WO2010026927A1 - 半導体パッケージ用プリント配線板の保護膜用感光性樹脂組成物 - Google Patents
半導体パッケージ用プリント配線板の保護膜用感光性樹脂組成物 Download PDFInfo
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- WO2010026927A1 WO2010026927A1 PCT/JP2009/065069 JP2009065069W WO2010026927A1 WO 2010026927 A1 WO2010026927 A1 WO 2010026927A1 JP 2009065069 W JP2009065069 W JP 2009065069W WO 2010026927 A1 WO2010026927 A1 WO 2010026927A1
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- photosensitive resin
- epoxy resin
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
-
- 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
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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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- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
-
- 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
- H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
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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
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
Definitions
- the present invention relates to a photosensitive resin composition for a protective film of a printed wiring board for a semiconductor package.
- a permanent mask resist (protective film) is formed on a printed wiring board.
- This permanent mask resist has a role of preventing the solder from adhering to unnecessary portions of the conductor layer of the printed wiring board in the process of flip chip mounting the semiconductor element on the printed wiring board via solder. Further, the permanent mask resist has a role of preventing corrosion of the conductor layer and maintaining electrical insulation between the conductor layers when the printed wiring board is used.
- thermosetting resin paste is screen printed except for a rigid wiring board, an IC chip, an electronic component, or an LCD panel and a connection wiring pattern portion,
- a permanent mask resist is formed by thermosetting (see, for example, Patent Document 1).
- a semiconductor element is flip-chip mounted on the semiconductor package substrate via solder.
- Such a photosensitive resin composition that can be easily removed is used as a permanent mask resist (see, for example, Patent Document 2).
- JP 2003-198105 A Japanese Patent Laid-Open No. 11-240930
- the alkali development type photosensitive resin composition still has a problem in terms of durability. That is, chemical resistance, water resistance, heat resistance, moist heat resistance and the like are inferior to those of conventional thermosetting type and solvent developing type. This is because the alkali-developable photosensitive resin composition contains a hydrophilic group as a main component so that alkali development is possible, and chemicals, water, water vapor, and the like easily permeate. In particular, in semiconductor packages such as BGA and CSP, resistance to PCT (pressure cooker resistance), which should be referred to as moisture and heat resistance, is necessary. The problem is that the adhesion between the underfill material filled between the solder resist and the solder resist and the cured film as the permanent mask resist is greatly reduced.
- PCT pressure cooker resistance
- the present invention has been made in view of the above-described problems of the prior art, and has excellent adhesion between an underfill material and a cured film that is a permanent mask resist even after a long-time PCT resistance test. It aims at providing the photosensitive resin composition for protective films of the printed wiring board for packages.
- the present invention provides (A) an acid-modified vinyl group-containing epoxy resin, (B) a phenolic compound, and (C) a compound having at least one ethylenically unsaturated group in the molecule;
- the photosensitive resin composition for protective films of the printed wiring board for semiconductor packages containing (D) a photoinitiator and (E) inorganic fine particles is provided.
- the photosensitive resin composition of the present invention is very useful as a photosensitive resin composition for a protective film of a printed wiring board for semiconductor packages.
- the (B) phenol compound improves the adhesion between the underfill material and the cured film that is a permanent mask resist even after a long-time PCT resistance test.
- a compound represented by the following general formula (1) is preferable.
- R 1 represents an alkyl group having 1 to 5 carbon atoms
- m represents an integer of 1 to 4
- n represents an integer of 1 to 4
- A represents an n-valent organic group.
- m and / or n is 2 or more, a plurality of R 1 may be the same or different.
- A is 2 to 4 from the viewpoint of further improving the adhesion between the underfill material and the cured film as the permanent mask resist even after a long-time PCT resistance test. It is preferably a monovalent hydrocarbon group having 1 to 5 carbon atoms, a trivalent organic group represented by the following general formula (2), or a trivalent organic group represented by the following general formula (3). . From the same viewpoint, in the general formula (1), at least one R 1 is preferably a tert-butyl group.
- R 2 represents an alkyl group having 1 to 5 carbon atoms, and t represents an integer of 1 to 3.
- the (A) acid-modified vinyl group-containing epoxy resin is represented by the following general formula (4) from the viewpoint of being capable of alkali development and being excellent in resolution and adhesiveness.
- Novolak type epoxy resin bisphenol type epoxy resin represented by the following general formula (5), salicylaldehyde type epoxy resin represented by the following general formula (6), and the following general formula (7) or (8)
- a resin obtained by reacting a saturated or unsaturated group-containing polybasic acid anhydride (c) is preferred.
- R 11 represents a hydrogen atom or a methyl group
- Y 1 represents a hydrogen atom or a glycidyl group
- n 1 represents an integer of 1 or more.
- a plurality of R 11 and Y 1 may be the same or different. However, at least one Y 1 represents a glycidyl group.
- R 12 represents a hydrogen atom or a methyl group
- Y 2 represents a hydrogen atom or a glycidyl group
- n2 represents an integer of 1 or more.
- a plurality of R 12 may be the same or different.
- Y 2 existing in plural numbers may be the same or different.
- Y 3 represents a hydrogen atom or a glycidyl group
- n3 is an integer of 1 or more.
- a plurality of Y 3 may be the same or different. However, at least one Y 3 represents a glycidyl group.
- R 13 represents a hydrogen atom or a methyl group
- Y 4 and Y 5 each independently represent a hydrogen atom or a glycidyl group.
- Two R 13 may be the same or different. However, at least one of Y 4 and Y 5 represents a glycidyl group.
- R 14 represents a hydrogen atom or a methyl group, respectively Y 6 and Y 7 are independently a hydrogen atom or a glycidyl group. Two R 14 may be the same or different. However, at least one of Y 6 and Y 7 represents a glycidyl group.
- the content of the inorganic fine particles (E) is preferably 15 to 80% by mass based on the total solid content of the photosensitive resin composition.
- the photosensitive resin composition of the present invention preferably further contains (F) a curing agent.
- a curing agent By containing a hardening
- the photosensitive resin composition of the present invention further contains (G) an elastomer.
- G By containing an elastomer, the flexibility of the cured film formed from the photosensitive resin composition, the adhesiveness with the underfill material, and the like can be further improved.
- a printed wiring board for a semiconductor package has excellent adhesion between an underfill material and a cured film that is a permanent mask resist and excellent solder heat resistance even after a long-time PCT resistance test.
- a photosensitive resin composition for a protective film can be provided.
- (meth) acryl means acryl and methacryl corresponding thereto
- (meth) acrylate means acrylate and methacrylate corresponding thereto.
- the photosensitive resin composition for a protective film of a printed wiring board for a semiconductor package includes (A) an acid-modified vinyl group-containing epoxy resin (hereinafter sometimes referred to as “component (A)”), and (B) a phenolic resin.
- component (B) an acid-modified vinyl group-containing epoxy resin
- component (C) a compound having at least one ethylenically unsaturated group in the molecule
- component (D) A photopolymerization initiator (hereinafter, sometimes referred to as “component (D)”)
- component (E) inorganic fine particles
- A As an acid-modified vinyl group-containing epoxy resin, for example, a resin obtained by modifying an epoxy resin with a vinyl group-containing monocarboxylic acid can be used.
- a novolac type epoxy represented by the following general formula (4) Resin, bisphenol type epoxy resin represented by the following general formula (5), salicylaldehyde type epoxy resin represented by the following general formula (6), and repetition represented by the following general formula (7) or (8)
- a resin (A ′) obtained by reacting at least one epoxy resin (a) selected from the group consisting of bisphenol-type novolak resins having units with a vinyl group-containing monocarboxylic acid (b) Is preferred.
- R 11 represents a hydrogen atom or a methyl group
- Y 1 represents a hydrogen atom or a glycidyl group
- n 1 represents an integer of 1 or more.
- a plurality of R 11 and Y 1 may be the same or different. However, at least one Y 1 represents a glycidyl group.
- R 12 represents a hydrogen atom or a methyl group
- Y 2 represents a hydrogen atom or a glycidyl group
- n2 represents an integer of 1 or more.
