WO2001053890A1 - Photosensitive resin composition - Google Patents
Photosensitive resin composition Download PDFInfo
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- WO2001053890A1 WO2001053890A1 PCT/JP2000/009333 JP0009333W WO0153890A1 WO 2001053890 A1 WO2001053890 A1 WO 2001053890A1 JP 0009333 W JP0009333 W JP 0009333W WO 0153890 A1 WO0153890 A1 WO 0153890A1
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- photosensitive resin
- epoxy resin
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- resin composition
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
- H01L23/49894—Materials of the insulating layers or coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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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 has excellent developability in a dilute alkaline aqueous solution used for a solder resist of a printed wiring board, and a cured coating film has flexibility, water resistance, adhesion, and solder heat resistance.
- the present invention relates to a photosensitive resin composition having excellent electroless gold plating resistance, PCT (pressure cooker test) resistance, and the like. ⁇
- a screen printing method has been widely used as a method of forming a resist pattern on a printed wiring board.
- a method described in Japanese Patent Publication No. A photosensitive resin that can be developed with a low strength is used.
- This photosensitive resin has a propyloxyl group in a side chain obtained by reacting a novolak type epoxy resin with acrylic acid as an unsaturated monobasic acid, and reacting a generated hydroxyl group with a saturated or unsaturated polybasic acid anhydride. It is a novolak epoxy (meth) acrylate.
- semiconductors such as BGA (ball grid array) and CSP (chip size package), packages, and the like are commercially available.
- the whole is heated by infrared rays, and the solder is reflowed and fixed. Therefore, the conventional solder resist coating as disclosed in Japanese Patent Publication No. Films have problems such as cracks caused by thermal shock. At present, improvements are required for resist coatings such as impact resistance, adhesion, solder heat resistance, electroless gold plating resistance, and PCT resistance.
- dimethylolpropionic acid having two or more hydroxyl groups in one molecule and acrylyl as an unsaturated monobasic acid are added to a novolak type epoxy resin as described in JP-A-6-324490.
- Reaction with an acid The cured product of the photosensitive resin obtained by the reaction with water is excellent in adhesion, soldering heat resistance, electroless gold plating resistance, etc., but the amount of saturated or unsaturated polybasic acid anhydride added is dimethylolpropione.
- the number of hydroxyl groups is less than the number of hydroxyl groups in the acid, and the number of hydroxyl groups may be excessive, resulting in a decrease in water resistance and a problem in PCT resistance.
- increasing the amount of saturated or unsaturated polybasic anhydride to reduce the amount of hydroxyl groups increases the amount of carboxyl groups.
- an object of the present invention is to provide a solder resist for a printed wiring board, which has excellent developability in a dilute alkaline aqueous solution, and has a cured coating film having flexibility, water resistance, adhesion, solder heat resistance,
- An object of the present invention is to provide a photosensitive resin composition having excellent electroless gold plating resistance and PCT (pressure cooker test) resistance.
- the present invention provides (A) an epoxy resin (a) and a compound (b) having, in one molecule, one primary alcoholic hydroxyl group and one functional group selected from a carboxyl group and a secondary amino group. ) And an unsaturated monobasic acid (c), and further reacting a saturated or unsaturated polybasic anhydride (d) with a hydroxyl group of the reactant (I). Resin,
- a photosensitive resin composition comprising:
- the present invention provides the photosensitive resin (A), wherein the amount of the saturated or unsaturated polybasic anhydride (d) is from 0.6 mol to 1.0 mol per 1 mol of the primary hydroxyl group of the reactant (I). It is intended to provide the above-mentioned photosensitive resin composition, which is obtained by reacting at a certain ratio.
- the present invention provides the photosensitive resin (A), wherein an epoxy group of the epoxy resin (a) is used.
- the compound (b) and the unsaturated monobasic acid (c) are reacted in a total amount of 0.8 to 1.2 equivalents to 1 equivalent, and the compound (b) becomes 0.05 to 0.5 equivalent.
- the present invention provides the above-mentioned photosensitive resin composition, characterized in that the reaction is carried out in a proportion.
- the present invention also provides the photosensitive resin composition described above, which is blended in an amount of 1 to 50% by weight based on the epoxy resin (B) power composition.
- the present invention also provides the above photosensitive resin composition, wherein the photopolymerization initiator (C) is incorporated in an amount of from 5 to 20% by weight based on the composition.
