WO2017169166A1 - インクジェット用硬化性組成物、硬化物およびプリント配線板 - Google Patents
インクジェット用硬化性組成物、硬化物およびプリント配線板 Download PDFInfo
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- WO2017169166A1 WO2017169166A1 PCT/JP2017/004809 JP2017004809W WO2017169166A1 WO 2017169166 A1 WO2017169166 A1 WO 2017169166A1 JP 2017004809 W JP2017004809 W JP 2017004809W WO 2017169166 A1 WO2017169166 A1 WO 2017169166A1
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- acrylate
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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
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
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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
-
- 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
-
- 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
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
-
- 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
-
- 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
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/01—Tools for processing; Objects used during processing
- H05K2203/0104—Tools for processing; Objects used during processing for patterning or coating
- H05K2203/013—Inkjet printing, e.g. for printing insulating material or resist
Definitions
- the present invention relates to a curable composition for inkjet, a cured product using the same, and a printed wiring board.
- etching resist When forming an etching resist, solder resist, symbol marking, etc. on a printed wiring board, after applying a high-viscosity composition to the substrate by a printing method such as screen printing, the ink is applied by irradiation with active energy rays.
- the method of hardening was common.
- a method for forming the etching resist, solder resist, symbol marking and the like by an ink jet method instead of screen printing has been developed.
- the amount of ink used can be reduced, a screen printing plate is not required, and direct drawing from digital data is possible.
- the coating film of the curable composition applied by the inkjet method is easily affected by oxygen in the air. Therefore, the curability of the coating film surface at the time of curing by irradiation of active energy rays due to the influence of oxygen inhibition, etc., resulting in blurring in the pattern of the composition formed by the inkjet method, When the substrate is turned over, the stage of the ink jet apparatus may become dirty. On the other hand, in order to improve the surface curability of the coating film, if the integrated light quantity of the active energy ray is increased, the curability of the coating film surface is improved, but the blurring occurs similarly. Further, when the amount of the photopolymerization initiator is increased in order to improve the surface curability of the coating film, there is a problem that various properties such as solder heat resistance and gold plating resistance are deteriorated.
- the present invention effectively solves the above problems, and improves the surface curability when a coating film is formed by an ink jet method, and has characteristics such as solder heat resistance and gold plating resistance.
- An object of the present invention is to provide a curable composition for inkjet that does not decrease, a cured product using the composition, and a printed wiring board.
- the present inventors can obtain a composition suitable for ink jet printing using a bifunctional (meth) acrylate monomer having an alkylene chain, and an aminoalkylphenone.
- a bifunctional (meth) acrylate monomer having an alkylene chain and an aminoalkylphenone.
- By adjusting the absorbance in an appropriate range with a combination of a photopolymerization initiator and an acylphosphine oxide photopolymerization initiator it was found that good surface curability and coating film properties can be obtained.
- a curable composition for inkjet according to the present invention was obtained.
- the inkjet curable composition of the present invention comprises (A) a bifunctional (meth) acrylate compound having an alkylene chain, (B) an ⁇ -aminoalkylphenone photopolymerization initiator, and (C) an acylphosphine oxide photopolymer.
- a polymerization initiator having a film thickness of 10 ⁇ m, an absorbance at a wavelength of 365 nm of 0.08 to 0.8, and an absorbance at a wavelength of 385 nm of 0.05 to 0.3.
- the film thickness of 10 ⁇ m is the film thickness before light irradiation for curing.
- the alkylene chain of the bifunctional (meth) acrylate compound (A) having an alkylene chain preferably has 4 to 12 carbon atoms.
- the curable composition for inkjet of the present invention may further contain (D) a bisphenol type epoxy (meth) acrylate compound.
- the curable composition for inkjet of the present invention preferably has a viscosity at 50 ° C. of 50 mPa ⁇ s or less.
- the cured product of the present invention is characterized by being obtained by irradiating light to the above curable composition for inkjet.
- the printed wiring board of the present invention is characterized in that the above-mentioned curable composition for inkjet is formed on a substrate and has a cured product obtained by irradiating it with light.
- the present invention it is possible to obtain a curable composition for inkjet that improves the surface curability of the coating film by the inkjet method and does not deteriorate the conventional characteristics such as solder heat resistance and gold plating resistance. Can do. Moreover, hardened
- the inkjet curable composition of the present invention comprises (A) a bifunctional (meth) acrylate compound having an alkylene chain, (B) an ⁇ -aminoalkylphenone photopolymerization initiator, and (C) an acylphosphine oxide photopolymer.
- a polymerization initiator having a thickness of 10 ⁇ m, an absorbance at a wavelength of 365 nm of 0.08 to 0.8, and an absorbance at a wavelength of 385 nm of 0.05 to 0.3.
- (meth) acrylate is a term generically referring to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
- the inkjet curable composition of the present invention contains a bifunctional (meth) acrylate compound having an alkylene chain.
- the bifunctional (meth) acrylate compound having an alkylene chain is preferably one having no hydroxyl group.
- bifunctional (meth) acrylate having an alkylene chain examples include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and 1,10-decanediol diacrylate. And diacrylates of diols such as acrylate.
- NK ester A-NOD-N (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), light acrylate 1,6HX-A, 1,9ND-A (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), HDDA, 1,9-NDA (trade name, manufactured by Daicel Ornex) and the like.
- the blending amount of these bifunctional (meth) acrylate compounds having an alkylene chain is preferably 20 to 90 parts by mass, more preferably 40 to 80 parts by mass in 100 parts by mass of the curable composition.
- the blending amount of the bifunctional (meth) acrylate is 20 parts by mass or more, the ink compatibility is good.
- the blending amount is 90 parts by mass or less, the ink adhesion is good.
- the viscosity at 25 ° C. of the bifunctional (meth) acrylate compound having an alkylene chain is preferably 5 to 50 mPa ⁇ s, particularly preferably 5 to 30 mPa ⁇ s.
- the handleability as a diluent of a bifunctional (meth) acrylate compound becomes good, and each component can be mixed uniformly. As a result, it can be expected that the entire surface of the coating film adheres uniformly to the substrate.