- a plurality of R 12 may be the same or different.
- Y 2 existing in plural numbers may be the same or different.
- Y 3 represents a hydrogen atom or a glycidyl group
- n3 is an integer of 1 or more.
- a plurality of Y 3 may be the same or different. However, at least one Y 3 represents a glycidyl group.
- R 13 represents a hydrogen atom or a methyl group
- Y 4 and Y 5 each independently represent a hydrogen atom or a glycidyl group.
- Two R 13 may be the same or different. However, at least one of Y 4 and Y 5 represents a glycidyl group.
- R 14 represents a hydrogen atom or a methyl group, respectively Y 6 and Y 7 are independently a hydrogen atom or a glycidyl group. Two R 14 may be the same or different. However, at least one of Y 6 and Y 7 represents a glycidyl group.
- the resin (A ′) has a hydroxyl group formed by an addition reaction between the epoxy group of the epoxy resin (a) and the carboxyl group of the vinyl group-containing monocarboxylic acid (b).
- Examples of the novolak type epoxy resin represented by the general formula (4) include a phenol novolak type epoxy resin and a cresol novolak type epoxy resin. These novolak-type epoxy resins can be obtained, for example, by reacting a phenol novolak resin, a cresol novolak resin and epichlorohydrin by a known method.
- epoxy resin (a) a novolac type epoxy resin represented by the general formula (4) is preferable from the viewpoint of excellent process tolerance and improved solvent resistance.
- Examples of the phenol novolak type epoxy resin or cresol novolak type epoxy resin represented by the general formula (4) include YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, and YDPN- 602 (above, manufactured by Toto Kasei Co., Ltd., trade name), DEN-431, DEN-439 (above, made by Dow Chemical Co., Ltd., trade name), EOCN-120, EOCN-102S, EOCN-103S, EOCN- 104S, EOCN-1012, EOCN-1025, EOCN-1027, BREN (above, Nippon Kayaku Co., Ltd., trade name), EPN-1138, EPN-1235, EPN-1299 (above, Ciba Specialty Chemicals ( Product name), N-730, N-770, N 865, N-665, N-673, VH-4150, VH-4240 (or more,
- Y 2 is a glycidyl group
- the bisphenol A type epoxy resin and the bisphenol F type epoxy resin can be obtained, for example, by reacting the hydroxyl group of the bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by the following general formula (9) with epichlorohydrin. it can.
- R 12 represents a hydrogen atom or a methyl group
- n2 represents an integer of 1 or more.
- the reaction is preferably carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethylsulfoxide in the presence of an alkali metal hydroxide at a reaction temperature of 50 to 120 ° C.
- a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethylsulfoxide
- an alkali metal hydroxide at a reaction temperature of 50 to 120 ° C.
- Examples of the bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by the general formula (5) include, for example, Epicoat 807, 815, 825, 827, 828, 834, 1001, 1004, 1007 and 1009 (above, Japan Epoxy Resin) (Trade name), DER-330, DER-301, DER-361 (above, trade name, manufactured by Dow Chemical Co., Ltd.), YD-8125, YDF-170, YDF-170, YDF-175S, YDF-2001, YDF-2004, YDF-8170 (manufactured by Toto Kasei Co., Ltd., trade name) and the like are commercially available.
- salicylaldehyde type epoxy resin represented by the general formula (6) for example, FAE-2500, EPPN-501H, EPPN-502H (above, Nippon Kayaku Co., Ltd., trade name) are commercially available. It is.
- the epoxy resin (a) is a repeating unit represented by the general formula (7) and / or the general formula (8) from the viewpoint of further reducing the warpage of the thin film substrate and further improving the thermal shock resistance. It is preferable to use an epoxy resin having
- vinyl group-containing monocarboxylic acid (b) examples include acrylic acid, a dimer of acrylic acid, methacrylic acid, ⁇ -furfurylacrylic acid, ⁇ -styrylacrylic acid, cinnamic acid, crotonic acid, ⁇ - Acrylic acid derivatives such as cyanocinnamic acid, half-ester compounds which are reaction products of hydroxyl group-containing acrylates and dibasic acid anhydrides, vinyl group-containing monoglycidyl ethers or vinyl group-containing monoglycidyl esters and dibasic acid anhydrides The half-ester compound which is a reaction product of is mentioned.
- the half ester compound is obtained by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride in an equimolar ratio.
- vinyl group-containing monocarboxylic acids (b) can be used singly or in combination of two or more.
- Examples of the hydroxyl group-containing acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester used in the synthesis of the half ester compound as an example of the vinyl group-containing monocarboxylic acid (b) include hydroxyethyl acrylate, hydroxyethyl Methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol tris Methacrylate, dipentaerythritol pentaacrylate, Pentaerythritol penta methacrylate, glycidyl acrylate, glycidyl methacrylate and the like
- dibasic acid anhydride used for the synthesis of the half ester compound one containing a saturated group or one containing an unsaturated group can be used.
- dibasic acid anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride.
- examples include acid, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.
- the vinyl group-containing monocarboxylic acid (b) is 0.6 to 0.6 to 1 equivalent of the epoxy group of the epoxy resin (a).
- the reaction is preferably carried out at a ratio of 1.05 equivalents, more preferably carried out at a ratio of 0.8 to 1.0 equivalents.
- the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b) can be reacted by dissolving in an organic solvent.
- organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic carbonization such as octane and decane
- petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha,
- a catalyst in order to promote the reaction.
- the catalyst for example, triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, triphenylphosphine, and the like can be used.
- the amount of the catalyst used is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b).
- a polymerization inhibitor for the purpose of preventing polymerization during the reaction.
- the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like.
- the amount of the polymerization inhibitor used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass in total of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b).
- the reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C.
- a vinyl group-containing monocarboxylic acid (b) and a phenolic compound such as p-hydroxyphenethyl alcohol, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic acid
- a polybasic acid anhydride such as an anhydride can be used in combination.
- the acid-modified vinyl group-containing epoxy resin is a resin (A ′′) obtained by reacting the above-mentioned resin (A ′) with a polybasic acid anhydride (c). Is also preferable.
- the hydroxyl group in the resin (A ′) (including the original hydroxyl group in the epoxy resin (a)) and the acid anhydride group of the polybasic acid anhydride (c) are half-esterified. It is presumed that
- polybasic acid anhydride (c) one containing a saturated group or one containing an unsaturated group can be used.
- specific examples of the polybasic acid anhydride (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexa Hydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like can be mentioned.
- the polybasic acid anhydride (c) is 0.1 to 1.0 equivalent per 1 equivalent of the hydroxyl group in the resin (A ′). By reacting, the acid value of the acid-modified vinyl group-containing epoxy resin can be adjusted.
- the acid value of the acid-modified vinyl group-containing epoxy resin is preferably 30 to 150 mgKOH / g, more preferably 40 to 120 mgKOH / g, and particularly preferably 50 to 100 mgKOH / g. If the acid value is less than 30 mg KOH / g, the solubility of the photosensitive resin composition in a dilute alkaline solution tends to be reduced, and if it exceeds 150 mg KOH / g, the electric properties of the cured film tend to be reduced.
- the reaction temperature between the resin (A ′) and the polybasic acid anhydride (c) is preferably 60 to 120 ° C.
- epoxy resin (a) for example, a hydrogenated bisphenol A type epoxy resin can be partially used together.
- the content of the component (A) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total solid content of the photosensitive resin composition.
- the content is preferably 15 to 40% by mass.
- (B) phenolic compound used in the present invention examples include 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6- Dicyclohexyl-4-methylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4 -N-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-2-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t-hexylphenol 2-cyclohexyl-4-n-butyl-6-isopropylphenol, dl- ⁇ -tocopherol, t-butylhydroquinone, 2,2′-methylenebis (4-methyl)
- Examples of the (B) phenolic compound include Irganox 1010 (Irganox 1010, manufactured by Ciba Specialty Chemicals), Irganox 1076 (Irganox 1076, manufactured by Ciba Specialty Chemicals), Irganox 1330 (Irganox 1330).