- the present invention also provides the above-mentioned photosensitive resin composition, wherein the polymerizable unsaturated compound and / or the solvent (D) is blended in an amount of 5 to 80% by weight based on the composition. Disclosure of the invention
- the photosensitive resin in the present invention comprises (A) an epoxy resin (a) and a compound (1) having one primary alcoholic hydroxyl group and one functional group selected from a carboxyl group and a secondary amino group in one molecule. It is obtained by reacting a reaction product (I) of b) with an unsaturated monobasic acid (c) with a saturated or unsaturated polybasic anhydride (d).
- the epoxy resin (a) include a cresol nopolak epoxy resin, a phenol novolak epoxy resin, a dicyclopentene phenol weight-added epoxy resin, or an epoxy resin composed of a combination thereof. Further, the novolak type epoxy resin may be halogenated.
- part of the cresol nopolak epoxy resin, phenol novolak epoxy resin, dicyclopentene phenol monoaddition epoxy resin is partially replaced with bisphenol A epoxy resin, bisphenol —F-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, phenol phenol resin co-condensation-type epoxy resin, bisphenol A novolak-type epoxy resin, bisphenol F-novolak-type epoxy resin, triphenyl alcohol epoxide Epoxy resin obtained by reacting epichlorohydrin with polyfunctional phenol such as resin, tetraphenyl ethane type epoxy resin, and epoxy resin obtained by reacting epichlorohydrin with polyfunctional hydroxynaphthalenes , Silicone modified Epoxy resins, epoxy-modified lactone-modified epoxy resins, glycidylamine-type epoxy resins obtained by the reaction of epichlorohydrin with primary or secondary amines, heterocyclic epoxy resins such as trigly
- glycolic acid compounds having a primary alcoholic hydroxyl group and a carboxyl group, such as, vivalic acid, 2-hydroxy-2-methylbutyric acid, 2-ethyl-2-hydroxybutyric acid, and 16-hydroxyhexadecanoic acid; and N-benzylethanolamine.
- Compounds having a primary alcoholic hydroxyl group and a secondary amino group can be mentioned.
- glycolic acid and the like can be mentioned.
- the alcoholic hydroxyl group of the compound (b) is a primary hydroxyl group, and is composed of an epoxy group of the epoxy resin (a) and a carboxyl group or a secondary amino group of the compound (b) or a carboxylic acid of an unsaturated monobasic acid (c).
- Saturated or unsaturated polybasic acid anhydride (d) reacts preferentially because saturated or unsaturated polybasic acid anhydride (d) has higher reactivity than secondary hydroxyl group formed by reaction of group I do. Therefore, this photosensitive resin (A) is formed by reacting acrylic acid as an unsaturated monobasic acid with a novolak-type epoxy resin as described in Japanese Patent Publication No.
- the distance between cross-linking points of a cured product becomes longer, so that flexibility can be increased. Also, the developability is improved. For this reason, addition of a saturated or unsaturated polybasic acid anhydride in a molar number greater than that of the primary hydroxyl group always produces a primary hydroxyl group reactant in an equimolar amount to the primary hydroxyl group.
- the added amount of the saturated or unsaturated polybasic acid anhydride increases (when the amount exceeds 0.7 mol per 1 mol of all the hydroxyl groups of the reactant (I)), the PCT resistance is increased.
- the reactivity is reduced to 0.7 mol or less with respect to 1 mol of all hydroxyl groups of the reactant (I), and more preferably 0.6 mol or more with respect to 1 mol of the primary hydroxyl group of the reactant (I). It is desirable to add up to 1.0 mole of a saturated or unsaturated polybasic anhydride. If the addition amount is less than 0.6 mol, the hydroxyl groups become excessive, and the PCT resistance and the developability also decrease.
- the unsaturated monobasic acid (c) is a monobasic acid having one carboxyl group and one or more polymerizable unsaturated bonds. Specific examples include acrylic acid and methacrylic acid. Can be used.
- Acrylic acid is particularly preferred for obtaining high active energy photocurability.
- a carboxyl group-containing polyfunctional acrylate or methacrylate which is a reaction product of methacrylate and a dibasic acid among polybasic acid anhydrides described later can be mentioned. Two or more of these unsaturated monobasic acids may be used in combination.
