60 seconds. The Stouffer Value is recorded.
Test example 3: TCT resistance
Test boards were prepared in the same manner as in test example 2 above, and the test boards were placed in a high-low temperature cycle test chamber (purchased from Weiss-Votch 7012S2, germany) to test TCT resistance. And (3) testing conditions are as follows: the cracking resistance was tested in a cycle of 30 minutes at low temperature (-40 ℃) and then rapidly switched (within 10 seconds) to a high temperature cabinet (140 ℃) for 30 minutes. After the test was completed, the condition of the board surface was visually checked with a 10-fold mirror. TCT resistance was evaluated according to the following criteria.
Very good: no cracking, no foaming and no peeling after 1000 cycles;
o: no cracking, peeling or falling after 750 times of circulation, and cracking, peeling or falling after 1000 times of circulation;
o: after 500 cycles, no cracking, peeling or falling off occurs, and after 750 cycles, cracking, peeling or falling off occurs;
and (delta): cracking, peeling, or peeling occurred after 500 cycles.
Test example 4: heat resistance
A test board prepared in the same manner as in test example 2 above was coated with a rosin flux, then immersed in a tin bath at 260 ℃ for 10 seconds, taken out, allowed to stand to room temperature, 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.
Very good: bubbling, stripping or falling does not occur after 3 times of tin immersion;
o: bubbling, peeling or falling off occurs after 3 times of tin immersion, and bubbling, peeling or falling off does not occur after 2 times of tin immersion;
o: bubbling, peeling or falling off occurs after tin immersion for 2 times, and bubbling, peeling or falling off does not occur after tin immersion for 1 time;
and (delta): bubbling, peeling or peeling occurred 1 time after tin immersion.
Test example 5: 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-650.4.28.1). The adhesion was evaluated based on the ratio of the ink drop area in 100 cells to the area of the cell, as follows.
Very good: all the lattices do not fall off, and the falling-off proportion is less than 10 percent;
o: all the lattices do not fall off, and the falling-off proportion is between 10 and 30 percent;
o: all the lattices do not fall off, and the falling-off proportion is between 30 and 80 percent;
and (delta): ink completely fell off in 1 or more of the 100 cells.
Test example 6: 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 testing was then performed using 3M tape. The solvent resistance was evaluated according to the following criteria.
Very good: the ink is not foamed, peeled or peeled off completely;
o: the ink has little bubbling, no peeling and no falling off;
o: the ink is slightly foamed, peeled and even dropped;
and (delta): a large amount of ink fell off.
Test example 7: acid resistance
Test panels prepared in the same manner as in test example 2 above were immersed in 10 vol% H at room temperature 2 SO 4 After 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.
Excellent: the ink does not generate bubbling, peeling or even falling completely;
o: the ink has little bubbling, no peeling and no falling off;
o: a small amount of foaming, stripping and even falling off of the printing ink occur;
and (delta): the ink was largely peeled off.
Test example 8: pencil hardness (refer to ASTM D3363 Pencil hardness test)
On a test specimen prepared in the same manner as in the above test example 2, a 6H pencil ground flat with the nib of the pencil lead was put into a standard hardness test cart and pushed flat at an angle of 45 ° to measure the pencil hardness of the coated film. The coating film hardness was evaluated according to the following criteria.
Very good: no scratch is generated;
o: slight scratch is formed;
o: a heavy scratch is formed;
and (delta): and (4) exposing copper.
TABLE 2 test results
As is clear from the results in table 2, the examples of the present invention using the photosensitive solder resist ink composition of the present invention have not only good screen printability, photosensitivity, heat resistance, adhesion, solvent resistance, acid resistance, hardness, but also good TCT resistance as compared with the comparative examples.
Claims (29)
1. A photosensitive solder resist ink composition comprising:
(A) A photosensitive resin having 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 of a photoinitiator,
(C) 0.1 to 20 parts by weight of a surface auxiliary,
(D) 2 to 200 parts by weight of a diluent,
(E) 8 to 25 parts by weight of a photopolymerizable monomer,
(F) 35 to 55 parts by weight of a thermosetting component, and
(G) 20-150 parts by weight of an inorganic filler;
wherein the photopolymerizable monomer (E) is a polyfunctional unsaturated monomer modified with a flexible group, and the flexible group is epsilon-caprolactone; the thermosetting component (F) is a polyfunctional epoxy compound having a core of a rigid compound, and the rigid compound is triphenolmethane;
wherein the multifunctional unsaturated monomer modified by the flexible group is epsilon-caprolactone modified (methyl) acrylate, and the multifunctional epoxy compound taking the rigid compound as the core is a multifunctional epoxy compound taking triphenolylmethane as the core.
2. The photosensitive solder resist ink composition of claim 1, wherein the composition comprises 5 to 30 parts by weight of a photoinitiator based on 100 parts by weight of the photosensitive resin.
3. The photosensitive solder resist ink composition of claim 2, wherein the composition comprises 10 to 25 parts by weight of the photoinitiator based on 100 parts by weight of the photosensitive resin.
4. The photosensitive solder resist ink composition according to claim 1 or 2, wherein the composition comprises 1 to 15 parts by weight of the surface assistant based on 100 parts by weight of the photosensitive resin.
5. The photosensitive solder resist ink composition of claim 4, wherein the composition comprises 2 to 10 parts by weight of the surface assistant based on 100 parts by weight of the photosensitive resin.