- the (B) phenolic compound can be used alone or in combination of two or more.
- the phenolic compound represented by the following general formula (1) is used as the phenolic compound. It is preferable to use it.
- R 1 represents an alkyl group having 1 to 5 carbon atoms, and at least one R 1 is preferably a tert-butyl group.
- M represents an integer of 1 to 4, and is preferably 2.
- N represents an integer of 1 to 4, preferably 2 to 4, and more preferably 2 to 3.
- A is an n-valent organic group, but from the viewpoint of further improving the solder heat resistance in addition to the adhesive strength between the underfill material after the PCT resistance test and the cured film, the number of divalent to tetravalent carbon atoms is 1 to 5
- the number of divalent to tetravalent carbon atoms is 1 to 5
- it is especially preferable that A in General formula (1) does not contain an ester bond.
- R 2 represents an alkyl group having 1 to 5 carbon atoms, and t represents an integer of 1 to 3.
- the compound represented by the following general formula (10) can be used as the (B) phenol compound. Most preferably, it is used.
- R 3 , R 4 , R 5 and R 6 each independently represents an alkyl group having 1 to 5 carbon atoms, and Z represents a hydrogen atom or an organic group represented by the following general formula (11). Indicates a group.
- R 7 and R 8 each independently represents an alkyl group having 1 to 5 carbon atoms.
- Examples of (B) phenolic compounds that can further improve the solder heat resistance and the adhesive strength between the underfill material after the PCT resistance test and the cured film are 2,2′-methylenebis (4-methyl-6-t-butylphenol) ), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6) -T-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis "6- (methylcyclohexyl) -p-cresol", 2,2'-ethylidene Bis (4,6-di-tert-butylphenol), 2,2′-butylidenebis (2-tert-butyl-4-methylphenol), Tris (3,5-di-tert-butyl) 4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl
- tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl- 4-hydroxybenzyl) benzene, tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl) Phenyl) butane, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) is particularly preferred.
- the content of the component (B) is preferably 0.01 to 10% by mass, and preferably 0.1 to 5% by mass based on the total solid content of the photosensitive resin composition. More preferred is 0.5 to 3% by mass.
- the content of the component (B) is less than 0.01% by mass, the effect of improving the adhesion between the cured film after the PCT resistance test and the underfill material tends to be difficult to obtain sufficiently, and 10% by mass. If it exceeds 1, the sensitivity tends to decrease.
- the compound having at least one ethylenically unsaturated group in the molecule is preferably a compound having a molecular weight of 1000 or less, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. Hydroxyalkyl (meth) acrylates, mono- or di (meth) acrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, etc.
- (Meth) acrylamides aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, Polyhydric alcohols such as pentaerythritol and tris-hydroxyethyl isocyanurate, or poly (meth) acrylates of these ethylene oxide or propylene oxide adducts, phenoxyethyl (meth) acrylate, polyethoxydi (meth) acrylate of bisphenol A, etc.
- aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, Polyhydric alcohols such as pent
- (Meth) acrylates of phenolic ethylene oxide or propylene oxide adducts glycidyl ether (meth) acrylates such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, and melamine (meth) acrylate Acrylamide, acrylonitrile, diacetone acrylamide, styrene, vinyltoluene and the like.
- These (C) compounds having at least one ethylenically unsaturated group in the molecule are used singly or in combination of two or more.
- the content of the component (C) is preferably 1 to 30% by mass, more preferably 2 to 20% by mass based on the total solid content of the photosensitive resin composition.
- the content is preferably 3 to 10% by mass.
- Photopolymerization initiator examples include benzoins such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] Acetophenones such as -2-morpholino-1-propanone and N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthr
- (D) light such as tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like.
- the polymerization initiation assistants can be used alone or in combination of two or more.
- the content of the component (D) is preferably 0.5 to 20% by mass, based on the total solid content of the photosensitive resin composition, and preferably 1 to 10% by mass. Is more preferable, and 2 to 6% by mass is particularly preferable.
- the content of the component (D) is less than 0.5% by mass, the exposed part tends to be eluted during development, and when it exceeds 20% by mass, the heat resistance tends to decrease.
- inorganic fine particles examples include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), tantalum oxide (Ta 2 O 5 ), zirconia (ZrO 2 ), and silicon nitride (Si 3 ).
- the content of the component (E) is preferably 15 to 80% by mass, more preferably 20 to 70% by mass based on the total solid content of the photosensitive resin composition. 25 to 50% by mass is particularly preferable, and 30 to 45% by mass is most preferable.
- the content of the component (E) is within the above range, film strength, heat resistance, insulation reliability, thermal shock resistance, resolution, and the like can be further improved.
- the inorganic fine particles preferably have a maximum particle size of 0.1 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m, particularly preferably 0.1 to 5 ⁇ m, and preferably 0.1 to 1 ⁇ m. Most preferred. When the maximum particle diameter exceeds 20 ⁇ m, the insulation reliability tends to be impaired.
- silica fine particles are preferably used from the viewpoint of improving heat resistance, solder heat resistance, HAST property (insulation reliability), crack resistance (heat shock resistance), and PCT resistance test.
- barium sulfate fine particles it is preferable to use barium sulfate fine particles.
- fine-particles are surface-treated with an alumina and / or an organosilane type compound from a viewpoint which can improve the aggregation prevention effect.
- the elemental composition of aluminum on the surface of the barium sulfate fine particles surface-treated with alumina and / or an organic silane compound is preferably 0.5 to 10 atomic%, more preferably 1 to 5 atomic%. 1.5 to 3.5 atomic% is particularly preferable.
- the elemental composition of silicon on the surface of the barium sulfate fine particles is preferably 0.5 to 10 atomic%, more preferably 1 to 5 atomic%, and more preferably 1.5 to 3.5 atomic%. It is particularly preferred.
- the elemental composition of carbon on the surface of the barium sulfate fine particles is preferably 10 to 30 atomic%, more preferably 15 to 25 atomic%, and particularly preferably 18 to 23 atomic%. These elemental compositions can be measured using XPS.
- the content is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and more preferably 20 to 40% by mass based on the total solid content of the photosensitive resin composition. % Is particularly preferred, with 25 to 35 weight being most preferred.
- the content of the barium sulfate fine particles is within the above range, the solder heat resistance and the adhesive strength between the underfill material after the PCT resistance test and the cured film can be further improved.
- the barium sulfate fine particles surface-treated with alumina and / or an organosilane compound are commercially available, for example, as NanoFine BFN40DC (trade name, manufactured by Nippon Solvay Co., Ltd.).
- the photosensitive resin composition of the present invention further contains (F) a curing agent, (H) an epoxy resin curing agent, and / or (G) an elastomer in addition to the components (A) to (E) described above. Also good.
- a curing agent e.g., a curing agent for curing a curing agent for curing a curing agent for curing a curing a curing agent for curing a curing agent, and / or (G) an elastomer in addition to the components (A) to (E) described above. Also good.
- each component will be described.
- the curing agent is preferably a compound that cures itself by heat, ultraviolet rays or the like, or (A) a compound that cures by reacting with carboxyl groups, hydroxyl groups, heat, ultraviolet rays, etc. of the acid-modified vinyl group-containing epoxy resin. .
- the curing agent By using a hardening
- Examples of the curing agent include thermosetting compounds such as epoxy compounds, melamine compounds, urea compounds, oxazoline compounds, and block type isocyanates.
- Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol S type epoxy resin, and biphenyl type epoxy resin. , Naphthalene type epoxy resin, dicyclo type epoxy resin, hydantoin type epoxy resin, heterocyclic epoxy resin such as triglycidyl isocyanurate, and bixylenol type epoxy resin.
- Examples of the melamine compound include triaminotriazine, hexamethoxymelamine, hexabutoxylated melamine and the like.
- Examples of the urea compound include dimethylol urea.
- curing agent contains an epoxy compound (epoxy resin) and / or block type isocyanate from a viewpoint which can improve the heat resistance of a cured film more, and an epoxy compound and block type isocyanate are included. It is more preferable to use together.
- the block type isocyanate an addition reaction product of a polyisocyanate compound and an isocyanate blocking agent is used.