- the compound (b) and the unsaturated monobasic acid (c) is reacted in a ratio of about 0.8 to 1.2 equivalents in total, and the compound (b) and the unsaturated monobasic acid (c) are reacted in about 0.9 to 1.1 equivalents in total.
- the reaction is carried out in such a ratio that the compound (b) becomes 0.05 to 0.5 equivalent.
- ketones such as methyl ethyl ketone and cyclohexanone
- aromatic hydrocarbons such as toluene, xylene, and tetramethyl benzene, dipropylene glycol dimethyl ether, dipropylene glycol dimethyl ether, etc.
- Esters such as glycol ethers, ethyl acetate, butyl acetate, sorbitol acetate, aliphatic hydrocarbons such as octane and decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha Solvents and other organic solvents or carbitol (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate Over DOO is preferred to use a reactive monomers of Jipen evening to erythritol Tall hexa (meth) Akurireto.
- catalysts such as triethylamine, benzyldimethylamine, methyltriethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenyl, etc. Stibine, octane Chromium acid, zirconium octoate, etc.), and the amount of the catalyst is preferably 0.01 to 1% by weight based on the reaction mixture.
- the reaction temperature is preferably from 60 to 150 ° C.
- the reaction time is preferably 5 to 60 hours.
- the reactant (I) can be obtained.
- saturated or unsaturated polybasic anhydride (d) examples include maleic anhydride, anhydrous succinic acid, itaconic anhydride, phthalic anhydride, tetrahydrofluoric anhydride, hexahydrophthalic anhydride, and endo.
- Dibasic anhydrides such as methylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, chlorendic anhydride, etc., trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyl
- polybasic acid anhydrides such as tetracarboxylic anhydride, and the use of tetrahydrofluoric anhydride, succinic anhydride, and hexahydrophthalic anhydride is particularly preferable.
- the reaction temperature is preferably from 60 to 150 ° C.
- the reaction time is preferably 1 to 10 hours.
- the amount of the photosensitive resin (A) contained in the composition of the present invention is preferably 10 to 80% by weight, particularly preferably 15 to 60% by weight in the composition.
- the epoxy resin (B) is a thermosetting component and has, for example, one or more epoxy groups in one molecule, and is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a hydrogenated bisphenol A type Epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, dicyclopentagen-phenol novolak epoxy resin, phenol-cresol novolac co-condensation epoxy resin, bisphenol A novolak epoxy resin, bisphenol F Novolak type epoxy resins or their halogenated epoxy compounds, triphenyl methane epoxy resin, alkyl-substituted triphenyl methane epoxy resin, tetraphenylol ethane type epoxy resin, etc.
- the epoxy resin (B) is used alone or as a mixture of two or more, and the amount of the epoxy resin (B) contained in the composition of the present invention is preferably 1 to 50% by weight in the composition. It is particularly preferably 3 to 45% by weight.
- epoxy resin S (B) When using epoxy resin S (B), it is desirable to use an epoxy curing agent in combination to further improve properties such as adhesion, chemical resistance, and heat resistance.
- epoxy resin curing agents include imidazoles, amines, guanamines, polyamines, triazine derivatives, tertiary amines, polyphenols, organic phosphines, phosphonium salts, quaternary ammonium salts, and optical power.
- thione polymerization catalysts Specific examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenylimidazole, and 2-phenylimidazole.
- the triazine derivatives include tertiary amines such as ethylamine S-triazine, 2,4-diaminol S-triazine, 2,4-diaminol S-triazine, 2,4-diamino-6-xylyl-1-S-triazine.
- Quaternary ammonium salts such as benzyltrimethylammonium chloride, phenyltributylammonium chloride, hexadecyltributylphosphonium bromide, and hexadecyltributylphosphonium bromide.
- the amount of the epoxy resin ⁇ -hardening agent used is preferably from 0.01 to 25 parts by weight, more preferably from 0.1 to 15 parts by weight, based on 100 parts by weight of the epoxy resin. Parts by weight.
- the photopolymerization initiator (C) include benzoins, acetophenones, anthraquinones, thioxanthones, benzophenones, and the like.
- the benzoins include benzoin, benzoin methyl ether, benzoin isopropyl ether, and the like.