- the curable composition for inkjet of the present invention contains an ⁇ -aminoalkylphenone photopolymerization initiator as one of photopolymerization initiators.
- ⁇ -aminoalkylphenone photopolymerization initiator examples include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, Examples include ⁇ -aminoacetophenone photopolymerization initiators such as N, N-dimethylaminoacetophenone, and commercially available products include Irgacure 369, Irgacure 379, and Irgacure 907 manufactured by BASF Japan. (B) The blending ratio of the ⁇ -aminoalkylphenone photopolymerization initiator is preferably in the range of 1 to 10 parts by mass in 100 parts by mass of the
- the inkjet curable composition of the present invention contains an acylphosphine oxide photopolymerization initiator as one of the photopolymerization initiators.
- the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6- And dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide.
- Examples of commercially available products include Irgacure TPO and Irgacure 819 manufactured by BASF Japan.
- the blending ratio of the (C) acylphosphine oxide photopolymerization initiator is preferably in the range of 1 to 10 parts by mass in 100 parts by mass of the curable composition.
- the blending ratio of the (B) ⁇ -aminoalkylphenone photopolymerization initiator is preferably larger than that of the (C) acylphosphine oxide photopolymerization initiator.
- the (B) ⁇ -aminoalkylphenone photopolymerization initiator and the (C) acylphosphine oxide photopolymerization initiator can be used alone or as a mixture of two or more, respectively.
- N, N-dimethylaminobenzoic acid Photoinitiator aids such as tertiary amines such as ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine can be added.
- the ink-jet curable composition of the present invention contains a bifunctional (meth) acrylate compound having an alkylene chain, whereby a low-viscosity composition suitable for ink-jet printing can be obtained.
- a bifunctional (meth) acrylate compound having an alkylene chain whereby a low-viscosity composition suitable for ink-jet printing can be obtained.
- the absorbance at a film thickness of 10 ⁇ m and a wavelength of 365 nm is preferably 0.11 to 0.7, and the absorbance at a wavelength of 385 nm is preferably 0.06 to 0.3.
- the film thickness is 10 ⁇ m and the absorbance at a wavelength of 365 nm is 0.08 or more, good surface curability is obtained, and when the absorbance at a wavelength of 365 nm is 0.8 or less, good ink jet printability, solder heat resistance, and gold plating resistance are obtained.
- the ink-jet curable composition of the present invention may contain various components in addition to the components described above. Even in this case, it is important to adjust the material and the amount of the curable composition for inkjet of the present invention so that the absorbance is in the above numerical range.
- a bisphenol-type epoxy (meth) acrylate compound is a compound in which (meth) acrylic acid is partially added to a bisphenol-type epoxy compound.
- acrylic resin is added to one epoxy group of a bisphenol A-type epoxy resin.
- examples thereof include trade name EA-1010N manufactured by Shin-Nakamura Chemical Co., Ltd., which is a compound to which an acid has been added.
- a monofunctional (meth) acrylate compound is preferably used from the viewpoint of easy viscosity adjustment.
- the bisphenol type epoxy (meth) acrylate compound can be used alone or in combination.
- the blending ratio of the bisphenol type epoxy (meth) acrylate compound is preferably in the range of 5 to 30 parts by mass in 100 parts by mass of the curable composition.
- the curable composition for inkjet of the present invention can contain a (meth) acrylate compound having a hydroxyl group.
- a (meth) acrylate compound having a hydroxyl group a low molecular weight material such as a monomer or an oligomer is used. Specifically, a material having a molecular weight in the range of 100 to 1000, preferably in the range of a molecular weight of 110 to 700 is used.
- the (meth) acrylate compound having a hydroxyl group examples include 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, and 1,4-cyclohexanedimethanol mono (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate , 2-hydroxypropyl (meth) acrylate and the like.
- Aronix M-5700 (trade name, manufactured by Toagosei Co., Ltd.), 4HBA, 2HEA, CHDMMA (above, product names manufactured by Nippon Kasei Co., Ltd.), BHEA, HPA, HEMA, HPMA (above, manufactured by Nippon Shokubai Co., Ltd.) Product name), light ester HO, light ester HOP, light ester HOA (above, product name manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
- the (meth) acrylate compound having a hydroxyl group can be used alone or in combination.
- 2-hydroxy-3-acryloyloxypropyl acrylate 2-hydroxy-3-phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 1,4-cyclohexanedimethanol Monoacrylate is preferably used.
- a monofunctional (meth) acrylate compound is preferably used because of easy viscosity adjustment.
- the compounding amount of the (meth) acrylate compound having a hydroxyl group is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass in 100 parts by mass of the curable composition.
- the compounding quantity of the (meth) acrylate which has a hydroxyl group is 1 mass part or more, the adhesiveness of a composition becomes more favorable.
- the blending amount is 20 parts by mass or less, a decrease in ink compatibility can be suppressed.
- the curable composition for inkjets of this invention can mix
- Diluents include diluent solvents, photoreactive diluents, heat reactive diluents, and the like. Of these diluents, photoreactive diluents are preferred.
- Photoreactive diluents include (meth) acrylates, vinyl ethers, ethylene derivatives, styrene, chloromethylstyrene, ⁇ -methylstyrene, maleic anhydride, dicyclopentadiene, N-vinylpyrrolidone, N-vinylformamide, xylyl
- examples thereof include compounds having an unsaturated double bond, oxetanyl group, and epoxy group, such as range oxetane, oxetane alcohol, 3-ethyl-3- (phenoxymethyl) oxetane, resorcinol diglycidyl ether, and the like.
- (meth) acrylates are preferable, and monofunctional (meth) acrylates are more preferable.
- monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2- Examples include (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and glycidyl methacrylate, acryloylmorpholine, and the like.
- the curable composition for inkjet of the present invention may contain (meth) acrylates having a cyclic skeleton.
- (meth) acrylates having a cyclic skeleton include (meth) acrylates having a cyclic hydrocarbon structure, and (meth) acrylates having a heterocyclic structure containing a nitrogen atom, an oxygen atom, or the like.