- the polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate.
- 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, lactic acid Alcohol-based blocking agents such as chill and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetoaldoxime, acetoxi
- the curing agent is used alone or in combination of two or more.
- a curing agent When (F) a curing agent is used, its content is preferably 2 to 40% by mass, more preferably 3 to 30% by mass, based on the total solid content of the photosensitive resin composition, It is particularly preferably 5 to 20% by mass.
- the content of the curing agent By setting the content of the curing agent in the range of 2 to 40% by mass, the heat resistance of the formed cured film can be further improved while maintaining good developability.
- the elastomer can be suitably used when the photosensitive resin composition of the present invention is used for a semiconductor package substrate.
- the crosslinking reaction proceeds by ultraviolet rays or heat, so that the (A) acid-modified vinyl group-containing epoxy resin is cured and contracted. Further, the problem that distortion (internal stress) is applied to the inside of the resin and flexibility and adhesiveness are lowered can be solved.
- (G) elastomers examples include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, and silicone elastomers.
- These (G) elastomers are composed of a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness.
- styrene elastomer examples include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, and styrene-ethylene-propylene-styrene block copolymer.
- styrene derivatives such as ⁇ -methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene and the like can be used in addition to styrene.
- the olefin elastomer is a copolymer of ⁇ -olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene.
- ⁇ -olefin having 2 to 20 carbon atoms
- specific examples thereof include ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene
- EPR ethylene-propylene copolymer
- EPDM ethylene-propylene-diene copolymer
- dicyclopentadiene 1,4-hexadiene
- cyclooctadiene methylene norbornene
- ethylidene norbornene butadiene
- ethylene / ⁇ -olefin copolymer rubber More specifically, ethylene / ⁇ -olefin copolymer rubber, ethylene / ⁇ -olefin / non-conjugated diene copolymer rubber, propylene / ⁇ -olefin copolymer rubber, butene / ⁇ -olefin copolymer rubber, etc. Is mentioned.
- Miralastoma Mitsubishi Chemical
- EXACT Exxon Chemical
- ENGAGE Low Chemical
- hydrogenated styrene-butadiene rubber “DYNABON HSBR” (Nippon Synthetic Rubber Co., Ltd.)
- butadiene -Acrylonitrile copolymer "NBR series” (manufactured by Nippon Synthetic Rubber Co., Ltd.)
- carboxyl group-modified butadiene-acrylonitrile copolymer "XER series” manufactured by Nippon Synthetic Rubber Co., Ltd.
- polybutadiene partially Epoxidized epoxidized polybudadiene such as BF-1000 (manufactured by Nippon Soda Co., Ltd.), PB-3600 (manufactured by Daicel Chemical Industries, Ltd.), etc.
- Urethane elastomers are composed of structural units consisting of a hard segment composed of low-molecular glycol and diisocyanate, and a soft segment composed of high-molecular (long-chain) diol and diisocyanate.
- low-molecular glycol for example, short-chain diols such as ethylene glycol, propylene glycol, 1,4-butanediol, bisphenol A and the like can be used.
- the number average molecular weight of the short chain diol is preferably 48 to 500.
- polymer (long chain) diol examples include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene / 1,4-butylene adipate), polycaprolactone, and poly (1,6 -Hexylene carbonate), poly (1,6-hexylene neopentylene adipate) and the like.
- the number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000.
- urethane elastomers include PANDEX T-2185, T-2983N (manufactured by Dainippon Ink), sylactolan E790, and the like.
- polyester elastomer examples include those obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof.
- dicarboxylic acid examples include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which hydrogen atoms of these aromatic nuclei are substituted with methyl groups, ethyl groups, phenyl groups, and the like, Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These compounds can be used individually by 1 type or in combination of 2 or more types.
- diol compound examples include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol.
- diol compound examples include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol.
- dihydric phenol represented by the following general formula (12).
- Y 11 represents a single bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, —O—, —S—, or —SO 2 —
- R 21 and R 22 represents a halogen atom or an alkyl group having 1 to 12 carbon atoms
- p and q represent an integer of 0 to 4
- r represents 0 or 1.
- dihydric phenol represented by the general formula (12) examples include bisphenol A, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane, and resorcin. These compounds can be used individually by 1 type or in combination of 2 or more types.
- a multi-block copolymer having an aromatic polyester (for example, polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) portion as a soft segment component can be used.
- aromatic polyester for example, polybutylene terephthalate
- aliphatic polyester for example, polytetramethylene glycol
- Polyamide elastomers are broadly classified into two types: polyether block amide type and polyether ester block amide type using polyamide for the hard segment and polyether or polyester for the soft segment.
- polyamide polyamide-6, 11, 12 or the like is used.
- polyether polyoxyethylene, polyoxypropylene, polytetramethylene glycol or the like is used.
- UBE polyamide elastomer manufactured by Ube Industries Co., Ltd.
- Daiamide manufactured by Daicel Huls Co., Ltd.
- PEBAX manufactured by Toray Industries, Inc.
- Grilon ELY manufactured by MMS Japan Co., Ltd.
- Nopamid Mitsubishi Chemical Co., Ltd.
- Glais Dainippon Ink Co., Ltd.
- the acrylic elastomer is mainly composed of acrylic acid ester, and ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, or the like is used. Moreover, glycidyl methacrylate, allyl glycidyl ether, etc. are used as a crosslinking point monomer. Furthermore, acrylonitrile and ethylene can be copolymerized.
- an acrylonitrile-butyl acrylate copolymer an acrylonitrile-butyl acrylate-ethyl acrylate copolymer, an acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, or the like can be used.
- Silicone elastomers are mainly composed of organopolysiloxane and are classified into polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Some are modified with vinyl groups, alkoxy groups, and the like. Specific examples include the KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series, SH series (above, manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like.
- a rubber-modified epoxy resin can also be used.
- the rubber-modified epoxy resin includes, for example, a part or all of the epoxy groups of the bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolac type epoxy resin or cresol novolac type epoxy resin. It can be obtained by modification with terminal carboxylic acid-modified butadiene-acrylonitrile rubber, terminal amino-modified silicone rubber or the like.
- both terminal carboxyl group-modified butadiene-acrylonitrile copolymers Espel which is a polyester-based elastomer having a hydroxyl group (Espel 1612, 1620, manufactured by Hitachi Chemical Co., Ltd.), Epoxidized polybutadiene, etc. are preferred.
- Espel 1612, 1620, manufactured by Hitachi Chemical Co., Ltd. Epoxidized polybutadiene, etc.
- An elastomer that is liquid at room temperature is particularly preferred.
- the elastomer (G) When the elastomer (G) is used, its content is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferable that the content be ⁇ 10% by mass. (G) By making the elastomer content in the range of 1 to 20% by mass, the thermal shock resistance and the adhesive strength between the underfill material and the cured film can be further improved while maintaining good developability. it can. Moreover, when using for a thin film substrate, the curvature property of a thin film substrate can be reduced.
- an epoxy resin curing agent can be added for the purpose of further improving various properties such as heat resistance, adhesion, and chemical resistance of the cured film to be formed. .
- (H) epoxy resin curing agent examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4- Imidazole derivatives such as methyl-5-hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide
- organic acid salts and / or epoxy adducts amine complexes of boron trifluoride; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl -S Tri
- an epoxy resin curing agent When (H) an epoxy resin curing agent is used, its content is preferably 0.01 to 20% by mass, based on the total solid content of the photosensitive resin composition, and preferably 0.1 to 10% by mass. More preferably.
- thermoplastic resin can be added to the photosensitive resin composition of the present invention in order to further improve the flexibility of the cured film.
- thermoplastic resin examples include acrylic resin and urethane resin.
- the content when the thermoplastic resin is contained is preferably 1 to 30% by mass, preferably 5 to 20% by mass, based on the total solid content of the photosensitive resin composition. More preferred.
- the photosensitive resin composition of the present invention includes, as necessary, organic fine particles such as melamine and organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene.
