WO2017170959A1 - Curable resin composition, dry film, cured product and printed wiring board - Google Patents
Curable resin composition, dry film, cured product and printed wiring board Download PDFInfo
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- WO2017170959A1 WO2017170959A1 PCT/JP2017/013454 JP2017013454W WO2017170959A1 WO 2017170959 A1 WO2017170959 A1 WO 2017170959A1 JP 2017013454 W JP2017013454 W JP 2017013454W WO 2017170959 A1 WO2017170959 A1 WO 2017170959A1
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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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
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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
- C08G59/20—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 characterised by the epoxy compounds used
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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
- C08G59/20—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 characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
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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
- C08G59/20—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 characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3281—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing silicon
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
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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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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- 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
- G03F7/075—Silicon-containing compounds
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
Definitions
- the present invention relates to a curable resin composition, a dry film, a cured product, and a printed wiring board.
- Patent Document 1 discloses a reaction product of a novolac epoxy compound and an unsaturated monocarboxylic acid, and a polybasic base.
- a composition containing an active energy ray-curable resin obtained by reacting with an acid anhydride, a photopolymerization initiator, a photopolymerizable monomer, and an epoxy resin is disclosed.
- a printed wiring board (also referred to as a package substrate) used in such an IC package has a narrow SRO (Solder Resist Opening) pitch and is formed close to each other, so that a short circuit or crosstalk noise occurs between the SROs. Is more likely to occur. Further, since the solder resist formed between the SROs is thin and thin, cracks are likely to occur. For this reason, permanent coatings such as solder resists used for package substrates are required to have long-term high reliability, specifically high crack resistance and high insulation reliability. In particular, it is considered that the demand for reliability will increase further as the density of package substrates increases in the future.
- SRO solder Resist Opening
- Patent Document 2 discloses an organopolysiloxane having an epoxy group-containing organic group, a phenol novolak having an acryloyl group, and a polyfunctional monomer having a photofunctional group. And / or the photosensitive resin composition containing the diluent which consists of a polyfunctional monomer which has a photofunctional group and a thermal functional group, and a photoinitiator is disclosed.
- the curable resin composition described in Patent Document 1 cannot obtain high crack resistance and high insulation reliability.
- the photosensitive resin composition described in Patent Document 2 since a phenol novolak having an acryloyl group is used, the curing temperature must be increased, and the adhesion to the printed wiring board is lowered. Therefore, it becomes difficult to obtain crack resistance. That is, permanent coatings such as solder resists used for conventional package substrates have room for improvement in crack resistance and insulation reliability.
- an object of the present invention is to provide a curable resin composition capable of obtaining a cured product having excellent crack resistance and insulation reliability, a dry film having a resin layer obtained from the composition, the composition, or the dry film. It is in providing the hardened
- the present inventors have found that the above problems can be solved by blending a carboxyl group-containing resin and an epoxy resin having a silsesquioxane skeleton, and have completed the present invention. It was. Further, by using a carboxyl group-containing resin having a structure obtained by modifying a compound having two or more phenolic hydroxyl groups in one molecule with an alkylene oxide as a carboxyl group-containing resin, heat resistance and insulation reliability are further improved. I found it to improve.
- the curable resin composition of the present invention is characterized by containing (A) a carboxyl group-containing resin and (B) an epoxy resin having a silsesquioxane skeleton.
- the curable resin composition of the present invention preferably further contains (C) a surface-treated inorganic filler.
- the (A) carboxyl group-containing resin preferably has a structure represented by the following general formula (1). (Wherein R 1 to R 4 each independently represents a hydrogen atom or an alkyl group, and k represents any value of 0.3 to 10)
- the (A) carboxyl group-containing resin preferably has a structure represented by the following general formula (2). (Wherein R 5 to R 7 each independently represents a hydrogen atom or an alkyl group, Z represents an acid anhydride residue, and m represents any value of 0.3 to 10)
- the epoxy resin (B) having a silsesquioxane skeleton preferably has a structure represented by the following general formula (3). (Wherein R 8 to R 11 are each independently a group having a SiO bond or an organic group, and at least one of R 8 to R 11 is a group having an epoxy group.)
- the dry film of the present invention is characterized by having a resin layer obtained by applying and drying the curable resin composition on a film.
- the cured product of the present invention is obtained by curing the curable resin composition or the resin layer of the dry film.
- the printed wiring board of the present invention is characterized by having the cured product.
- a curable resin composition capable of obtaining a cured product having excellent crack resistance and insulation reliability, a dry film having a resin layer obtained from the composition, the composition, or a resin of the dry film A cured product of the layer and a printed wiring board having the cured product can be provided.
- the curable resin composition of the present invention contains (A) a carboxyl group-containing resin and (B) an epoxy resin having a silsesquioxane skeleton.
- the resulting cured product has a high glass transition temperature (Tg) and a linear expansion coefficient (CTE ⁇ 1, ⁇ 2) is low and the elastic modulus (E) at high temperature is high. Therefore, the fluidity of the cured product is suppressed at a high temperature, the generated stress is reduced, and the heat resistance is excellent. In other words, it can be said that the cured product of the present invention has a high crosslinking density and hardly undergoes a change in physical properties at high temperatures.
- the curable resin composition of this invention can suppress the curvature at the time of hardening by containing the epoxy resin which has silsesquioxane frame
- the cured product of the present invention has a high elastic modulus at high temperatures, it is considered that the crosslink density is high and the water absorption is low.