- acetophenones such as acetophenone and 2,2-dimethoxy-2-phenylacetophenone; and anthraquinones, 2-methylanthraquinone, 2-chloroanthraquinone, 2-ethylanthraquinone, Derivatives such as 2--butylanthraquinone and the like
- thioxanthones include thioxanthone, derivatives such as 2,4-dimethylthioxanthone
- benzophenones include benzophenone, 4-benzoyl-1,4-methyldiphenyl sulfide and 4,4'- Dichloroben Derivatives such as zophenone and N, N-dimethylaminobenzozophenone, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are available, and they can be used alone or in combination of two or more.
- the photopolymerization initiator (C) may be used alone or in combination of two or more photosensitizers such as tertiary amines.
- tertiary amines include N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine. Min and the like.
- 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinolpropan-1-one, 2,4-getylthioxanthone, 4-benzoylthioxanthone and 2-isopro It is better to combine with at least one selected from birchoxanthon.
- the proportion of the photopolymerization initiator (C) used in the composition of the present invention is preferably 0.5 to 20% by weight, and particularly preferably 1 to 10% by weight.
- a polymerizable unsaturated compound and / or a solvent (D) can be used as the diluent.
- This component is used for the purpose of improving curability to active energy rays and / or coatability when the photosensitive resin composition is used as a resist ink.
- a monomer having an active energy ray-curable property is preferable, and 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isoamyl acrylate, butoxyshethyl acrylate, Toxipoly Ethylene glycol acrylate, ethoxy polyethylene glycol acrylate, melamine acrylate, phenoxyshetyl acrylate, phenoxypropyl acrylate, ethylene glycol diacrylate, dipropylene glycol diacrylate, polydipropylene glycol diacrylate, Phenylglycidyl ether acrylate Tolylene diisocyanate urethane prepolymer, PO adduct of bisphenol A diacrylate, N-pyrrolidone, N-acryloyl morpholy ⁇ , ,, ⁇ -dimethyl acrylamide, ⁇ , ⁇ -getyl acrylate, ⁇ , ⁇ -dimethyla
- examples of the solvent include ketones, aromatic hydrocarbons, carbitols, acetates, and the like.
- ketones include methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- Aromatic hydrocarbons include toluene and xylene
- carbitols include ethyl sorb and butyl sorb
- acetates include ethyl acetate, butyl acetate, sorb acetate and butyl acetate.
- Solvent acetate, carbitol acetate and the like These solvents may be used alone or in combination of two or more.
- the polymerizable unsaturated compound and / or the solvent (D) is used alone or as a mixture of two or more.
- the amount of the component (D) to be used is preferably 5 to 80% by weight, more preferably 10 to 70% by weight in the photosensitive resin composition of the present invention.
- inorganic fillers such as silica, calcium carbonate, barium sulfate, clay and talc, phthalocyanine green, phthalocyanine blue, titanium oxide, carbon black, etc.
- polymerization inhibitors such as hydroquinone, resorcinol, catechol, pyroganol, quinone monomethyl ether, t-butylcatechol, phenothiazine, etc. May be used.
- the amount used is preferably 0 to 60% by weight, particularly preferably 5 to 40% by weight, in the photosensitive resin composition of the present invention.
- binder resins such as copolymers of ethylenically unsaturated compounds, polyester resins, polyester (meth) acrylate, and polyurethane (medium) as long as the properties of the solder resist are not affected.
- Polymerizable oligomers containing an unsaturated group such as acrylate and epoxy (meth) acrylate can be used.
- the photosensitive resin composition of the present invention is preferably obtained by blending the blending components in the ratio described above and uniformly mixing them with a three-roll mill or the like.
- the photosensitive resin composition of the present invention is cured, for example, as follows, obtain.
- composition of the present invention is applied in a thickness of 10 to 160 m by a method such as an electrostatic coating method or a curtain coating method, and the coating film is dried at 60 to 110 ° C, and a negative film is applied.
- a method such as an electrostatic coating method or a curtain coating method
- unexposed parts are diluted with alkaline aqueous solution (for example, 0.5-2% sodium carbonate aqueous solution or caustic soda aqueous solution, etc.) ) (Dissolution and removal), and then, in order to further improve various physical properties, sufficiently cure by irradiation with ultraviolet light and / or heating (for example, at 100 to 200 ° C for 0.5 to 1.0 hours).