- organic fine particles such as melamine and organic bentonite
- phthalocyanine blue such as a melamine and organic bentonite
- phthalocyanine green such as phthalocyanine green
- iodine green diazo yellow
- crystal violet titanium oxide
- carbon black naphthalene
- Known colorants such as black
- polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol and pyrogallol
- thickeners such as benton and montmorillonite
- silicone-based such as fluorine-based and vinyl resin-based antifoaming agents
- silane Various commonly known additives such as coupling agents and
- flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate compounds of phosphorous compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters can also be added.
- an organic solvent can be used as the diluent.
- the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic carbonization such as octane and decane
- Examples thereof include petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.
- the photosensitive resin composition of the present invention can be obtained by uniformly kneading and mixing the above-described components with a roll mill, a bead mill or the like.
- the photosensitive resin composition of the present invention can be used, for example, to form an image and produce a cured film as follows.
- the negative film is directly contacted (or non-contacted through a transparent film) and irradiated with active light (eg, ultraviolet light) with an exposure dose of preferably 10 to 1,000 mJ / cm 2 , Thereafter, the unexposed portion is dissolved and removed (developed) with a dilute alkaline aqueous solution or an organic solvent. Next, the exposed portion is sufficiently cured by post-exposure (ultraviolet exposure) and / or post-heating to obtain a cured film.
- the post-exposure is preferably performed at an exposure amount of 1 to 5 J / cm 2 , for example, and the post-heating is preferably performed at 100 to 200 ° C. for 30 minutes to 12 hours.
- the photosensitive resin composition of the present invention can be laminated on a support to form a photosensitive element.
- the thickness of the layer made of the photosensitive resin composition is preferably 10 to 100 ⁇ m.
- As the support a film having a thickness of 5 to 100 ⁇ m such as polyethylene terephthalate is preferably used.
- the layer made of the photosensitive resin composition is preferably formed by applying and drying a solution of the photosensitive resin composition on a support film.
- THPAC tetrahydrophthalic anhydride
- carbitol acetate 100 parts by mass of tetrahydrophthalic anhydride (THPAC) and 85 parts by mass of carbitol acetate are added, heated to 80 ° C. and reacted for about 6 hours, and then cooled to obtain a solid content concentration of 75. % Of a THPAC-modified cresol novolac epoxy acrylate (hereinafter referred to as “acid-modified vinyl group-containing epoxy resin (A-2)”) as a component (A).
- A-2 THPAC-modified cresol novolac epoxy acrylate
- Examples 1 to 10, Comparative Examples 1 to 11 The materials shown in Tables 1 and 2 below were blended in the blending amounts (unit: parts by mass) shown in the same table, then kneaded with a three-roll mill, and carbitol acetate was added so that the solid content concentration would be 70% by weight. In addition, a photosensitive resin composition was obtained. In addition, the compounding quantity of each material in following Table 1 and 2 shows the compounding quantity of solid content.
- the photosensitive resin compositions of Examples and Comparative Examples were applied to a copper-clad laminate (MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.) by screen printing so that the film thickness after drying was 25 ⁇ m. Then, it was dried using a hot air circulation dryer at 75 ° C. for 30 minutes.
- the density region is 0.00 to 2.00
- the density step is 0.05
- the size of the tablet (rectangle) is 20 mm ⁇ 187 mm
- the size of each step (rectangle) is 3 mm ⁇ 12 mm.
- a phototool (Stofer) having a 41-step tablet is closely attached, irradiated with ultraviolet rays with an integrated exposure amount of 600 mJ / cm 2 , developed with a 1% by weight aqueous sodium carbonate solution for 60 seconds, and the number of remaining step steps is set.
- the sensitivity was evaluated. The greater the number of remaining step steps, the higher the sensitivity, and it is preferable that 18 steps or more remain.
- the evaluation results are shown in Tables 3 and 4.
- the obtained coating film was irradiated with ultraviolet rays having an accumulated exposure amount of 600 mJ / cm 2 through a negative film in which light non-transmission portions of ⁇ 80 ⁇ m and ⁇ 110 ⁇ m were scattered in an area of 1 ⁇ 1 cm square, and 1% by mass of sodium carbonate Spray development was performed with an aqueous solution for 60 seconds at a pressure of 1.8 kgf / cm 2 , and an unexposed portion was dissolved and developed to form an image. Thereafter, the opening diameter was measured using a microscope (manufactured by HIROX, model number: KH-3000), and evaluated according to the following criteria. The evaluation results are shown in Tables 3 and 4.
- A Opening diameter of 80% or more (64 ⁇ m or more for ⁇ 80 ⁇ m negative film, 88 ⁇ m or more for ⁇ 110 ⁇ m negative film).
- B Opening diameter of 70% or more and less than 80% (56 ⁇ m or more and less than 64 ⁇ m for ⁇ 80 ⁇ m negative film, 77 ⁇ m or more and less than 88 ⁇ m for ⁇ 110 ⁇ m negative film).
- C Opening diameter is less than 70% (less than 56 ⁇ m for ⁇ 80 ⁇ m negative film, less than 77 ⁇ m for ⁇ 110 ⁇ m negative film).
- Thermal shock resistance The test piece was subjected to thermal history with one cycle of ⁇ 55 ° C./30 minutes and 125 ° C./30 minutes, and after 1,000 cycles, the test piece was visually observed and observed with a microscope, and evaluated according to the following criteria. The evaluation results are shown in Tables 3 and 4. A: No crack occurred B: Crack occurred
- the shear strength at room temperature was measured using a bond tester (Dage 4000, manufactured by Dage), and the unit per unit area was measured. The adhesive strength was determined. Each material was measured with 5 samples, and the average values were compared. The unit is MPa. At this time, the height of the test head was 100 ⁇ m from the top of the coating film, and the speed of the test head was 100 ⁇ m / second.
- the composition of the underfill material is CEL-C-3801 (trade name, manufactured by Hitachi Chemical Co., Ltd.) composed of bisphenol F type epoxy resin, acid anhydride as a curing agent, and silica fine particles (67% by mass). Was used. The evaluation results are shown in Tables 3 and 4.
- a photosensitive resin composition for a protective film of a printed wiring board for a semiconductor package can be provided.