- the detailed mechanism is not clear, based on such heat resistance, low warpage, low temperature curability, and low water absorption, the cured product of the curable resin composition of the present invention is considered to have excellent crack resistance and insulation reliability. It is done. Further, as will be described later, it is considered that stable crack resistance can be obtained because the maximum value of Tan ⁇ in the temperature range of 25 to 300 ° C. of the cured product is small.
- cured material excellent in resolution can also be obtained.
- (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
- the (A) carboxyl group-containing resin is a component that is cured by polymerization or (B) crosslinking with the epoxy resin, and can be alkali-soluble by including a carboxyl group. From the viewpoint of photocurability and development resistance, it is preferable to have an ethylenically unsaturated group in the molecule in addition to the carboxyl group, but only use a carboxyl group-containing resin that does not have an ethylenically unsaturated group. May be. As the ethylenically unsaturated group, those derived from acrylic acid, methacrylic acid or derivatives thereof are preferable.
- carboxyl group-containing resins there are carboxyl group-containing resins having a copolymer structure, carboxyl group-containing resins having a urethane structure, carboxyl group-containing resins starting from an epoxy resin, and carboxyl group-containing resins starting from a phenol compound. preferable.
- Specific examples of the carboxyl group-containing resin include compounds listed below (which may be either oligomers or polymers).
- a difunctional or higher polyfunctional epoxy resin is reacted with (meth) acrylic acid, and the hydroxyl group present in the side chain is dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.
- the bifunctional or higher polyfunctional epoxy resin is preferably solid.
- a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group.
- a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group.
- the bifunctional epoxy resin is preferably solid.
- An epoxy compound having two or more epoxy groups in one molecule is combined with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and (meth) acrylic acid or the like.
- the resulting reaction product has many alcoholic hydroxyl groups such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic anhydride.
- a carboxyl group-containing photosensitive resin obtained by reacting a basic acid anhydride.
- An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate.
- a carboxyl group-containing photosensitive resin obtained by reacting the resulting reaction product with a polybasic acid anhydride.
- Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems
- a terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
- a carboxyl group-containing urethane resin by polyaddition reaction between a diisocyanate, a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid and dimethylolbutyric acid, and a diol compound, a molecule such as hydroxyalkyl (meth) acrylate
- a carboxyl group-containing urethane resin in which a compound having one hydroxyl group and one or more (meth) acryloyl groups is added and terminally (meth) acrylated.
- a carboxyl group-containing urethane resin obtained by adding a compound having two isocyanate groups and one or more (meth) acryloyl groups, and then terminally (meth) acrylating.
- Carboxy group-containing photosensitivity obtained by copolymerization of unsaturated carboxylic acid such as (meth) acrylic acid and unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate and isobutylene. resin.
- unsaturated carboxylic acid such as (meth) acrylic acid
- unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate and isobutylene. resin.
- a carboxyl group-containing polyester resin obtained by reacting a difunctional acid such as adipic acid, phthalic acid or hexahydrophthalic acid with a polyfunctional oxetane resin and adding a dibasic acid anhydride to the primary hydroxyl group produced.
- a carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth) acryloyl group in one molecule to the carboxyl group-containing resin of any one of (1) to (10) described above.
- the carboxyl group-containing resin As the carboxyl group-containing resin, the carboxyl group-containing resins of the above (1), (4), (5) and (9) are preferable, and (1) from the viewpoint of improving the heat resistance (glass transition temperature) of the cured product.
- the carboxyl group-containing resins (4) and (5) are preferred. Among these, from the viewpoint of insulation reliability, the carboxyl group-containing resins (4) and (5) are more preferable.
- a carboxyl group-containing resin having a structure represented by the following general formula (1) can be suitably used. (Wherein R 1 to R 4 each independently represents a hydrogen atom or an alkyl group, and k represents any value of 0.3 to 10)
- the alkyl group that R 1 to R 4 can take is preferably an alkyl group having 1 to 20 carbon atoms.
- the carboxyl group containing resin which has a structure represented by following General formula (2) like said (4) and (5) can be used suitably.
- R 5 to R 7 each independently represents a hydrogen atom or an alkyl group
- Z represents an acid anhydride residue
- m represents any value of 0.3 to 10
- the alkyl group that R 5 to R 7 can take is preferably an alkyl group having 1 to 20 carbon atoms.
- Examples of the carboxyl group-containing resin having the structure represented by the general formula (1) and the structure represented by the general formula (2) include two per one molecule as in the above (4) or (5).
- Examples include a carboxyl group-containing resin that is a reaction product of a reaction product of the above compound having a phenolic hydroxyl group with an alkylene oxide or a cyclic carbonate compound, a carboxylic acid having an ethylenically unsaturated group, and a polybasic acid anhydride. .
- the reaction product of a compound having two or more phenolic hydroxyl groups in one molecule and an alkylene oxide or cyclic carbonate compound includes not only a carboxylic acid having an ethylenically unsaturated group, but also a saturated aliphatic monocarboxylic acid. After reacting at least one of an acid and an aromatic monocarboxylic acid, a carboxylic acid having an ethylenically unsaturated group and a polybasic acid anhydride may be reacted.