- the curable composition can mix
- Trifunctional or higher (meth) acrylate compounds include trimethylolpropane triacrylate, trimethylolmethane triacrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane triacrylate, epichlorohydrin modified trimethylolpropane triacrylate, penta Erythritol tetraacrylate, tetramethylol methane tetraacrylate, ethylene oxide modified phosphate triacrylate, propylene oxide modified phosphate triacrylate, epichlorohydrin modified glycerol triacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, or their silsesquioxanes For de
- thermosetting component can be added to the curable composition. It can be expected that adhesion and heat resistance are improved by adding a thermosetting component.
- thermosetting components used in the present invention include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, and benzoguanamine derivatives, blocked isocyanate compounds, cyclocarbonate compounds, thermosetting components having a cyclic (thio) ether group, bismaleimide, Known thermosetting resins such as carbodiimide resins can be used.
- thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is a compound having any one of the three, four or five-membered cyclic (thio) ether groups in the molecule or a plurality of two types of groups.
- a compound having a plurality of epoxy groups in the molecule that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, That is, episulfide resin etc. are mentioned.
- polyfunctional epoxy compound examples include epoxidized vegetable oils such as Adekasizer O-130P, Adekasizer O-180A, Adekasizer D-32, and Adekasizer D-55 manufactured by ADEKA; jER828, jER834 manufactured by Mitsubishi Chemical Corporation; jER1001, jER1004, EHPE3150 made by Daicel Chemical Industries, Epicron 840, Epicron 850, Epicron 1050, Epicron 1050, Epicron 2055, Epototo YD-011, YD-013, YD-127, YD-128 made by Tohto Kasei Co., Ltd. D. Chemicals manufactured by Dow Chemical Company. E. R. 317, D.E. E. R.
- Brominated epoxy resins such as 714 (both trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd. EPPN-201, EOCN-1025, EOCN manufactured by Nippon Kayaku Co., Ltd. -1020, EOCN-104S, RE-306, Sumitomo Epoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Co., Ltd. E. R.
- Novolak type epoxy resins such as ECN-235 and ECN-299 (both trade names); biphenol novolak type epoxy resins such as NC-3000 and NC-3100 manufactured by Nippon Kayaku; Epicron 830 manufactured by DIC, Mitsubishi Chemical JER807 manufactured by Toto Kasei Co., Ltd. Etototo YDF-170, YDF-175, YDF-2004, etc. (all trade names) bisphenol F type epoxy resin; Toto Kasei Co., Ltd.
- Epototo ST-2004, ST-2007, ST- Hydrogenated bisphenol A type epoxy resin such as 3000 (trade name); jER604 manufactured by Mitsubishi Chemical Co., Ltd., Epotot YH-434 manufactured by Tohto Kasei Co., Ltd., Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. ) Glycidylamine type epoxy resin; hydantoin type epoxy resin; Alicyclic epoxy resins GMBH made CELLOXIDE 2021, etc. (all trade names); manufactured by Mitsubishi Chemical Corporation YL-933, Dow Chemical Co. of T. E. N. , EPPN-501, EPPN-502, etc.
- epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC
- glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50
- the present invention is not limited to these.
- These epoxy resins can be used alone or in combination of two or more.
- novolak-type epoxy resins bixylenol-type epoxy resins, biphenol-type epoxy resins, biphenol novolac-type epoxy resins, naphthalene-type epoxy resins or mixtures thereof are particularly preferable.
- polyfunctional oxetane compound examples include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3- Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3- In addition to polyfunctional oxetanes such as oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin , Poly (p-hydroxy
- Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.
- amino resins such as melamine derivatives and benzoguanamine derivatives
- amino resins include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.
- the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group.
- the type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like.
- a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.
- thermosetting component examples include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156. 1158, 1123, 1170, 1174, UFR65, 300 (all manufactured by Mitsui Cyanamid), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx- 290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw- 750LM (all manufactured by Sanwa Chemical Co., Ltd.).
- Such a thermosetting component may be used individually by 1 type, and may be used in combination of 2 or more type.
- An isocyanate compound and a blocked isocyanate compound are compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule.
- Examples of such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule include polyisocyanate compounds or blocked isocyanate compounds.
- the blocked isocyanate group is a group in which the isocyanate group is protected by the reaction with the blocking agent and temporarily inactivated, and the blocking agent is dissociated when heated to a predetermined temperature. Produces. It was confirmed that the curability and toughness of the resulting cured product were improved by adding the polyisocyanate compound or the blocked isocyanate compound.
- polyisocyanate compound for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
- aromatic polyisocyanate include, for example, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, and m-xylylene diisocyanate and 2,4-tolylene dimer.
- aliphatic polyisocyanate examples include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate.
- alicyclic polyisocyanate examples include bicycloheptane triisocyanate.
- adducts, burettes and isocyanurates of the above-mentioned isocyanate compounds can be used.
- the blocked isocyanate compound an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used.
- an isocyanate compound which can react with a blocking agent the above-mentioned polyisocyanate compound etc. are mentioned, for example.
- isocyanate blocking agent examples include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ⁇ -caprolactam, ⁇ -palerolactam, ⁇ -butyrolactam and ⁇ -propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, Alcohol blocking agents such as methyl acid and ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl e
- the blocked isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Death Module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117.
- the blending amount of such a thermosetting component is preferably 1 to 30 parts by mass in 100 parts by mass of the curable composition.
- the blending amount is 1 part by mass or more, sufficient toughness and heat resistance of the coating film can be obtained.
- it is 30 mass parts or less, it can suppress that storage stability falls.
- the inkjet curable composition of the present invention may contain a known and commonly used colorant such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black.
- a known and commonly used colorant such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black.
- Such colorants may be used alone or in admixture of two or more, and the blending amount is 0.1 to 30 parts by weight with respect to 100 parts by weight of the nonvolatile content of the curable composition for inkjet. Yes, preferably 0.5 to 20 parts by mass.