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Abstract
Description
[式(1)中、R1は炭素数1~5のアルキル基を示し、mは1~4の整数を示し、nは1~4の整数を示し、Aはn価の有機基を示す。なお、m及び/又はnが2以上の場合、複数存在するR1は同一でも異なっていてもよい。]
[式(4)中、R11は水素原子又はメチル基を示し、Y1は水素原子又はグリシジル基を示し、n1は1以上の整数を示す。なお、複数存在するR11及びY1はそれぞれ同一でも異なっていてもよい。但し、少なくとも一つのY1はグリシジル基を示す。]
[式(5)中、R12は水素原子又はメチル基を示し、Y2は水素原子又はグリシジル基を示し、n2は1以上の整数を示す。なお、複数存在するR12は同一でも異なっていてもよい。また、n2が2以上の場合、複数存在するY2は同一でも異なっていてもよい。]
[式(7)中、R13は水素原子又はメチル基を示し、Y4及びY5はそれぞれ独立に水素原子又はグリシジル基を示す。なお、2つのR13は同一でも異なっていてもよい。但し、Y4及びY5の少なくとも一方はグリシジル基を示す。]
[式(8)中、R14は水素原子又はメチル基を示し、Y6及びY7はそれぞれ独立に水素原子又はグリシジル基を示す。なお、2つのR14は同一でも異なっていてもよい。但し、Y6及びY7の少なくとも一方はグリシジル基を示す。]
(A)酸変性ビニル基含有エポキシ樹脂としては、例えば、エポキシ樹脂をビニル基含有モノカルボン酸で変性した樹脂を用いることができるが、特に、下記一般式(4)で表されるノボラック型エポキシ樹脂、下記一般式(5)で表されるビスフェノール型エポキシ樹脂、下記一般式(6)で表されるサリチルアルデヒド型エポキシ樹脂、並びに、下記一般式(7)又は(8)で表される繰り返し単位を有するビスフェノール型ノボラック樹脂からなる群より選択される少なくとも1種のエポキシ樹脂(a)と、ビニル基含有モノカルボン酸(b)と、を反応させて得られる樹脂(A’)を用いることが好ましい。
[式(4)中、R11は水素原子又はメチル基を示し、Y1は水素原子又はグリシジル基を示し、n1は1以上の整数を示す。なお、複数存在するR11及びY1はそれぞれ同一でも異なっていてもよい。但し、少なくとも一つのY1はグリシジル基を示す。]
[式(5)中、R12は水素原子又はメチル基を示し、Y2は水素原子又はグリシジル基を示し、n2は1以上の整数を示す。なお、複数存在するR12は同一でも異なっていてもよい。また、n2が2以上の場合、複数存在するY2は同一でも異なっていてもよい。]
[式(7)中、R13は水素原子又はメチル基を示し、Y4及びY5はそれぞれ独立に水素原子又はグリシジル基を示す。なお、2つのR13は同一でも異なっていてもよい。但し、Y4及びY5の少なくとも一方はグリシジル基を示す。]
[式(8)中、R14は水素原子又はメチル基を示し、Y6及びY7はそれぞれ独立に水素原子又はグリシジル基を示す。なお、2つのR14は同一でも異なっていてもよい。但し、Y6及びY7の少なくとも一方はグリシジル基を示す。]
であるビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂は、例えば、下記一般式(9)で示されるビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂の水酸基とエピクロルヒドリンとを反応させることにより得ることができる。
本発明に用いられる(B)フェノール系化合物としては、例えば、2,6-ジ-t-ブチル-4-メチルフェノール、2,6-ジ-t-ブチル-4-エチルフェノール、2,6-ジシクロへキシル-4-メチルフェノール、2,6-ジ-t-アミル-4-メチルフェノール、2,6-ジ-t-オクチル-4-n-プロピルフェノール、2,6-ジシクロへキシル-4-n-オクチルフェノール、2-イソプロピル-4-メチル-6-t-ブチルフェノール、2-t-ブチル-2-エチル-6-t-オクチルフェノール、2-イソブチル-4-エチル-6-t-へキシルフェノール、2-シクロへキシル-4-n-ブチル-6-イソプロピルフェノール、dl-α-トコフェロール、t-ブチルヒドロキノン、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、4,4’-ブチリデンビス(3-メチル-6-t-ブチルフェノール)、4-4’-チオビス(3-メチル-6-t-ブチルフェノール)、2,2’-チオビス(4-メチル-6-t-ブチルフェノール)、4,4’-メチレンビス(2,6-ジ-t-ブチルフェノール)、2,2’-メチレンビス「6-(メチルシクロへキシル)-p-クレゾール」、2,2’-エチリデンビス(4,6-ジ-t-ブチルフェノール)、2,2’-ブチリデンビス(2-t-ブチル-4-メチルフェノール)、2-t-ブチル-6-(3-t-ブチル-2-ヒドロキシン-5-メチルベンジル)-4-メチルフェニルアクリレート、2-[1-(2-ヒドロキシン-3,5-ジ-t-ベンチルフェニル)エチル]-4,6-ジ-t-ベンチルフェニルアクリレート、1,1,3-トリス(2-メチル-4-ヒドロキシ-5-t-ブチルフェニル)ブタン、トリエチレングリコールビス[3-(3-t-ブチル-5-メチル-4-ヒドロキシフェニル)プロピオネート]、1,6-へキサンジオールビス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]、2,2-チオジエチレンビス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]、N,N’-ヘキサメチレンビス(3,5-ジ-t-ブチル-4-ヒドロキシ-ヒドロシンナミド)、3-5-ジ-t-ブチル-4-ヒドロキシベンジンホスホネートジエチルエステル、トリス(2,6-ジ-メチル-3-ヒドロキシ-4-t-ブチルベンジル)イソシアヌレート、トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)イソシアヌレート、トリス[(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオニルオキシエチル]イソシアヌレート、トリス(4-t-ブチル-2,6-ジメチル-3-ヒドロキシベンジル)イソシアヌレート、2,4-ビス(n-オクチルオチ)-6-(4-ヒドロキシ-3,5-ジ-t-ブチルアニリノ)-1,3,5-トリアジン、テトラキス[メチレン-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]メタン、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)テレフタレート、1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-t-ブチル-4-ヒドロキベンジル)ベンゼン、3,9-ビス[1,1-ジメチル2-{β-(3-t-ブチル-4ヒドロキシ-5-メチルフェニル)プロピオニルオキシ}エチル]-2,4,8,10-テトラオキサスピロ「5,5」ウンデカン、2,2-ビス「4-(2,3,5-ジ-t-ブチル-4-ヒドロキシヒドロシンナモイルオキシ)」エトキシフェニル]プロパン、β-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリルエステルなどが挙げられる。
(C)分子内に少なくとも1つのエチレン性不飽和基を有する化合物としては、分子量が1000以下である化合物が好ましく、例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレート類、エチレングリコール、メトキシテトラエチレングリコール、ポリエチレングリコール等のグリコールのモノ又はジ(メタ)アクリレート類、N,N-ジメチル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド等の(メタ)アクリルアミド類、N,N-ジメチルアミノエチル(メタ)アクリレート等のアミノアルキル(メタ)アクリレート類、ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジトリメチロールプロパン、ジペンタエリスリトール、トリス-ヒドロキシエチルイソシアヌレート等の多価アルコール又はこれらのエチレンオキサイドあるいはプロピレンオキサイド付加物の多価(メタ)アクリレート類、フェノキシエチル(メタ)アクリレート、ビスフェノールAのポリエトキシジ(メタ)アクリレート等のフェノール類のエチレンオキサイドあるいはプロピレンオキサイド付加物の(メタ)アクリレート類、グリセリンジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレートなどのグリシジルエーテルの(メタ)アクリレート類、及びメラミン(メタ)アクリレート、アクリルアミド、アクリロニトリル、ジアセトンアクリルアミド、スチレン、ビニルトルエン等が挙げられる。これらの(C)分子内に少なくとも1つのエチレン性不飽和基を有する化合物は、1種を単独で又は2種以上を組み合わせて用いられる。