- Examples of the compound having two or more phenolic hydroxyl groups in one molecule include catechol, resorcinol, hydroquinone, dihydroxytoluene, naphthalenediol, t-butylhydroquinone, t-butylhydroquinone, pyrogallol, phloroglucinol, bisphenol A, bisphenol.
- the compound having a phenolic hydroxyl group as described above has a functional group containing a halogen atom, oxygen, nitrogen, sulfur or the like on the hydrocarbon skeleton bonded to the phenol ring or the phenol ring, such as a halogen group, an ether group, an ester group.
- compounds having a phenolic hydroxyl group compounds having 3 or more phenolic hydroxyl groups in one molecule are preferred, and more preferred are novolak type phenol resins, phenols and aromatics having a phenolic hydroxyl group. Examples include condensates with aldehydes.
- the addition ratio of alkylene oxide to the compound having a phenolic hydroxyl group is preferably 0.3 to 10.0 moles per equivalent of the phenolic hydroxyl group of the compound having a phenolic hydroxyl group.
- the photocurable carboxy group-containing resin to be obtained has good photocurability.
- photocurability and thermosetting will become favorable.
- the addition reaction of alkylene oxide to the compound having a phenolic hydroxyl group is preferably performed at room temperature to 250 ° C.
- the reaction solvent benzene, toluene, xylene, tetramethylbenzene, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, octane, methyl isobutyl ketone, diisopropyl ether and the like are preferably used.
- These organic solvents can be used alone or in admixture of two or more.
- Reaction catalysts include alkali metal compounds such as potassium carbonate, sodium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide and barium hydroxide, tertiary amines such as triethylamine, and imidazole compounds such as 2-ethyl-4-methylimidazole.
- Quaternary compounds such as phosphorus compounds such as triphenylphosphine, tetramethylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium halide, tetramethylammonium benzoate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetramethylphosphonium hydroxide Basic salt compounds, naphthenic acid, lauric acid, stearic acid, oleic acid and octoenoic acid lithium, chromium, zirconium Potassium, such as metal salts of organic acids such as sodium is preferably used. These catalysts can be used alone or in admixture of two or more.
- alkylene oxide examples include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran.
- cyclic carbonate compound known and commonly used carbonate compounds can be used, for example, ethylene carbonate, propylene carbonate, butylene carbonate, 2,3-carbonate propyl methacrylate, and the like.
- 5-membered ethylene carbonate and propylene carbonate are used. This is preferable from the viewpoint of reactivity.
- These alkylene oxides and cyclic carbonate compounds can be used alone or in admixture of two or more.
- the reaction product obtained by reacting the compound having a phenolic hydroxyl group with an alkylene oxide or a cyclic carbonate compound can be reacted with an unsaturated group-containing monocarboxylic acid to obtain a reaction product.
- the reaction temperature in the esterification reaction is preferably 50 to 120 ° C., and the reaction can be carried out under reduced pressure, normal pressure or increased pressure.
- the unsaturated group-containing monocarboxylic acid has a double bond equivalent of 300 to 800 g / eq. It is desirable that the amount of addition be such that
- reaction solvent benzene, toluene, xylene, tetramethylbenzene, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, octane, methyl isobutyl ketone, diisopropyl ether and the like are preferably used.
- organic solvents can be used alone or in admixture of two or more.
- esterification catalyst sulfuric acid, hydrochloric acid, phosphoric acid, boron fluoride, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, cation exchange resin and the like are appropriately used.
- the esterification reaction is preferably performed in the presence of a polymerization inhibitor, and hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like are preferably used as the polymerization inhibitor.
- unsaturated group-containing monocarboxylic acid examples include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, ⁇ -cyanocinnamic acid, ⁇ -styrylacrylic acid, ⁇ -furfurylacrylic acid and the like. . Particularly preferred here are acrylic acid and methacrylic acid. These unsaturated group-containing monocarboxylic acids can be used alone or in admixture of two or more.
- the reaction product of the reaction product and unsaturated group-containing monocarboxylic acid is reacted with a polybasic acid anhydride to obtain a carboxyl group-containing photosensitive resin (photosensitive prepolymer).
- the polybasic acid anhydride is used in such an amount that the acid value of the resulting carboxyl group-containing photosensitive resin is preferably 20 to 200 mgKOH / g, more preferably 50 to 120 mgKOH / g.
- the reaction is usually carried out at about 50 to 150 ° C. in the presence or absence of an organic solvent described later in the presence of a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol or pyrogallol.
- a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, a phosphorus compound such as triphenylphosphine, naphthenic acid, laurin Metal salts of organic acids such as lithium, chromium, zirconium, potassium, and sodium such as acid, stearic acid, oleic acid, and octoenoic acid may be added as a catalyst. These catalysts can be used alone or in admixture of two or more.
- polybasic acid anhydride examples include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylene Alicyclic dibasic acid anhydrides such as tetrahydrophthalic anhydride and tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, trimellitic anhydride Aliphatic or aromatic dibasic or tribasic acid anhydrides such as biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic
- the acid value of the carboxyl group-containing resin is preferably 20 to 200 mgKOH / g.
- the acid value of the carboxyl group-containing resin is 20 to 200 mgKOH / g, it is easy to form a cured product pattern. More preferably, it is 50 to 130 mgKOH / g.
- the compounding amount of the carboxyl group-containing resin is, for example, 15 to 60% by mass, preferably 20 to 60% by mass, based on the total amount of the curable resin composition excluding the solvent. By setting the content to 15% by mass or more, preferably 20% by mass or more, the coating film strength can be improved. Further, when the content is 60% by mass or less, viscosity becomes appropriate and workability is improved. More preferably, it is 30 to 50% by mass.