- Kure V-Lunovolak type epoxy resin (Toto Kasei Co., Ltd., Epotote YDC N-704, softening point 80 ° C, epoxy equivalent 210) 2100 parts (10 equivalents), acrylic acid 576 parts (8 mol), glycol After adding 152 parts (2 moles) of the acid, 2.8 parts of methylhydroquinone and 2097 parts of carbitol acetate, heating the mixture to 90 ° C, and confirming that the mixture was uniformly dissolved, the triphenylphosphine 14.1 was added. The reaction mixture was heated to 100 ° C and reacted for about 40 hours to obtain a reaction product having an acid value of 0.5 KOHmg / g (hydroxyl group equivalent of 12).
- Cresol novolak type epoxy resin of Synthesis Example 1 acrylic acid, glycolic acid , Methylhydroquinone, carbitol acetate, triphenylphosphine, and tetrahydrophthalic anhydride were changed as shown in Table 1 or 2, and the reaction was carried out in the same manner as in Synthesis Example 1. A-2) to (A-5) and (B-1) to (B-3) were obtained. Synthesis Example 9
- Cresol novolak type epoxy resin manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C, epoxy equivalent 220) 2200 parts (10 equivalents), dimethicone-lepropionic acid 134 parts (1 Mol), 648.5 parts (9 mol) of acrylic acid, 4.6 parts of methylhydroquinone, 131 parts of carbitol acetate 1 and 484.9 parts of sorbent naphtha, heated to 90 ° C. and stirred, and the reaction mixture was stirred. Was dissolved.
- Photosensitive resin B— 1 B— 2 ⁇ -3 ⁇ -4 Ink compositions (i) and (ii) were separately kneaded by a three-roll mill using the photosensitive resin obtained in each synthesis example according to the composition shown in Table 3, and then the ink composition ( i) 500 g and (ii) 128 g were mixed to prepare a photosensitive resin composition (iii).
- the photosensitive resin composition (iii) was screen-printed on a 100-mesh polyester screen using a 100-mesh polyester screen to form a buffing-processed printed wiring board on a printed wiring board with a thickness of 40 to 8 OAim.
- test piece was immersed in a solder bath at 260 ° C. for 10 seconds three times, and the change in appearance was observed.
- the evaluation was performed as follows. ⁇ : No change in appearance. ⁇ : Discoloration of the cured film was observed. X: Floating, peeling, and solder latent of the cured film.
- immersion water washing As a pretreatment of the test piece, immerse in a 30 ° C acidic degreasing solution ⁇ immersion water washing ⁇ soft etching treatment immersion water washing ⁇ apply a catalyst (immerse in a 30 ° C nickel plating catalyst solution for ⁇ minute) ⁇ immersion water washing ⁇ electroless nickel plating was performed.
- the electroless gold plating was completed in the drying process, and the test pieces were subjected to a change in appearance and a pickling test using cellophane tape to observe the coating film.
- the evaluation was performed as follows. ⁇ : No change in appearance and no peeling of resist. ⁇ : No change in appearance, but slight peeling of resist. X: The resist was lifted, the dipping was observed, and the peeling of the resist was large in the peeling test.
- the test piece was left standing at 121 ° C, 2 atm, and a saturated steam atmosphere for 100 hours, and the appearance of the coating film was evaluated.
- the evaluation was performed as follows. ⁇ : No blistering or peeling of the coating. X: blister, peeling.
- Irgacure 907 of the composition in Table 3 is manufactured by Ciba's Geigy Corporation (2-methyl-1- [4- (methylthio) phenyl] —2 morpholinopropane-1-one), kyacure DETX—S Nippon Kayaku Co., Ltd. (2,4-Jetylthioki Sandton), Solvesso 150: Exxon Chemical Co., Ltd. (Solvent Naphtha), Light Acrylate DP E-6A: Kyoeisha Chemical Co., Ltd.
- Example 1 A— 1 ⁇ XXX XXX Example 2 A— 2 ⁇ ⁇ ⁇ XX Example 3 A— 3 ⁇ ⁇ ⁇ ⁇ Example 4 A-4 ⁇ ⁇ ⁇ ⁇ Example 5 A— 5 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Comparative example 1 B-1 ⁇ ⁇ XXX Comparative example 2 B- 2 ⁇ XXXX Comparative example 3 B— 3 XXXXX Comparative example 4 B-4 ⁇ XXX XXXXXXXXXXX Table 5
- the photosensitive resin composition of the present invention has a resistance to a developing solution in an exposed portion in the formation of a solder resist pattern by selectively exposing to ultraviolet light through a film on which a pattern is formed and by developing an unexposed portion,
- the obtained cured product has excellent electroless gold plating resistance, and sufficiently satisfies adhesiveness, solder heat resistance, PCT resistance, etc., and is particularly suitable for a photosensitive resin composition for a liquid solder resist.