(D)光重合開始剤としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル等のベンゾイン類;アセトフェノン、2,2-ジメトキシ-2-フェニルアセトフェノン、2,2-ジエトキシ-2-フェニルアセトフェノン、1,1-ジクロロアセトフェノン、1-ヒドロキシシクロヘキシルフェニルケトン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン-1、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノ-1-プロパノン、N,N-ジメチルアミノアセトフェノン等のアセトフェノン類;2-メチルアントラキノン、2-エチルアントラキノン、2-tert-ブチルアントラキノン、1-クロロアントラキノン、2-アミルアントラキノン、2-アミノアントラキノン等のアントラキノン類;2,4-ジメチルチオキサントン、2,4-ジエチルチオキサントン、2-クロロチオキサントン、2,4-ジイソプロピルチオキサントン等のチオキサントン類;アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類;ベンゾフェノン、メチルベンゾフェノン、4,4’-ジクロロベンゾフェノン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、ミヒラーズケトン、4-ベンゾイル-4’-メチルジフェニルサルファイド等のベンゾフェノン類;2-(o-クロロフェニル)-4,5-ジフェニルイミダゾール二量体、2-(o-クロロフェニル)-4,5-ジ(m-メトキシフェニル)イミダゾール二量体、2-(o-フルオロフェニル)-4,5-ジフェニルイミダゾール二量体、2-(o-メトキシフェニル)-4,5-ジフェニルイミダゾール二量体、2-(p-メトキシフェニル)-4,5-ジフェニルイミダゾール二量体、2,4-ジ(p-メトキシフェニル)-5-フェニルイミダゾール二量体、2-(2,4-ジメトキシフェニル)-4,5-ジフェニルイミダゾール二量体等の2,4,5-トリアリールイミダゾール二量体類、9-フェニルアクリジン、1,7-ビス(9,9’-アクリジニル)ヘプタン等のアクリジン類;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等のアシルフォスフィンオキサイド類、1,2-オクタンジオン-1-[4-(フェニルチオ)フェニル]-2-(O-ベンゾイルオキシム)、1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]エタノン1-(O-アセチルオキシム)、1-フェニル-1,2-プロパンジオン-2-[O-(エトキシカルボニル)オキシム]等のオキシムエステル類が挙げられる。これらの(D)光重合開始剤は、1種を単独で又は2種以上を組み合わせて用いることができる。
(E)無機微粒子としては、例えば、シリカ(SiO2)、アルミナ(Al2O3)、チタニア(TiO2)、酸化タンタル(Ta2O5)、ジルコニア(ZrO2)、窒化ケイ素(Si3N4)、チタン酸バリウム(BaO・TiO2)、炭酸バリウム(BaCO3)、炭酸マグネシウム、酸化アルミニウム、水酸化アルミニウム、水酸化マグネシウム、チタン酸鉛(PbO・TiO2)、チタン酸ジルコン酸鉛(PZT)、チタン酸ジルコン酸ランタン鉛(PLZT)、酸化ガリウム(Ga2O3)、スピネル(MgO・Al2O3)、ムライト(3Al2O3・2SiO2)、コーディエライト(2MgO・2Al2O3/5SiO2)、タルク(3MgO・4SiO2・H2O)、チタン酸アルミニウム(TiO2-Al2O3)、イットリア含有ジルコニア(Y2O3-ZrO2)、ケイ酸バリウム(BaO・8SiO2)、窒化ホウ素(BN)、炭酸カルシウム(CaCO3)、硫酸バリウム(BaSO4)、硫酸カルシウム(CaSO4)、酸化亜鉛(ZnO)、チタン酸マグネシウム(MgO・TiO2)、ハイドロタルサイト、雲母、焼成カオリン、カーボン(C)等を使用することができる。これらの(E)無機微粒子は、1種を単独で又は2種以上を組み合わせて使用することができる。
(F)硬化剤としては、それ自体が熱、紫外線等で硬化する化合物、あるいは(A)酸変性ビニル基含有エポキシ樹脂のカルボキシル基、水酸基と熱、紫外線等で反応して硬化する化合物が好ましい。(F)硬化剤を用いることで、感光性樹脂組成物から形成される硬化膜の耐熱性、接着性、耐薬品性等を向上させることができる。
(G)エラストマーは、本発明の感光性樹脂組成物を半導体パッケージ基板に用いる場合に好適に使用することができる。本発明の感光性樹脂組成物に(G)エラストマーを添加することにより、紫外線や熱により橋架け反応(硬化反応)が進行することで(A)酸変性ビニル基含有エポキシ樹脂が硬化収縮して、樹脂の内部に歪み(内部応力)が加わり、可とう性や接着性が低下するという問題を解消することができる。
[式中、Y11は単結合、炭素数1~10のアルキレン基、炭素数4~8のシクロアルキレン基、-O-、-S-、又は、-SO2-を示し、R21及びR22はハロゲン原子又は炭素数1~12のアルキル基を示し、p及びqは0~4の整数を示し、rは0又は1を示す。]
上記一般式(8)で表される繰り返し単位(R14=水素原子、Y6及びY7=グリシジル基)を有するビスフェノールFノボラック型エポキシ樹脂(EXA-7376、大日本インキ化学工業社製)350質量部、アクリル酸70質量部、メチルハイドロキノン0.5質量部、カルビトールアセテート120質量部を仕込み、90℃に加熱して攪拌することにより反応させ、混合物を完全に溶解した。次に、得られた溶液を60℃に冷却し、トリフェニルホスフィン2質量部を加え、100℃に加熱して、溶液の酸価が1mgKOH/gになるまで反応させた。反応後の溶液に、テトラヒドロ無水フタル酸(THPAC)98質量部とカルビトールアセテート85質量部とを加え、80℃に加熱して約6時間反応させた後に冷却し、固形分の濃度が73質量%である(A)成分としてのTHPAC変性ビスフェノールF型ノボラックエポキシアクリレート(以下、「酸変性ビニル基含有エポキシ樹脂(A-1)」という)の溶液を得た。
上記一般式(4)で表される(R11=水素原子、Y1=グリシジル基)クレゾールノボラック型エポキシ樹脂(ESCN-195、住友化学社製)382質量部、アクリル酸90質量部、メチルハイドロキノン0.5質量部、カルビトールアセテート120質量部を仕込み、90℃に加熱して攪拌することにより反応させ、混合物を完全に溶解した。次に、得られた溶液を60℃に冷却し、トリフェニルホスフィン2質量部を加え、100℃に加熱して、溶液の酸価が1mgKOH/g以下になるまで反応させた。反応後の溶液に、テトラヒドロ無水フタル酸(THPAC)100質量部とカルビトールアセテート85質量部とを加え、80℃に加熱して約6時間反応させた後に冷却して、固形分の濃度が75%である(A)成分としてのTHPAC変性クレゾールノボラック型エポキシアクリレート(以下、「酸変性ビニル基含有エポキシ樹脂(A-2)」という)の溶液を得た。
下記表1及び2に示す各材料を、同表に示す配合量(単位:質量部)で配合した後、3本ロールミルで混練し、固形分濃度が70質量%になるようにカルビトールアセテートを加えて、感光性樹脂組成物を得た。なお、下記表1及び2中の各材料の配合量は、固形分の配合量を示す。
*1(酸変性ビニル基含有エポキシ樹脂(A-1)):合成例1で作製したTHPAC変性ビスフェノールF型ノボラックエポキシアクリレート、
*2(酸変性ビニル基含有エポキシ樹脂(A-2)):THPAC変性クレゾールノボラック型エポキシアクリレート、
*3(PB-3600):エポキシ化ポリブタジエン(ダイセル化学(株)製、商品名)、
*4(エピコート828):ビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン(株)製、商品名)、
*5(カヤラッドDPHA):ジペンタエリスリトールヘキサアクリレート(日本化薬(株)製、商品名)、
*6(イルガキュア907):2-メチル-[4-(メチルチオ)フェニル]モルホリノ-1-プロパノン(チバ・スペシャルティ・ケミカルズ(株)製、商品名)、
*7(カヤキュアDETX-S):2,4-ジエチルチオキサントン(日本化薬(株)製、商品名)、
*8(AO-20):フェノール系抗酸化剤(アデカ社製、商品名)、下記式(I)で表される化合物、
*9(AO-30):フェノール系抗酸化剤(アデカ社製、商品名)、下記式(II)で表される1,1,3-トリス(2-メチル-4-ヒドロキシ-5-t-ブチルフェニル)ブタン、
*10(AO-40):フェノール系抗酸化剤(アデカ社製、商品名)、下記式(III)で表される4,4’-ブチリデンビス(3-メチル-6-t-ブチルフェノール)、
*11(AO-50):フェノール系抗酸化剤(アデカ社製、商品名)、下記式(IV)で表されるステアリル-β-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート、