- a carboxyl group-containing resin can be used alone or in combination of two or more.
- (B) Epoxy resin having silsesquioxane skeleton (B) An epoxy resin having a silsesquioxane skeleton (hereinafter also simply referred to as “(B) epoxy resin”) is obtained by hydrolyzing silsesquioxane, that is, trifunctional silane ( RSiO 1.5 ) Network type polymer or polyhedral cluster having a structure of n , and is not particularly limited as long as it is a compound having a group containing an epoxy group. Each silicon of silsesquioxane is bonded with an average of 1.5 oxygen atoms and one hydrocarbon group.
- the (B) epoxy resin is preferably an epoxy resin containing no halogen atom.
- the epoxy resin preferably has a silsesquioxane skeleton represented by the following general formula (3).
- R 8 to R 11 are each independently a group having a SiO bond or an organic group, and at least one of R 8 to R 11 is a group having an epoxy group
- a group refers to a group containing a carbon atom.
- the structure of the silsesquioxane is not particularly limited, and a silsesquioxane having a known and conventional structure such as a random structure, a ladder structure, a complete cage structure, or an incomplete cage structure can be used.
- the group having a SiO bond that can be taken by R 8 to R 11 is not particularly limited, a group having a SiO bond and an aliphatic skeleton, a group having a SiO bond and an aromatic skeleton, a group having a SiO bond and a hetero atom, etc. And is preferably within the range of the following epoxy equivalents.
- the organic group that R 8 to R 11 can take is not particularly limited, and examples thereof include an aliphatic group such as a methyl group, an aromatic group such as a phenyl group, and an organic group having a hetero atom. Preferably, it is an organic group having 1 to 30 carbon atoms, and is preferably within the following epoxy equivalent range.
- At least one of R 8 to R 11 is a group having an epoxy group, and the group having an epoxy group is not particularly limited as long as a group having an SiO bond or an organic group has an epoxy group. .
- the epoxy equivalent of the epoxy resin is 100 to 400 g / eq. It is preferably 150 to 250 g / eq. It is more preferable that 100 g / eq. In the above case, the storage stability is good. 400 g / eq. In the following cases, the CTE ( ⁇ 1, ⁇ 2) of the cured product can be reduced.
- the blending amount of the (B) epoxy resin is, for example, 1 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 10 to 80 parts by weight with respect to 100 parts by weight of the (A) carboxyl group-containing resin. 10 to 60 parts by mass is more preferable, 20 to 60 parts by mass is particularly preferable, and 25 to 60 parts by mass is most preferable. (B) Crack resistance and insulation reliability improve more as the compounding quantity of an epoxy resin is 1 mass part or more, and storage stability improves that it is 100 mass parts or less.
- the curable resin composition of the present invention preferably contains an inorganic filler, and the inorganic filler is a (C) surface-treated inorganic filler (hereinafter simply referred to as “(C) inorganic filler”). It is more preferable.
- cured material improves more by including an inorganic filler.
- the surface treatment of the inorganic filler refers to a treatment for improving compatibility with (A) a carboxyl group-containing resin or (B) an epoxy resin.
- the surface treatment of the inorganic filler is not particularly limited, and a surface treatment capable of introducing a curable reactive group to the surface of the inorganic filler is preferable.
- the inorganic filler is not particularly limited, and known and commonly used fillers such as silica, crystalline silica, Neuburg silica, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, Inorganic fillers such as aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate and zinc white can be used.
- silica is preferable, and since the surface area is small and stress is dispersed throughout, it is difficult to become a starting point of cracks, and from the viewpoint of excellent resolution, spherical silica is more preferable.
- the inorganic filler preferably has a curable reactive group on the surface that reacts with at least one of (A) a carboxyl group-containing resin and (B) an epoxy resin.
- the curable reactive group may be a thermosetting reactive group or a photocurable reactive group.
- thermosetting reactive groups include hydroxyl groups, carboxyl groups, isocyanate groups, amino groups, imino groups, epoxy groups, oxetanyl groups, mercapto groups, methoxymethyl groups, methoxyethyl groups, ethoxymethyl groups, ethoxyethyl groups, oxazoline groups, etc. Is mentioned.
- the photocurable reactive group examples include a vinyl group, a styryl group, a methacryl group, and an acrylic group.
- a methacryl group, an acrylic group, and a vinyl group are preferable, and as the thermosetting reactive group, an epoxy group is preferable.
- an epoxy group is preferable.
- (C) inorganic filler may have 2 or more types of curable reactive groups.
- the surface-treated silica is preferable. By including the surface-treated silica, the glass transition temperature can be increased.
- the method for introducing the curable reactive group onto the surface of the inorganic filler is not particularly limited, and may be introduced using a known and commonly used method.
- a surface treatment agent having a curable reactive group for example, a curable reactive group is introduced. What is necessary is just to process the surface of an inorganic filler with the coupling agent etc. which have.
- the surface treatment of the inorganic filler is preferably a surface treatment with a coupling agent.
- a coupling agent a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, or the like can be used. Among these, a silane coupling agent is preferable.
- (C) a silane coupling agent capable of introducing a curing reactive group into the inorganic filler is preferable.