- a coating film having excellent developability in a dilute alkaline aqueous solution used for a solder resist of a printed wiring board, and having been cured, has flexibility, water resistance, adhesion, soldering heat resistance,
- a photosensitive resin composition having excellent resistance to electroless gold plating and resistance to PCT (pressure reduction test) is provided.
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- Power Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Epoxy Resins (AREA)
- Materials For Photolithography (AREA)
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/169,927 US6727042B2 (en) | 2000-01-17 | 2000-12-27 | Photosensitive resin composition |
AU2001222286A AU2001222286A1 (en) | 2000-01-17 | 2000-12-27 | Photosensitive resin composition |
JP2001554121A JP3416129B2 (ja) | 2000-01-17 | 2000-12-27 | 感光性樹脂組成物 |
HK03108066A HK1055802A1 (en) | 2000-01-17 | 2003-11-06 | Photosensitive resin composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000-8082 | 2000-01-17 | ||
JP2000008082 | 2000-01-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001053890A1 true WO2001053890A1 (en) | 2001-07-26 |
Family
ID=18536417
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2000/009333 WO2001053890A1 (en) | 2000-01-17 | 2000-12-27 | Photosensitive resin composition |
Country Status (6)
Country | Link |
---|---|
US (1) | US6727042B2 (ja) |
JP (1) | JP3416129B2 (ja) |
CN (1) | CN1218219C (ja) |
AU (1) | AU2001222286A1 (ja) |
HK (1) | HK1055802A1 (ja) |
WO (1) | WO2001053890A1 (ja) |
Cited By (2)
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KR100895691B1 (ko) * | 2001-08-29 | 2009-04-30 | 스미또모 가가꾸 가부시키가이샤 | 레지스트 조성물 |
WO2023218876A1 (ja) * | 2022-05-13 | 2023-11-16 | 株式会社日本触媒 | アルカリ可溶性樹脂、感光性樹脂組成物及びその硬化物 |
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JP2003098658A (ja) * | 2001-09-25 | 2003-04-04 | Tamura Kaken Co Ltd | 感光性樹脂組成物及びプリント配線板 |
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KR100606655B1 (ko) * | 2004-09-22 | 2006-08-01 | 한국전자통신연구원 | 광반응성 유기고분자 게이트 절연막 조성물 및 이를이용한 유기박막 트랜지스터 |
JP4641861B2 (ja) * | 2005-05-11 | 2011-03-02 | 株式会社Adeka | アルカリ現像性樹脂組成物 |
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JP4985768B2 (ja) * | 2007-05-11 | 2012-07-25 | 日立化成工業株式会社 | 感光性樹脂組成物、感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法 |
JP5376793B2 (ja) * | 2007-11-07 | 2013-12-25 | 太陽ホールディングス株式会社 | 光硬化性樹脂組成物及びその硬化物パターン、並びに該硬化物パターンを具備するプリント配線板 |
CN101246310B (zh) * | 2008-03-19 | 2010-11-03 | 吉林大学 | 负性含氟光刻胶组合物及在聚合物光波导器件中的应用 |
JP5279423B2 (ja) * | 2008-05-19 | 2013-09-04 | 富士フイルム株式会社 | 感光性組成物、感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板 |
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US9223212B2 (en) * | 2011-07-31 | 2015-12-29 | Nippon Kayaku Kabushiki Kaisha | Photosensitive resin composition and cured product thereof |
WO2013022068A1 (ja) * | 2011-08-10 | 2013-02-14 | 日立化成工業株式会社 | 感光性樹脂組成物、感光性フィルム、永久レジスト及び永久レジストの製造方法 |