*12(AO-80):フェノール系抗酸化剤(アデカ社製、商品名)、下記式(V)で表される化合物、
*13(ヨシノックスBHT):フェノール系抗酸化剤(吉冨製薬社製、商品名)、下記式(VI)で表されるジブチルヒドロキシトルエン、
*14(PEP-4C):リン系抗酸化剤(アデカ社製、商品名)、下記式(VII)で表される化合物、
*15(PEP-8):リン系抗酸化剤(アデカ社製、商品名)、下記式(VIII)で表されるジステアリルペンタエリスリトールジフォスファイト、
*16(PEP-24G):リン系抗酸化剤(アデカ社製、商品名)、下記式(IX)で表される化合物、
*17(HP-10):リン系抗酸化剤(アデカ社製、商品名)、下記式(X)で表される化合物、
*18(AO-23):イオウ系抗酸化剤(アデカ社製、商品名)、下記式(XI)で表される化合物、
*19(AO-412S):イオウ系抗酸化剤(アデカ社製、商品名)、下記式(XII)で表される化合物、
*20(AO-503A):イオウ系抗酸化剤(アデカ社製、商品名)、下記式(XIII)で表される化合物、
*21(FLB-1):シリカ微粒子(タツモリ(株)製、商品名)、
*22(NanoFine BFN40DC):硫酸バリウム微粒子(日本ソルベイ(株)製、商品名)。
実施例及び比較例の感光性樹脂組成物を、銅張積層基板(MCL-E-67、日立化成工業(株)製)に、乾燥後の膜厚が25μmになるようにスクリーン印刷法で塗布した後、75℃で30分間熱風循環式乾燥機を用いて乾燥させた。得られた塗膜の表面に、濃度領域0.00~2.00、濃度ステップ0.05、タブレット(矩形)の大きさが20mm×187mmで、各ステップ(矩形)の大きさが3mm×12mmである41段ステップタブレットを有するフォトツール(ストーファー社製)を密着させ、積算露光量600mJ/cm2の紫外線を照射し、1質量%の炭酸ナトリウム水溶液で60秒間現像し、残存ステップ段数を感度として評価した。残存ステップ段数が多いほど高感度であり、18段以上残存していることが好ましい。評価結果を表3及び表4に示す。
実施例及び比較例の感光性樹脂組成物を、銅張積層基板(MCL-E-67、日立化成工業(株)製)に、乾燥後の膜厚が25μmになるようにスクリーン印刷法で塗布した後、75℃で30分間熱風循環式乾燥機を用いて乾燥させた。得られた塗膜に、1×1cm四方の面積にφ80μm及びφ110μmの光非透過部が点在するネガフィルムを介して積算露光量600mJ/cm2の紫外線を照射し、1質量%の炭酸ナトリウム水溶液で60秒間、1.8kgf/cm2の圧力でスプレー現像し、未露光部を溶解現像して像形成した。その後、マイクロスコープ(HIROX社製、型番:KH-3000)を用いて開口径を測定し、以下の基準で評価した。評価結果を表3及び表4に示す。
A:開口径が80%以上(φ80μmネガフィルムで64μm以上、φ110μmネガフィルムで88μm以上)のもの。
B:開口径が70%以上80%未満(φ80μmネガフィルムで56μm以上64μm未満、φ110μmネガフィルムで77μm以上88μm未満)のもの。
C:開口径が70%未満(φ80μmネガフィルムで56μm未満、φ110μmネガフィルムで77μm未満)のもの。
実施例及び比較例の感光性樹脂組成物を、厚さ0.6mmの銅張積層基板(MCL-E-67、日立化成工業(株)製)に、乾燥後の膜厚が25μmになるようにスクリーン印刷法で塗布した後、80℃で20分間熱風循環式乾燥機を用いて乾燥させた。次に、所定のパターンを有するネガマスクを塗膜に密着させ、紫外線露光装置を用いて600mJ/cm2の露光量で露光した。その後、1質量%の炭酸ナトリウム水溶液で60秒間、1.8kgf/cm2の圧力でスプレー現像し、未露光部を溶解現像した。次に、紫外線露光装置を用いて1000mJ/cm2の露光量で露光し、150℃で1時間加熱して、試験片を作製した。
上記試験片に水溶性フラックスを塗布し、265℃のはんだ槽に10秒間浸漬した。これを1サイクルとして、6サイクル繰り返した後、塗膜外観を目視観察し、以下の基準で評価した。評価結果を表3及び表4に示す。
A:外観変化なし
B:塗膜50mm2内に、塗膜のウキ又はフクレが1個~2個あり
C:塗膜50mm2内に、塗膜のウキ又はフクレが3個~5個あり
D:塗膜50mm2内に、塗膜のウキ又はフクレが6個以上あり
上記試験片を、-55℃/30分間、125℃/30分間を1サイクルとして熱履歴を加え、1,000サイクル経過後、試験片を目視観察及び顕微鏡観察し、以下の基準により評価した。評価結果を表3及び表4に示す。
A:クラック発生なし
B:クラック発生あり
上記試験片を15mm×15mmの大きさに切り出し、120℃、12時間乾燥させた。φ3.0mmの開口を設けた15mm×15mm×厚み1.0mmのシリコーンゴムを、試験片上に配置し、110℃のホットプレート上で開口部にアンダフィル材を注入した後、クリーンオーブンにて165℃で2時間硬化させた。室温に冷却した後、シリコーンゴムを取り外し、アンダフィル材との接着性評価用基板を得た。この接着性評価用基板を用いてPCT試験(121℃、2気圧、96時間)を行った後、ボンドテスタ(Dage4000、Dage社製)を用いて室温でのシェア強度を測定し、単位面積当たりの接着力を求めた。各材料ともに、試料数5個で測定し、平均値を比較した。単位はMPaである。このとき、テストヘッドの高さは塗膜上から100μm、テストヘッドの速度は100μm/秒とした。アンダフィル材の組成は、ビスフェノールF型エポキシ樹脂と、硬化剤である酸無水物、シリカ微粒子(67質量%)で構成されたCEL-C-3801(日立化成工業(株)製、商品名)を用いた。評価結果を表3及び表4に示す。
縦5cm、横5cm、厚さ18μmの銅箔に、実施例及び比較例の感光性樹脂組成物を、乾燥後の膜厚が25μmになるようにスクリーン印刷法で塗布した後、75℃で30分間熱風循環式乾燥機を用いて乾燥させ、紫外線露光装置を用いて600mJ/cm2の露光量で露光した。その後、1質量%の炭酸ナトリウム水溶液で60秒間、1.8kgf/cm2の圧力でスプレーした。次に、紫外線露光装置を用いて、1000mJ/cm2の露光量で露光し、150℃で1時間加熱して、反り性評価用試験片を得た。得られた試験片について、塗布面を下にして定盤上に置き、反り高さを評価した。評価結果を表3及び表4に示す。
Claims (8)
- (A)酸変性ビニル基含有エポキシ樹脂と、
(B)フェノール系化合物と、
(C)分子内に少なくとも1つのエチレン性不飽和基を有する化合物と、
(D)光重合開始剤と、
(E)無機微粒子と、
を含有する半導体パッケージ用プリント配線板の保護膜用感光性樹脂組成物。 - 前記一般式(1)中、少なくとも一つのR1がtert-ブチル基である、請求項2又は3に記載の半導体パッケージ用プリント配線板の保護膜用感光性樹脂組成物。
- 前記(A)酸変性ビニル基含有エポキシ樹脂が、下記一般式(4)で表されるノボラック型エポキシ樹脂、下記一般式(5)で表されるビスフェノール型エポキシ樹脂、下記一般式(6)で表されるサリチルアルデヒド型エポキシ樹脂、並びに、下記一般式(7)又は(8)で表される繰り返し単位を有するビスフェノール型ノボラック樹脂からなる群より選択される少なくとも1種のエポキシ樹脂(a)と、ビニル基含有モノカルボン酸(b)と、を反応させて得られる樹脂に、飽和若しくは不飽和基含有多塩基酸無水物(c)を反応させて得られる樹脂である、請求項1~4のいずれか一項に記載の半導体パッケージ用プリント配線板の保護膜用感光性樹脂組成物。
- 前記(E)無機微粒子の含有量が、感光性樹脂組成物の固形分全量を基準として15~80質量%である、請求項1~5のいずれか一項に記載の半導体パッケージ用プリント配線板の保護膜用感光性樹脂組成物。
- (F)硬化剤を更に含有する、請求項1~6のいずれか一項に記載の半導体パッケージ用プリント配線板の保護膜用感光性樹脂組成物。
- (G)エラストマーを更に含有する、請求項1~7のいずれか一項に記載の半導体パッケージ用プリント配線板の保護膜用感光性樹脂組成物。
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KR20110013495A (ko) | 2011-02-09 |
TWI396046B (zh) | 2013-05-11 |
US9075307B2 (en) | 2015-07-07 |
JP4900510B2 (ja) | 2012-03-21 |
TW201024918A (en) | 2010-07-01 |
CN102138104A (zh) | 2011-07-27 |
JPWO2010026927A1 (ja) | 2012-02-02 |
CN102138104B (zh) | 2013-01-23 |
US20110223539A1 (en) | 2011-09-15 |
KR101323928B1 (ko) | 2013-10-31 |
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