- a silane coupling agent capable of introducing a thermosetting reactive group a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having a mercapto group, and a silane coupling having an isocyanate group Among them, a silane coupling agent having an epoxy group is more preferable.
- silane coupling agent having a vinyl group As a silane coupling agent capable of introducing a photo-curing reactive group, a silane coupling agent having a vinyl group, a silane coupling agent having a styryl group, a silane coupling agent having a methacryl group, and a silane coupling having an acrylic group A silane coupling agent having a methacryl group is more preferable.
- examples of the (C) inorganic filler having no curable reactive group include an inorganic filler subjected to alumina surface treatment.
- the inorganic filler should just be mix
- an inorganic filler may be surface-treated, it is preferable to blend an inorganic filler that has been surface-treated in advance. By blending the inorganic filler that has been surface-treated in advance, it is possible to prevent a decrease in crack resistance or the like due to the surface treatment agent that has not been consumed by the surface treatment that may remain when blended separately.
- the surface treatment it is preferable to blend a predispersed liquid in which the inorganic filler (C) is predispersed in the solvent or the resin component. It is more preferable that the pre-dispersed liquid is blended in the composition after the surface is sufficiently surface-treated when the surface-untreated inorganic filler is pre-dispersed in the solvent.
- the inorganic filler preferably has an average particle size of 2 ⁇ m or less because of excellent crack resistance. More preferably, it is 1 ⁇ m or less.
- an average particle diameter is the value of D50 measured using the Nikkiso Co., Ltd Microtrac particle size analyzer.
- the blending amount of the inorganic filler is preferably 20 to 80% by mass, more preferably 30 to 80% by mass, and more preferably 35 to 80% by mass with respect to the total solid content of the curable resin composition. Further preferred.
- (C) an inorganic filler and an inorganic filler that has not been surface-treated may be used in combination.
- the (C) inorganic filler is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 70% by mass, based on the total amount of the (C) inorganic filler and the non-surface-treated inorganic filler. % Or more is more preferable.
- the inorganic filler which is not surface-treated is spherical silica.
- At least one of a photopolymerization initiator and a photobase generator At least one of a photopolymerization initiator and a photobase generator is preferably used. Any photopolymerization initiator can be used as long as it is a known photopolymerization initiator as a photopolymerization initiator or a photoradical generator.
- photopolymerization initiator examples include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) -phenylphosphine oxide Bisacylphosphine oxides such as (IR
- a photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type.
- monoacylphosphine oxides and oxime esters are preferable, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Il]-, 1- (O-acetyloxime) is more preferred.
- the blending amount of the photopolymerization initiator is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.
- the amount is 0.5 parts by mass or more, the surface curability is good, and when the amount is 20 parts by mass or less, halation hardly occurs and good resolution is obtained.
- the photobase generator generates one or more basic substances that can function as a catalyst for a thermosetting reaction by changing the molecular structure upon irradiation with light such as ultraviolet rays or visible light, or by cleaving the molecules.
- a compound examples include secondary amines and tertiary amines.
- Examples of the photobase generator include ⁇ -aminoacetophenone compounds, oxime ester compounds, N-formylated aromatic amino compounds, N-acylated aromatic amino compounds, nitrobenzyl carbamate compounds, alcoholoxybenzyl carbamate compounds, and the like. . Of these, oxime ester compounds and ⁇ -aminoacetophenone compounds are preferred, oxime ester compounds are more preferred, and ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) is more preferred. As the ⁇ -aminoacetophenone compound, those having two or more nitrogen atoms are particularly preferable. A photobase generator may be used individually by 1 type, and may be used in combination of 2 or more type.
- examples of the photobase generator include quaternary ammonium salts.
- WPBG-018 (trade name: 9-anthrylmethyl N, N'-diethylcarbamate)
- WPBG-027 trade name: (E) -1- [3- (2-hydroxyphenyl) -2- (propenoyl] piperidine
- WPBG-082 (trade name: guanidinium2- (3-benzoylphenyl) propionate
- WPBG-140 (trade name: 1- (anthraquinon-2-yl) ethylidazole)
- photopolymerization initiators also function as photobase generators.
- the photopolymerization initiator that also functions as a photobase generator an oxime ester photopolymerization initiator and an ⁇ -aminoacetophenone photopolymerization initiator are preferable.
- the blending amount of the photobase generator is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.
- the amount is 0.1 parts by mass or more, the surface curability is good, and when the amount is 20 parts by mass or less, halation hardly occurs and good resolution is obtained.
- a compound having one or more ethylenically unsaturated groups in the molecule is preferably used.
- a photopolymerizable oligomer, a photopolymerizable vinyl monomer, or the like that is a known and commonly used photosensitive monomer can be used.
- the compound which has an ethylenically unsaturated group said here shall not contain the (A) carboxyl group-containing resin which has an ethylenically unsaturated group, and the (C) surface-treated inorganic filler.
- Examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers.
- Examples of (meth) acrylate oligomers include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, epoxy (meth) acrylates such as bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meta ) Acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like.
- photopolymerizable vinyl monomer known and commonly used monomers, for example, styrene derivatives such as styrene, chlorostyrene and ⁇ -methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide (Meth) acrylamides such as rilamide and N-butoxymethylacrylamide; allyl compounds such as triallyl isocyan
- the compounding amount of the compound having an ethylenically unsaturated bond is preferably 3 to 40 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. In the case of 3 parts by mass or more, the surface curability is improved, and in the case of 40 parts by mass or less, halation is suppressed. More preferably, it is 5 to 30 parts by mass.