- the blending amount of the colorant is less than 0.1 parts by mass, the visibility is inferior, and when it exceeds 30 parts by mass, the photocuring property at the lower part of the coating film is lowered, which is not preferable. Since the type and amount of the colorant have an influence on the absorbance of the curable composition for inkjet, the colorant is adjusted so as to be within the above-described preferred range of absorbance.
- titanium oxide When a white pigment is included as a colorant, titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, sulfide
- a known white pigment such as zinc can be used.
- titanium oxide is preferable because of its high colorability and reflectance.
- These white pigments may be used alone or in combination of two or more.
- the titanium oxide may be a rutile type titanium oxide or an anatase type titanium oxide, but it is preferable to use a rutile type titanium from the viewpoint of colorability, concealability and stability.
- Anatase-type titanium oxide which is the same titanium oxide, has higher whiteness compared to rutile-type titanium oxide and is often used as a white pigment.
- the emitted light may cause discoloration of the resin in the insulating resin composition.
- rutile-type titanium oxide is slightly inferior to anatase-type in whiteness, but has almost no photoactivity, so that the resin is deteriorated by light due to the photoactivity of titanium oxide (yellowing). Is remarkably suppressed and is stable against heat. For this reason, when it is used as a white pigment in the insulating layer of the printed wiring board on which the LED is mounted, a high reflectance can be maintained over a long period of time.
- a well-known thing can be used as rutile type titanium oxide.
- rutile type titanium oxide There are two types of production methods for rutile titanium oxide, a sulfuric acid method and a chlorine method.
- the sulfuric acid method uses ilmenite ore or titanium slag as a raw material, dissolves this in concentrated sulfuric acid, separates iron as iron sulfate, and hydrolyzes the solution to obtain a hydroxide precipitate.
- the chlorine method uses synthetic rutile or natural rutile as a raw material, reacts with chlorine gas and carbon at a high temperature of about 1000 ° C to synthesize titanium tetrachloride, and oxidizes this to extract rutile titanium oxide.
- rutile-type titanium oxide produced by the chlorine method is particularly effective in suppressing the deterioration (yellowing) of the resin due to heat, and is more preferably used in the present invention.
- Examples of commercially available rutile-type titanium oxides include, for example, Typek R-820, Typek R-830, Typek R-930, Typek R-550, Typek R-630, Typek R-680, Typek R-670, and Typek R.
- anatase type titanium oxide known ones can be used.
- Commercially available anatase-type titanium oxide includes TITON A-110, TITON TCA-123E, TITON A-190, TITON A-197, TITON SA-1, TITON SA-1L (manufactured by Sakai Chemical Industry Co., Ltd.), TA -100, TA-200, TA-300, TA-400, TA-500, TP-2 (manufactured by Fuji Titanium Industry Co., Ltd.), TITANIX JA-1, TITANIX JA-3, TITANIX JA-4, TITANIX JA-5 , TITANIX JA-C (manufactured by Takeka Co., Ltd.), KA-10, KA-15, KA-20, KA-30 (manufactured by Titanium Industry Co., Ltd.), Taipei A-100, Taipei A-220, Taipei W-10 ( Ishihara Sangyo Co.,
- the blending amount of the white pigment has a great influence on the absorbance, and is preferably 3 to 50 parts by mass, more preferably 5 to 30 parts by mass, and particularly preferably 5 to 25 parts by mass in 100 parts by mass of the curable composition. If a white pigment is 3 mass parts or more, the reflectance of a composition will become enough. When the amount is 50 parts by mass or less, an excessive increase in the viscosity of the composition and a decrease in printability can be suppressed.
- a black pigment When a black pigment is included as a colorant, carbon, aniline black, iron oxide, or the like can be used.
- the blending amount of the black pigment has a great influence on the absorbance, and is preferably 3 to 50 parts by weight, more preferably 5 to 30 parts by weight, and particularly preferably 5 to 25 parts by weight in 100 parts by weight of the curable composition.
- a well-known dye may be included, for example, a phthalocyanine dye, an anthraquinone dye, and an azo dye are mentioned.
- the ink-jet curable composition of the present invention may contain a wetting and dispersing agent.
- a wetting and dispersing agent those having an effect of assisting the dispersion of the pigment can be generally used.
- examples of such a wetting and dispersing agent include compounds having a polar group such as a carboxyl group, a hydroxyl group, and an acid ester, polymer compounds such as acid-containing compounds such as phosphate esters, copolymers containing an acid group, and hydroxyl group-containing compounds.
- Polycarboxylic acid esters, polysiloxanes, salts of long-chain polyaminoamides and acid esters, and the like can be used.
- wetting and dispersing agents those having an acid value are preferable because they are more effective for dispersing inorganic pigments such as titanium oxide.
- Specific examples of the wetting and dispersing agent having an acid value include Anti-Terra-U, Anti-Terra-U100, Anti-Terra-204, Anti-Terra-205, Disperbyk-101, Disperbyk-102, Disperbyk-106, Disperbyk.
- the acid value of the wetting and dispersing agent having these acid values is preferably 10 to 300 mgKOH / g.
- the amount of the wet dispersant is preferably 5 to 75 parts by mass with respect to 100 parts by mass of the colorant.
- the curable composition for inkjet of the present invention can contain a surface tension adjusting agent.
- the compounding amount of the surface tension modifier is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the composition.
- the curable composition for inkjet of the present invention includes a surfactant, a matting agent, a polyester resin for adjusting the film properties, a polyurethane resin, a vinyl resin, an acrylic resin, as necessary.
- a surfactant e.g., a surfactant for adjusting the film properties
- a matting agent e.g., a polyurethane resin
- a vinyl resin e.g., polyurethane resin
- acrylic resin e.g., acrylate-based
- At least one kind of antifoaming agent and leveling agent such as resin, rubber-based resin, wax, silicone-based, fluorine-based, and polymer-based, adhesion-imparting agent such as imidazole-based, thiazole-based, triazole-based, and silane coupling agent
- the known and conventional additives such as can be blended.
- a resin can be blended in the curable composition for inkjet of the present invention within a range that does not impair the characteristics.
- skeleton is preferable.