6. The photosensitive solder resist ink composition according to claim 1 or 2, wherein the composition comprises 5 to 100 parts by weight of the diluent based on 100 parts by weight of the photosensitive resin.
7. The photosensitive solder resist ink composition of claim 6, wherein the composition comprises 6 to 60 parts by weight of the diluent based on 100 parts by weight of the photosensitive resin.
8. The photosensitive solder resist ink composition according to claim 1 or 2, wherein the composition comprises 50 to 120 parts by weight of the inorganic filler based on 100 parts by weight of the photosensitive resin.
9. The photosensitive solder resist ink composition of claim 8, wherein the composition comprises 60 to 110 parts by weight of the inorganic filler based on 100 parts by weight of the photosensitive resin.
10. The photosensitive solder resist ink composition of claim 1 or 2, wherein the polyfunctional unsaturated monomer modified with a flexible group is e-caprolactone modified dipentaerythritol hexa (meth) acrylate.
11. The photosensitive solder resist ink composition according to claim 1 or 2, wherein the viscosity of the polyfunctional unsaturated monomer modified with a flexible group is 100 to 5000 mpa.s.
12. The photosensitive solder resist ink composition of claim 11, wherein the viscosity of the polyfunctional unsaturated monomer modified with a flexible group is 200 to 4000 mpa.s.
13. The photosensitive solder resist ink composition of claim 12, wherein the viscosity of the polyfunctional unsaturated monomer modified with a flexible group is 300 to 3000 mpa.s.
14. The photosensitive solder resist ink composition of claim 13, wherein the viscosity of the multifunctional unsaturated monomer modified with a flexible group is 500-2500 mpa.s.
15. The photosensitive solder resist ink composition of claim 14, wherein the viscosity of the multifunctional unsaturated monomer modified with a flexible group is 900-2000mpa.s.
16. The photosensitive solder resist ink composition according to claim 1 or 2, wherein the weight ratio of the polyfunctional unsaturated monomer modified with a flexible group to the polyfunctional epoxy compound having a rigid compound as a core is from 0.01 to 4.
17. The photosensitive solder resist ink composition of claim 16, wherein the weight ratio of the flexible group-modified polyfunctional unsaturated monomer to the rigid compound-cored polyfunctional epoxy compound is from 0.05 to 3.
18. The photosensitive solder resist ink composition of claim 17, wherein the weight ratio of the flexible group-modified polyfunctional unsaturated monomer to the rigid compound-cored polyfunctional epoxy compound is from 0.1 to 2.
19. The photosensitive solder resist ink composition according to claim 18, wherein the weight ratio of the polyfunctional unsaturated monomer modified with a flexible group to the polyfunctional epoxy compound having a core of a rigid compound is 0.15 to 1.5.
20. The photosensitive solder resist ink composition of claim 19, wherein the weight ratio of the flexible group-modified polyfunctional unsaturated monomer to the rigid compound-cored polyfunctional epoxy compound is 0.15 to 1.
21. The photosensitive solder resist ink composition according to claim 1 or 2, wherein the epsilon-caprolactone-modified (meth) acrylate is epsilon-caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the polyfunctional epoxy compound having a triphenolmethane core is triphenolmethane triglycidyl ether.
22. The photosensitive solder resist ink composition according to claim 1 or 2, wherein the introduced equivalent of epsilon-caprolactone in the molecule of epsilon-caprolactone-modified dipentaerythritol hexa (meth) acrylate is 2 to 8.
23. The photosensitive solder resist ink composition of claim 22, wherein the incorporated equivalent of e-caprolactone in the molecule of e-caprolactone-modified dipentaerythritol hexa (meth) acrylate is from 3 to 6.
24. The photosensitive solder resist ink composition according to claim 1 or 2, wherein the weight relationship among the photopolymerizable monomer (m), the photosensitive resin (n), and the thermosetting component (q) satisfies the following relationship:0.10≤m/[nq/(n+q)]≤2.0。
25. according to claimThe photosensitive solder resist ink composition of claim 24, wherein the weight relationship among the photopolymerizable monomer (m), the photosensitive resin (n), and the thermosetting component (q) satisfies the following relationship:0.15≤m/[nq/(n+q)]≤1.5。
26. the photosensitive solder resist ink composition according to claim 25, wherein the weight relationship among the photopolymerizable monomer (m), the photosensitive resin (n), and the thermosetting component (q) satisfies the following relationship:0.20≤m/[nq/(n+q)]≤1.0。
27. the photosensitive solder resist ink composition according to claim 26, wherein the weight relationship among the photopolymerizable monomer (m), the photosensitive resin (n), and the thermosetting component (q) satisfies the following relationship:0.25≤m/[nq/(n+q)]≤0.8。
28. use of the photosensitive solder resist ink composition according to any one of claims 1 to 27 for the preparation of printed circuit boards.
29. A wiring board comprising a cured film formed from the photosensitive solder resist ink composition described in any one of claims 1 to 27.
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| KR101799845B1 (en) * | 2015-11-02 | 2017-11-22 | 고오 가가쿠고교 가부시키가이샤 | Photosensitive resin composition, dry film, and printed wiring board |
| CN106380929A (en) * | 2016-08-30 | 2017-02-08 | 江门市阪桥电子材料有限公司 | UV-cured liquid photosensitive solder resist soft board printing ink and preparation method thereof |
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