- thermosetting catalyst The curable resin composition of the present invention preferably contains a thermosetting catalyst.
- thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole.
- Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine.
- the blending amount of the thermosetting catalyst is, for example, 0.05 to 80 parts by mass, preferably 0.05 to 50 parts by mass, more preferably 0.05 to 40 parts by mass with respect to 100 parts by mass of the (B) epoxy resin. Part by mass, more preferably 0.1 to 30 parts by mass.
- the curable resin composition of the present invention can contain a curing agent.
- the curing agent include phenol resins, polycarboxylic acids and acid anhydrides thereof, cyanate ester resins, active ester resins, maleimide compounds, and alicyclic olefin polymers.
- curing agent can be used individually by 1 type or in combination of 2 or more types.
- the curable resin composition of the present invention may contain a colorant.
- a colorant known colorants such as red, blue, green, yellow, black, and white can be used, and any of pigments, dyes, and pigments may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.
- the addition amount of the colorant is not particularly limited, but is preferably 10 parts by mass or less, particularly preferably 0.1 to 7 parts by mass with respect to (A) 100 parts by mass of the carboxyl group-containing resin.
- the curable resin composition of the present invention can contain an organic solvent for the purpose of preparing the composition and adjusting the viscosity when applied to a substrate or a carrier film.
- organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether , Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol
- additives include thermal polymerization inhibitors, UV absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial / antifungal agents, antifoaming agents, leveling agents, thickening agents Agent, adhesion imparting agent, thixotropic agent, photoinitiator aid, sensitizer, thermoplastic resin, organic filler, mold release agent, surface treatment agent, dispersant, dispersion aid, surface modifier, stabilizer And phosphors.
- the curable resin composition of the present invention may contain (B) a thermosetting resin other than the epoxy resin as long as the effects of the present invention are not impaired.
- the thermosetting resin may be any resin that is cured by heating and exhibits electrical insulation, and examples thereof include (B) epoxy compounds other than epoxy resins, oxetane compounds, melamine resins, and silicone resins. These may be used in combination.
- thermosetting resin other than the (B) epoxy resin a compound having a plurality of cyclic (thio) ether groups in the molecule is preferable.
- the compound having a plurality of cyclic (thio) ether groups in the molecule is a compound having a plurality of 3, 4 or 5-membered cyclic (thio) ether groups in the molecule.
- Polyfunctional epoxy compounds include epoxidized vegetable oils; bisphenol A type epoxy resins; hydroquinone type epoxy resins; bisphenol type epoxy resins; thioether type epoxy resins; brominated epoxy resins; novolac type epoxy resins; biphenol novolac type epoxy resins; Type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; trihydroxyphenylmethane type epoxy resin; alkylphenol type epoxy resin (for example, bixylenol type epoxy resin) Biphenol type epoxy resin; Bisphenol S type epoxy resin; Bisphenol A novolac type epoxy resin; Tetraphenylolethane type epoxy resin; Complex Diglycidyl phthalate resin; Tetraglycidyl xylenoyl ethane resin; Naphthalene group-containing epoxy resin; Epoxy resin having dicyclopentadiene skeleton; Triphenylmethane type epoxy resin; Epoxy resin having si
- epoxy resins can be used alone or in combination of two or more.
- triphenylmethane type epoxy resin, novolak type epoxy resin, bisphenol type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, biphenol novolak type epoxy resin, naphthalene type epoxy resin, or a mixture thereof is particularly preferable.
- cured material can be made high by using together the epoxy resin which has silsesquioxane frame
- the maximum value of Tan ⁇ in the temperature range of 25 to 300 ° C. of the cured product is preferably less than 0.25. With such physical properties, stable crack resistance can be obtained even when the temperature of the cured film is near Tg or above Tg.
- Tan ⁇ is measured with a UV conveyor furnace equipped with a high-pressure mercury lamp after irradiation of the resin layer after drying the resin composition with ultraviolet rays at about 500 mJ / cm 2 . It means the physical properties of a cured product having a thickness of 40 ⁇ m obtained by irradiation at an exposure amount of 1 J / cm 2 and then heating at 160 ° C. for 60 minutes to completely cure the resin layer.
- Ultraviolet rays are electromagnetic waves having a wavelength of 10 to 400 nm.
- Tan ⁇ is a frequency of 1 Hz, This is based on a chart obtained by measuring from 25 ° C. to 300 ° C. under a temperature rising rate of 5 ° C./min.
- the loss elastic modulus (viscous component) is decreased, the storage elastic modulus (elastic component) is increased, or both are performed.
- the elastic component may be increased as much as possible in the cured product rather than the viscous component.
- the means for setting the maximum value of Tan ⁇ to less than 0.25 is not particularly limited.
- Tan ⁇ is less than 0.20, preferably 0.15 or less, particularly 0.13 or less, crack resistance is further improved.
- (B) by reducing the equivalent of the epoxy group of the thermosetting component such as an epoxy resin, or when compounding a compound having an ethylenically unsaturated group, by reducing the blending amount, etc.
- the Tan ⁇ of the cured product can be reduced.
- the epoxy group equivalent of the epoxy resin is 400 g / eq. The following is preferable.
- the curable resin composition of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-component or two-component or more.