- the polyene skeleton is preferably formed by polymerization using, for example, polybutadiene or isoprene, or both, and in particular, the general formula (I), (In the formula, n represents 10 to 300.) It is preferable that it is comprised from the repeating unit represented by these. Due to the olefinic double bonds of such repeating units, flexibility is imparted to the curable resist composition for printed wiring boards, the followability to the substrate is increased, and good adhesion is obtained.
- the repeating unit represented by the general formula (I) is preferably 50% or more, and more preferably 80% or more.
- polyene skeleton of the (meth) acrylate compound has the following general formula (II), The unit represented by may be included.
- liquid polybutadiene urethane (meth) acrylate obtained by subjecting 2-hydroxyethyl (meth) acrylate to a urethane addition reaction with a hydroxyl group of liquid polybutadiene via 2,4-tolylene diisocyanate, and maleic anhydride were added.
- Examples of commercially available products include NISSO PB TE-2000, NISSO PB TEA-1000, NISSO PB TE-3000, NISSO PB TEAI-1000 (all of which are manufactured by Nippon Soda Co., Ltd.), CN301, CN303, CN307 (SARTOMER) , BAC-15 (manufactured by Osaka Organic Chemical Industry), BAC-45 (manufactured by Osaka Organic Chemical Industry), EY RESIN BR-45UAS (manufactured by Light Chemical Industry), and the like.
- (Meth) acrylate having a polyene skeleton can be used alone or in combination of two or more.
- the viscosity of the curable composition at 50 ° C. is preferably 5 to 50 mPa ⁇ s, and preferably 5 to 20 mPa ⁇ s. More preferred. As a result, smooth printing can be performed without applying an unnecessary load to the inkjet printer.
- the viscosity of the curable composition refers to a viscosity measured at room temperature (25 ° C.) or 50 ° C. according to JIS K2283. If the viscosity is 150 mPa ⁇ s or less at room temperature or the viscosity at 50 ° C. is 5 to 50 mPa ⁇ s, smooth printing by the ink jet printing method is possible.
- the maximum particle size of the particles contained in the curable composition is preferably 0.1 to 5 ⁇ m or less, and more preferably 0.1 to 1 ⁇ m. If the maximum particle size is 0.1 ⁇ m or more, the cohesive force of the particles will not be too high, and if it is 5 ⁇ m or less, the possibility of problems such as nozzle clogging during ink jet printing is reduced, which is preferable. .
- the maximum particle size of the particles contained in the composition can be measured with a particle size distribution meter, and the D100 value is taken as the maximum particle size.
- the curable composition can be used as an ink for an ink jet system due to the above composition, and for example, can be printed on a flexible wiring board by a roll-to-roll system.
- the light irradiation is performed by irradiation with ultraviolet rays or active energy rays, but ultraviolet rays are preferable.
- a light source for light irradiation a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, an LED lamp, or the like is appropriate.
- electron beams, ⁇ rays, ⁇ rays, ⁇ rays, X rays, neutron rays, and the like can also be used.
- the heating temperature is, for example, 70 to 200 ° C. By setting this heating temperature range, it can be sufficiently cured.
- the heating time is, for example, 10 to 100 minutes.
- the curable composition is excellent in adhesion to a printed wiring board including a plastic substrate mainly composed of polyimide and the like and a conductor circuit provided thereon, and has solder heat resistance, chemical resistance, Pattern cured products excellent in various properties such as solvent resistance, pencil hardness, electroless gold plating resistance, and bendability can be formed.
- a printed wiring board has the hardened
- the printed wiring board can be manufactured by the following method.
- a curable composition is applied onto a substrate on which a circuit has been formed by an inkjet method to form a cured product having a pattern.
- a curable composition contains a photobase generator, it is preferable to heat hardened
- the heating temperature is, for example, 70 to 200 ° C.
- the curable composition is suitable as a material for forming a cured product of a printed wiring board, but is particularly suitable as a material for forming a permanent film of a printed wiring board, and particularly suitable as a material for forming a permanent insulating film such as a solder resist. is there.
- the curable composition of the present invention can also be used as a symbol marking material, a coverlay forming material, or an interlayer insulating layer forming material formed on a substrate or a cured film.
- part means part by mass unless otherwise specified.
- the absorbance and coating film properties of the curable composition for inkjet prepared as described above and the coating film thereof were evaluated.
- the results of measuring the absorbance at a film thickness of 10 ⁇ m are shown in Table 2, and the coating film properties are shown in Table 3.
- the absorbance indicates the absorbance at a film thickness of 10 ⁇ m, and was measured by the method described below.
- the ink-jet curable compositions of each Example and each Comparative Example were diluted to 1/1000 using tetrahydrofuran, and the absorbance was measured with a spectrophotometer. At this time, a measurement cell having an optical path length of 1 cm was used so as to have the same value as the absorbance at a film thickness of 10 ⁇ m of the composition before dilution.
- the viscosity indicates the viscosity at 50 ° C. and 100 rpm of the curable composition for inkjet obtained by preparing according to the formulations of Examples 1 to 6 and Comparative Examples 1 to 5 in Table 1.
- a cone plate viscometer This is a value measured with (TVH-33H manufactured by Toki Sangyo Co., Ltd.). ⁇ Less than 150 mPa ⁇ s at 25 ° C ⁇ More than 150 mPa ⁇ s at 25 ° C
- IJ printability confirmed the following criteria by confirming the state of injection by an ink jet head when performing ink jet printing.
- ⁇ Good injection
- ⁇ Good injection
- ⁇ Injection not possible
- Film thickness 20 ⁇ m
- Equipment Piezo-type inkjet printer (using Fujifilm Global Graphic Systems' material printer DMP-2831 (head temperature 50 ° C))
- Wavelength 385nm
- the surface curability was evaluated based on the following criteria by confirming the touch drying property (tack property) of the cured coating film in a pattern formed by inkjet printing.
- A There is no tackiness on the coating surface.
- ⁇ The coating film surface is sticky and tackiness is confirmed.
- ⁇ Sliminess is observed on the surface of the coating film.
- X The coating film surface is not hardened and is liquid.