US9795752B2 (en) | 2012-12-03 | 2017-10-24 | Mhs Care-Innovation, Llc | Combination respiratory therapy device, system, and method |
CN106589320A (zh) * | 2016-11-30 | 2017-04-26 | 江苏芯锐传感科技有限公司 | 多功能环氧固化剂组合物及其制备方法 |
JP6830808B2 (ja) | 2016-12-21 | 2021-02-17 | 日東電工株式会社 | 光導波路形成用感光性エポキシ樹脂組成物、光導波路形成用硬化性フィルムおよびそれを用いた光導波路、光・電気伝送用混載フレキシブルプリント配線板 |
JP7363105B2 (ja) * | 2019-05-31 | 2023-10-18 | 株式会社レゾナック | 感光性樹脂組成物、感光性樹脂フィルム、プリント配線板及び半導体パッケージ、並びにプリント配線板の製造方法 |
Citations (5)
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JPH0327044A (ja) * | 1989-06-23 | 1991-02-05 | Mitsubishi Electric Corp | 感光性樹脂組成物 |
JPH04225355A (ja) * | 1990-12-27 | 1992-08-14 | Hitachi Chem Co Ltd | 感光性樹脂組成物及びこれを用いた感光性エレメント |
JPH0912654A (ja) * | 1995-06-26 | 1997-01-14 | Nippon Kayaku Co Ltd | エネルギー線硬化性樹脂組成物及びその硬化物 |
JPH09137109A (ja) * | 1995-09-14 | 1997-05-27 | Nippon Shokubai Co Ltd | 光硬化性液状ソルダーレジスト用インキ組成物 |
JPH09316149A (ja) * | 1996-05-31 | 1997-12-09 | Nippon Kayaku Co Ltd | 樹脂組成物、そのフィルム及びその硬化物 |
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JP2877659B2 (ja) | 1993-05-10 | 1999-03-31 | 日本化薬株式会社 | レジストインキ組成物及びその硬化物 |
JP3659825B2 (ja) * | 1997-12-19 | 2005-06-15 | 太陽インキ製造株式会社 | アルカリ現像可能な光硬化性・熱硬化性組成物及びそれから得られる硬化皮膜 |
JP2000321765A (ja) * | 1999-05-13 | 2000-11-24 | Showa Highpolymer Co Ltd | 感光性樹脂組成物 |
-
2000
- 2000-12-27 US US10/169,927 patent/US6727042B2/en not_active Expired - Fee Related
- 2000-12-27 CN CN008187754A patent/CN1218219C/zh not_active Expired - Fee Related
- 2000-12-27 AU AU2001222286A patent/AU2001222286A1/en not_active Abandoned
- 2000-12-27 WO PCT/JP2000/009333 patent/WO2001053890A1/ja active Application Filing
- 2000-12-27 JP JP2001554121A patent/JP3416129B2/ja not_active Expired - Fee Related
-
2003
- 2003-11-06 HK HK03108066A patent/HK1055802A1/xx not_active IP Right Cessation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0327044A (ja) * | 1989-06-23 | 1991-02-05 | Mitsubishi Electric Corp | 感光性樹脂組成物 |
JPH04225355A (ja) * | 1990-12-27 | 1992-08-14 | Hitachi Chem Co Ltd | 感光性樹脂組成物及びこれを用いた感光性エレメント |
JPH0912654A (ja) * | 1995-06-26 | 1997-01-14 | Nippon Kayaku Co Ltd | エネルギー線硬化性樹脂組成物及びその硬化物 |
JPH09137109A (ja) * | 1995-09-14 | 1997-05-27 | Nippon Shokubai Co Ltd | 光硬化性液状ソルダーレジスト用インキ組成物 |
JPH09316149A (ja) * | 1996-05-31 | 1997-12-09 | Nippon Kayaku Co Ltd | 樹脂組成物、そのフィルム及びその硬化物 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100895691B1 (ko) * | 2001-08-29 | 2009-04-30 | 스미또모 가가꾸 가부시키가이샤 | 레지스트 조성물 |
WO2023218876A1 (ja) * | 2022-05-13 | 2023-11-16 | 株式会社日本触媒 | アルカリ可溶性樹脂、感光性樹脂組成物及びその硬化物 |
Also Published As
Publication number | Publication date |
---|---|
CN1433532A (zh) | 2003-07-30 |
US20030087189A1 (en) | 2003-05-08 |
JP3416129B2 (ja) | 2003-06-16 |
HK1055802A1 (en) | 2004-01-21 |
AU2001222286A1 (en) | 2001-07-31 |
CN1218219C (zh) | 2005-09-07 |
US6727042B2 (en) | 2004-04-27 |
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