- the dry film of the present invention has a resin layer obtained by applying and drying the curable resin composition of the present invention on a carrier film.
- the curable resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and then a comma coater, a blade coater, a lip coater, a rod coater, and a squeeze coater. Apply a uniform thickness on the carrier film using a reverse coater, transfer roll coater, gravure coater, spray coater or the like. Thereafter, the applied composition is usually dried at a temperature of 40 to 130 ° C. for 1 to 30 minutes to form a resin layer.
- the coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 3 to 150 ⁇ m, preferably 5 to 60 ⁇ m.
- a plastic film is used as the carrier film.
- a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used.
- the thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 ⁇ m. More preferably, it is in the range of 15 to 130 ⁇ m.
- the peelable cover film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used.
- a cover film what is necessary is just a thing smaller than the adhesive force of a resin layer and a carrier film when peeling a cover film.
- the resin layer may be formed by applying and drying the curable resin composition of the present invention on the cover film, and a carrier film may be laminated on the surface. That is, as the film to which the curable resin composition of the present invention is applied when producing a dry film in the present invention, either a carrier film or a cover film may be used.
- the printed wiring board of the present invention has a cured product obtained from the curable resin composition of the present invention or the resin layer of the dry film.
- the curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using the organic solvent, and a dip coating method is performed on a substrate.
- the organic solvent contained in the composition is volatilized and dried (temporary drying) at a temperature of 60 to 100 ° C.
- a tack-free resin layer is formed.
- a resin layer is formed on a base material by peeling a carrier film.
- Examples of the base material include printed wiring boards and flexible printed wiring boards that have been previously formed with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy.
- PEN polyethylene naphthalate
- Volatile drying performed after the application of the curable resin composition of the present invention is performed in a dryer using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (equipped with a heat source of an air heating method using steam).
- the method can be carried out using a method in which hot air is brought into countercurrent contact and a method in which the hot air is blown onto the support.
- the curable resin composition of the present invention is thermosetting, for example, it is heated to a temperature of 100 to 220 ° C. to be cured by heat, heat resistance, chemical resistance, moisture absorption resistance, adhesion, electrical characteristics It is possible to form a cured film (cured product) having excellent characteristics such as the above.
- the curable resin composition of the present invention When the curable resin composition of the present invention is light-hardened, after forming a resin layer on a printed wiring board, it is selectively exposed with active energy rays through a photomask having a predetermined pattern, and unexposed portions are diluted. Development with an alkaline aqueous solution (for example, 0.3 to 3% by mass aqueous sodium carbonate solution) forms a pattern of a cured product. Further, the cured product is irradiated with active energy rays and then heat-cured (for example, 100 to 220 ° C.), irradiated with active energy rays after heat-curing, or is subjected to final finish curing (main curing) only by heat-curing.
- an alkaline aqueous solution for example, 0.3 to 3% by mass aqueous sodium carbonate solution
- a cured film having excellent properties such as properties and hardness is formed.
- the curable resin composition of the present invention contains a photobase generator, it is preferably heated after exposure and before development.
- the heating conditions before development after exposure are, for example, 1 to 1 at 60 to 150 ° C. It is preferable to heat for 60 minutes.
- the exposure apparatus used for the active energy ray irradiation may be any apparatus that irradiates ultraviolet rays in the range of 350 to 450 nm, equipped with a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, etc.
- a direct drawing apparatus for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer
- the lamp light source or laser light source of the direct drawing machine may have a maximum wavelength in the range of 350 to 450 nm.
- the exposure amount for image formation varies depending on the film thickness and the like, but can be generally in the range of 10 to 1000 mJ / cm 2 , preferably 20 to 800 mJ / cm 2 .
- the developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.
- the curable resin composition of the present invention is preferably used for forming a cured film on a printed wiring board, more preferably used for forming a permanent film, and more preferably a solder resist, Used to form interlayer insulation layers and coverlays. Further, according to the curable resin composition of the present invention, since a cured product excellent in crack resistance and insulation reliability can be obtained, a printed wiring board provided with a fine pitch wiring pattern that requires high reliability, for example, it can be suitably used for forming a permanent film (especially a solder resist) for a package substrate, particularly FC-BGA.
- reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide.
- the nonvolatile content was 62.1%, and the hydroxyl value was 182.2 mgKOH / g (307. 9 g / eq.) Of a novolak-type cresol resin propylene oxide reaction solution. This was an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
- reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution.
- 332.5 parts of the obtained novolak acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was supplied at a rate of 10 ml / min.
- Diethylene glycol monoethyl ether acetate was added to obtain an acrylate resin solution having a solid content of 67%.
- 322 parts of the obtained acrylate resin solution, 0.1 part of hydroquinone monomethyl ether, and 0.3 part of triphenylphosphine were charged.
- 60 parts of tetrahydrophthalic anhydride was added, reacted for 4 hours, cooled and taken out.
- the photosensitive carboxyl group-containing resin solution thus obtained had a solid content of 70% and a solid content acid value of 81 mgKOH / g.
- this carboxyl group-containing photosensitive resin solution is referred to as Resin Solution A-2.
- Resin Solution A-4 this carboxyl group-containing photosensitive resin solution was referred to as Resin Solution A-4.
- Examples 1 to 16 Comparative Examples 1 to 5
- the above resin solution (varnish) is blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and curable resin composition A product was prepared.