- pattern bleeding is a pattern formed by inkjet printing, from the boundary line between the cured coating film and the copper foil of the base substrate, observe and measure the width of the blur generated on the base substrate side with an optical microscope, Evaluation was made according to the following criteria.
- a copper-clad laminate for printed wiring boards (FR-4, 150 mm ⁇ 95 mm ⁇ 1.6 mm) was used as the base substrate.
- A: The blur width is 0 to 10 ⁇ m.
- ⁇ The blur width is 11 to 20 ⁇ m.
- Smudge width is 21-30 ⁇ m
- Bleeding width is more than 30 ⁇ m
- the adhesiveness was obtained by applying a curable composition on a copper foil with a thickness of 30 ⁇ m using an ink jet coating apparatus, and curing at an exposure amount of 150 mJ / cm 2 using a high-pressure mercury lamp (HMW-713 manufactured by ORC). Then, heat processing was performed for 60 minutes in a 150 degreeC hot-air circulation type drying furnace. A cross-cut tape peel test was performed on the samples thus obtained and evaluated according to the following criteria. ⁇ : No peeling. (Triangle
- Pencil Hardness Using the same sample obtained in the above adhesion test, the pencil hardness on the surface of the cured coating film was measured according to JIS K 5600-5-4. ⁇ : Hardness of 3H or more ⁇ : Hardness of 2H or less
- Electroless gold plating resistance Using the same sample obtained in the above adhesion test, using a commercially available electroless nickel plating bath and electroless gold plating bath, under conditions of nickel 0.5 ⁇ m and gold 0.03 ⁇ m The cured coating film was plated, and the surface state of the obtained cured coating film was observed.
- the judgment criteria are as follows. Evaluation criteria ⁇ : No change is observed. ⁇ : Whitening or clouding occurred. X: Remarkably whitened or clouded.
- Examples 1 to 6 containing the components of the present invention were excellent in surface curability, no pattern bleeding, excellent adhesion, and excellent coating film properties.
- Comparative Example 1 that does not contain an acylphosphine oxide photopolymerization initiator is confirmed to be inferior in IJ printability, surface curability, pattern bleeding, adhesion, pencil hardness, solder heat resistance, and gold plating resistance. It was done. It was confirmed that Comparative Example 2 having a high absorbance at 385 nm was inferior in viscosity, ink jet printability, solder heat resistance, and gold plating resistance.
- Comparative Example 3 which did not contain an ⁇ -aminoalkylphenone photopolymerization initiator and had low absorbance at 365 nm and 385 nm, was inferior in all properties. It was confirmed that Comparative Example 4 having low absorbance at 365 nm and 385 nm was inferior in IJ printability, pattern bleeding, adhesion, pencil hardness, solder heat resistance, and gold plating resistance. Comparative Example 5 having a low absorbance at 365 nm was confirmed to be inferior in IJ printability, surface curability, pattern bleeding, adhesion, pencil hardness, solder heat resistance, and gold plating resistance.
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Abstract
Description
近年、スクリーン印刷の代わりに、インクジェット方式により上記エッチングレジスト、ソルダーレジスト、シンボルマーキングなどを形成する方法が開発された。インクジェット方式の特徴として、インキの使用量が削減でき、スクリーン印刷用の版も不要であり、デジタルデータからの直接描画が可能である。また、インクジェットプリンタのヘッド若しくはその近傍にUV照射装置を備え付けることにより、パターン印刷とUVによる仮硬化を同時に行うことが可能であり、工程にかかわる時間も削減できる。インクジェットノズルからの吐出を考慮し、従来の印刷法に用いられる硬化性組成物とは異なる物性が求められる。
例えば、粘度が25℃で150mPa・s以下のような低粘度であるインクジェット用硬化性組成物がある(特許文献1)。
また、上記本発明のインクジェット用硬化性組成物は、さらに、(D)ビスフェノール型エポキシ(メタ)アクリレート化合物を含むことができる。
更に、上記本発明のインクジェット用硬化性組成物は、50℃における粘度が50mPa・s以下であることが好ましい。
本発明のインクジェット硬化性組成物は、アルキレン鎖を有する2官能(メタ)アクリレート化合物を含む。アルキレン鎖を有する2官能(メタ)アクリレート化合物は、水酸基を有しないものであることが好ましい。アルキレン鎖を有する2官能(メタ)アクリレート化合物を含むことにより、インクジェット印刷に適した低粘度の組成物を得ることができる。
本発明のインクジェット用硬化性組成物は、光重合開始剤の一つとして、α-アミノアルキルフェノン系光重合開始剤を含む。
(B)α-アミノアルキルフェノン系光重合開始剤の配合割合は、硬化性組成物100質量部中、1~10質量部の範囲が好ましい。
本発明のインクジェット用硬化性組成物は、光重合開始剤の一つとして、アシルホスフィンオキサイド系光重合開始剤を含む。
アシルホスフィンオキサイド系光重合開始剤としては、具体的には2,4,6-トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォフィンオキサイド、ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチル-ペンチルホスフィンオキサイドなどが挙げられる。市販品としては、BASFジャパン社製のイルガキュアーTPO、イルガキュアー819などが挙げられる。
(C)アシルホスフィンオキサイド系光重合開始剤の配合割合は、硬化性組成物100質量部中、1~10質量部の範囲が好ましい。
ここで、(B)α-アミノアルキルフェノン系光重合開始剤の配合割合は、(C)アシルホスフィンオキサイド系光重合開始剤よりも多いことが好ましい。(B)α-アミノアルキルフェノン系光重合開始剤の配合割合を多くすることにより、酸素の影響等による表面硬化性の低下を抑え、鉛筆硬度等に優れた硬化膜を得ることができる。
膜厚10μm、波長365nmにおける吸光度が0.08以上で良好な表面硬化性が得られ、波長365nmにおける吸光度が0.8以下で良好なインクジェット印刷性、はんだ耐熱性、金めっき耐性が得られる。波長385nmにおける吸光度が0.05以上で良好な表面硬化性が得られ、波長385nmにおける吸光度が0.3以下で良好なインクジェット印刷性、はんだ耐熱性、金めっき耐性が得られる。
ビスフェノール型エポキシ(メタ)アクリレート化合物は、ビスフェノール型エポキシ化合物に対し、部分的に(メタ)アクリル酸を付加させた化合物であり、具体例としては、ビスフェノールA型エポキシ樹脂の片方のエポキシ基にアクリル酸を付加させた化合物である、新中村化学工業社製の商品名EA-1010Nなどが挙げられる。このうち、粘度調整の容易さ等から単官能(メタ)アクリレート化合物が好ましく用いられる。ビスフェノール型エポキシ(メタ)アクリレート化合物は、1種類又は複数種類を組み合わせて用いることができる。
ビスフェノール型エポキシ(メタ)アクリレート化合物の配合割合は、硬化性組成物100質量部中、5~30質量部の範囲が好ましい。
ビスフェノール型エポキシ(メタ)アクリレート化合物を含むことにより、インクジェット塗布に適した低粘度で、かつ、各種特性が良好な組成物が得られる。
本発明のインクジェット用硬化性組成物は、水酸基を有する(メタ)アクリレート化合物を含むことができる。この水酸基を有する(メタ)アクリレート化合物は、モノマーまたはオリゴマー等の低分子量の材料が使用され、具体的には分子量100~1000の範囲、好ましくは分子量110~700の範囲の材料が用いられる。
希釈剤としては、希釈溶剤、光反応性希釈剤、熱反応性希釈剤等が挙げられる。これらの希釈剤の中でも光反応性希釈剤が好ましい。
光反応性希釈剤としては、(メタ)アクリレート類、ビニルエーテル類、エチレン誘導体、スチレン、クロロメチルスチレン、α-メチルスチレン、無水マレイン酸、ジシクロペンタジエン、N-ビニルピロリドン、N-ビニルホルムアミド、キシリレンジオキセタン、オキセタンアルコール、3-エチル-3-(フェノキシメチル)オキセタン、レゾルシノールジグリシジルエーテル等の不飽和二重結合やオキセタニル基、エポキシ基を有する化合物が挙げられる。
これらの中でも(メタ)アクリレート類が好ましく、さらに好ましくは単官能(メタ)アクリレート類が好ましい。単官能(メタ)アクリレート類としては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、ヒドロキシブチル(メタ)アクリレート、グリシジルメタクリレート等の(メタ)アクリレート類や、アクリロイルモルホリン等を挙げることができる。
また、本発明のインクジェット用硬化性組成物においては、環状骨格を有する(メタ)アクリレート類を含んでいてもよい。環状骨格を有する(メタ)アクリレート類としては、環状炭化水素構造を有する(メタ)アクリレート、窒素原子や酸素原子等を含む複素環構造を有する(メタ)アクリレートが挙げられる。
3官能以上の(メタ)アクリレート化合物としては、トリメチロールプロパントリアクリレート、トリメチロールメタントリアクリレート、エチレンオキシド変性トリメチロールプロパントリアクリレート、プロピレンオキシド変性トリメチロールプロパントリアクリレート、エピクロルヒドリン変性トリメチロールプロパントリアクリレート、ペンタエリスリトールテトラアクリレート、テトラメチロールメタンテトラアクリレート、エチレンオキシド変性リン酸トリアクリレート、プロピレンオキシド変性リン酸トリアクリレート、エピクロルヒドリン変性グリセロールトリアクリレート、ジペンタエリスリトールヘキサアクリレート、ジトリメチロールプロパンテトラアクリレート、あるいはこれらのシルセスキオキサン変性物等に代表される多官能アクリレート、あるいはこれらに対応するメタアクリレートモノマー、εカプロラクトン変性トリスアクリロキシエチルイソシアヌレートが挙げられる。
硬化性組成物には、熱硬化成分を加えることができる。熱硬化成分を加えることにより密着性や耐熱性が向上することが期待できる。本発明に用いられる熱硬化成分としては、メラミン樹脂、ベンゾグアナミン樹脂、メラミン誘導体、ベンゾグアナミン誘導体等のアミノ樹脂、ブロックイソシアネート化合物、シクロカーボネート化合物、環状(チオ)エーテル基を有する熱硬化成分、ビスマレイミド、カルボジイミド樹脂等の公知の熱硬化性樹脂が使用できる。その他、ベンゼン環を有する芳香族アミンや、アミン化合物とエポキシ化合物との反応物等を使用してもよい。特に好ましいのは、保存安定性に優れる点より、ブロックイソシアネート化合物である。
芳香族ポリイソシアネートの具体例としては、例えば、4,4’-ジフェニルメタンジイソシアネート、2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、ナフタレン-1,5-ジイソシアネート、o-キシリレンジイソシアネート、m-キシリレンジイソシアネートおよび2,4-トリレンダイマー等が挙げられる。
本発明のインクジェット用硬化性組成物は、フタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック、ナフタレンブラックなどの公知慣用の着色剤を含むことができる。
このような着色剤は、単独または2種類以上を混合して用いても良く、その配合量は、インクジェット用硬化性組成物の不揮発分100質量部に対して、0.1~30重量部であり、好ましくは0.5~20質量部である。着色料の配合量が0.1質量部未満では視認性が劣り、30質量部を越えた場合、塗膜下部の光硬化性低下が起こり、好ましくない。
着色剤の種類、配合量は、インクジェット用硬化性組成物の吸光度に影響があるので、上述した吸光度の好適範囲内になるように調整する。
なお、着色剤としては、公知の染料を含んでいてもよく、例えば、フタロシアニン系染料、アントラキノン系染料、アゾ系染料が挙げられる。
本発明のインクジェット用硬化性組成物には、湿潤分散剤を含むことができる。湿潤分散剤としては、一般的に顔料の分散を補助する効果のあるものを用いる事が出来る。このような湿潤分散剤としては、カルボキシル基、水酸基、酸エステルなどの極性基を有する化合物や高分子化合物、例えばリン酸エステル類などの酸含有化合物や、酸基を含む共重合物、水酸基含有ポリカルボン酸エステル、ポリシロキサン、長鎖ポリアミノアマイドと酸エステルの塩などを用いることができる。
また、これらの湿潤分散剤の中でも酸価を有するものが、酸化チタンなどの無機顔料の分散により有効である為好ましい。
酸価を有する湿潤分散剤の具体例としては、Anti-Terra-U、Anti-Terra-U100、Anti-Terra-204、Anti-Terra-205、Disperbyk-101、Disperbyk-102、Disperbyk-106、Disperbyk-110、Disperbyk-111、Disperbyk-130、Disperbyk-140、Disperbyk-142、Disperbyk-145、Disperbyk-170、Disperbyk-171、Disperbyk-174、Disperbyk-180、Disperbyk-2001、Disperbyk-2025、Disperbyk-2070、Disperbyk-2096、BYK-P104、BYK-P104S、BYK-P105、BYK-9076、BYK-220S(何れもBYK Chemie社製)等が挙げられる。
これらの酸価を有する湿潤分散剤の酸価は10~300mgKOH/gが好ましい。
上記湿潤分散剤の配合量は、着色剤100質量部に対して、好ましくは5~75質量部である。
(式中、nは10~300を示す。)
で表わされる繰り返し単位から構成されることが好ましい。このような繰り返し単位のオレフィン性二重結合に起因して、プリント配線板用硬化性レジスト組成物に柔軟性が与えられ、基材への追従性が増し、良好な密着性が得られる。
(メタ)アクリル酸とのエステル化反応により得られる液状ポリブタジエン(メタ)アクリレート、ヒドロキシル基を有する液状ポリブタジエンと、(メタ)アクリル酸クロリドとの脱塩素反応によって得られる液状ポリブタジエン(メタ)アクリレート、分子両末端にヒドロキシル基を有する液状ポリブタジエンの不飽和二重結合を水素添加した液状水素化1,2ポリブタジエングリコールを、ウレタン(メタ)アクリレート変成した液状水素化1,2ポリブタジエン(メタ)アクリレート等である。
組成物中に含まれる粒子の最大粒径は、粒度分布計により測定することができ、そのD100値を最大粒径とする。
更に、硬化性組成物は、ポリイミド等を主成分とするプラスチック基板と、その上に設けられた導体回路とを含むプリント配線板に対し密着性に優れ、かつ、はんだ耐熱性、耐薬品性、耐溶剤性、鉛筆硬度、無電解金めっき耐性、折り曲げ性等の諸特性に優れたパターン硬化物を形成できる。
プリント配線板は、回路パターンを有する基材上に、硬化性組成物からなる硬化物を有する。プリント配線板は以下の方法により製造することができる。
硬化性組成物は、プリント配線板の硬化物形成用材料として好適であるが、特にプリント配線板の永久被膜形成用材料として好適であり、中でもソルダーレジストなどの永久絶縁膜形成用材料として好適である。また、本発明の硬化性組成物は、基材や硬化膜上に形成するシンボルマーキング材料、カバーレイ形成用材料、層間絶縁層形成用材料として用いることもできる。
○25℃で150mPa・s以下
×25℃で150mPa・s超
○:射出良好
△:射出良好ではないが、射出可能
×:射出不可
<インクジェットプリンタによる描画条件>
・膜厚:20μm
・装置:ピエゾ方式インクジェットプリンタ(富士フィルムグローバルグラフィックシステムズ製マテリアルプリンタDMP-2831を使用(ヘッド温度50℃))
<UV硬化条件>
・露光量:1000mJ/cm2
・波長:385nm
◎:塗膜表面にタック性なし。
○:塗膜表面がべたつき、タック性が確認される。
△:塗膜表面にぬめりが観察される。
×:塗膜表面が硬化しておらず、液状である。
◎:にじみの幅が0~10μm
○:にじみの幅が11~20μm
△:にじみの幅が21~30μm
×:にじみの幅が30μm超
○:剥離なし。
△:若干の剥離あり。
×:剥離あり。
上記密着性試験で得られたのと同じサンプルを用いて、硬化塗膜に対し、表面における鉛筆硬度をJIS K 5600-5-4に準拠して測定を行った。
○:3H以上の硬度
×:2H以下の硬度
上記密着性試験で得られたのと同じサンプルを用いて、硬化塗膜に対し、JIS C 5012の方法に準拠し、260℃のはんだ槽に10秒間浸漬後、セロハン粘着テープによるピーリング試験を行った後の塗膜状態を目視にて観察し、以下の基準で評価した。
評価基準
○:塗膜に剥がれや膨れなし。
×:塗膜に剥がれや膨れあり。
上記密着性試験で得られたのと同じサンプルを用いて、市販の無電解ニッケルめっき浴および無電解金めっき浴を用いて、ニッケル0.5μm、金0.03μmの条件で、硬化塗膜に対しめっきを行ない、得られた硬化塗膜表面状態の観察を行った。判定基準は以下のとおりである。
評価基準
○:変化が認められないもの。
△:白化若しくは曇りが生じたもの。
×: 顕著に白化若しくは曇りが生じたもの。
Claims (6)
- (A)アルキレン鎖を有する2官能(メタ)アクリレート化合物と、
(B)α-アミノアルキルフェノン系光重合開始剤と、
(C)アシルホスフィンオキサイド系光重合開始剤と、
を含み、膜厚10μm、波長365nmにおける吸光度が0.08~0.8、波長385nmにおける吸光度が0.05~0.3であることを特徴とするインクジェット用硬化性組成物。 - 前記(A)アルキレン鎖を有する2官能(メタ)アクリレート化合物のアルキレン鎖の炭素数が4~12である請求項1記載のインクジェット用硬化性組成物。
- さらに、(D)ビスフェノール型エポキシ(メタ)アクリレート化合物を含む請求項1記載のインクジェット用硬化性組成物。
- 50℃における粘度が50mPa・s以下である請求項1に記載のインクジェット硬化性組成物。
- 請求項1~4のいずれか一項に記載のインクジェット用硬化性組成物を硬化して得られることを特徴とする硬化物。
- 請求項5に記載の硬化物を有することを特徴とするプリント配線板。
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