- ⁇ Glass transition temperature Tg and thermal expansion coefficient CTE> (Examples 1 to 15, Comparative Examples 1 to 5)
- the entire surface of the curable resin composition was applied by screen printing to a dry film thickness of about 40 ⁇ m. This was dried at 80 ° C. and allowed to cool to room temperature, thereby forming a resin layer made of a curable resin composition, and obtaining an evaluation substrate having an uncured sample for each example and comparative example.
- exposure was performed through a strip-shaped negative mask of 50 mm ⁇ 3 mm at an optimum exposure amount: 800 mJ with ORC HMW680GW (metal halide lamp, scattered light). Thereafter, 1 wt.
- Example 16 On the copper foil substrate, the entire surface of the curable resin composition was applied by screen printing to a dry film thickness of about 40 ⁇ m. This was dried at 80 ° C. and allowed to cool to room temperature, thereby forming a resin layer made of a curable resin composition. This was heated and cured at 160 ° C. for 1 hour to obtain an evaluation substrate having a cured film. The cured film of the evaluation board
- TMA measuring apparatus manufactured by Shimadzu Corporation, model name: TMA6000
- Tg, CTE ⁇ 1 (0 ° C.-50 ° C.), and CTE ⁇ 2 200 ° C.-250 ° C.
- the evaluation criteria are as follows. (Tg) ⁇ ... 150 ° C. or higher ⁇ ... 145 ° C. or higher and lower than 150 ° C. ⁇ ... 140 ° C. or higher and lower than 145 ° C. ⁇ ... less than 40 ppm ⁇ ... 40 ppm or more and less than 50 ppm ⁇ ... 50 ppm or more and less than 60 ppm ⁇ ...
- CTE ⁇ 2 60 ppm or more (CTE ⁇ 2) ⁇ ... less than 110 ppm ⁇ ... 110 ppm or more and less than 120 ppm ⁇ ... 120 ppm or more and less than 130 ppm ⁇ ... 130 ppm or more
- the substrate was heat cured at 160 ° C. for 1 hour to obtain an evaluation substrate having a cured film.
- substrate obtained by the above was peeled off from copper foil, and evaluation was implemented.
- the measurement was performed using a DMA measuring device (model name: DMS6100, manufactured by Shimadzu Corporation), and E at 260 ° C. was evaluated. Tan ⁇ was measured with a DMS6100 manufactured by Hitachi High-Tech Co., Ltd. from 25 ° C. to 300 ° C.
- Example 16 On the copper foil substrate, the entire surface of the curable resin composition was applied by screen printing to a dry film thickness of about 40 ⁇ m. This was heat-cured at 160 ° C. for 1 hour to obtain an evaluation substrate having a cured film. The cured film of the evaluation board
- a DMA measuring device model name: DMS6100, manufactured by Shimadzu Corporation
- Tan ⁇ was measured with a DMS6100 manufactured by Hitachi High-Tech Co., Ltd. from 25 ° C. to 300 ° C. at a rate of 5 ° C./min, a frequency of 1 Hz, and a tensile sine wave mode, and the maximum value in the temperature measurement region was taken.
- the evaluation criteria are as follows. (Elastic modulus E) ⁇ ... 1 ⁇ 10 9 Pa or more ⁇ ... 5 ⁇ 10 8 Pa or more and less than 1 ⁇ 10 9 Pa ⁇ ... 1 ⁇ 10 8 Pa or more and less than 5 ⁇ 10 8 Pa ⁇ ... 1 ⁇ 10 8 Pa or less (Tan ⁇ ) ⁇ ... less than 0.20 ⁇ ... 0.20 or more and less than 0.25 ⁇ ... 0.25 or more and less than 0.30 ⁇ ... 0.30 or more
- the film was cured by heating at 160 ° C. for 1 hour.
- the cured film of the evaluation substrate obtained as described above was cut out to 50 mm ⁇ 50 mm, and left on a horizontal table with the cured film surface facing down. After standing, the distance from the horizontal base to the Cu foil was measured for each of the four corners of the cut out cured film, and the average value was obtained and evaluated as follows.
- Example 16 The entire surface of the curable resin composition was applied to a dry film thickness of 20 ⁇ m by screen printing on a CZ-treated 35 ⁇ m copper foil substrate. This was dried at 80 ° C.
- a cured film was obtained by treatment with an aqueous sodium carbonate solution. Furthermore, after irradiating with ultraviolet rays with an integrated exposure amount of 1000 mJ, the substrate was heated and cured under the following conditions to obtain an evaluation substrate ⁇ . FT-IR measurement was performed on the evaluation substrates ⁇ and ⁇ obtained as described above, and the reaction rate of the epoxy group was measured. The reaction rate of the epoxy group was calculated from the peak height in the vicinity of 913 cm ⁇ 1, which is vibration derived from the epoxy group, using Microscope spotlight 200 as a measuring device.
- Example 16 The plated copper substrate was treated with CZ8101 at an etching rate of 1 ⁇ m / m 2 , and the entire surface of the curable resin composition was applied by screen printing to a dry film thickness of about 20 ⁇ m. This was dried at 80 ° C. and allowed to cool to room temperature, whereby a resin layer made of a curable resin composition was formed, and an evaluation substrate ⁇ was obtained. This was heated and cured under the following conditions to obtain an evaluation substrate ⁇ . FT-IR measurement was performed on the evaluation substrates ⁇ and ⁇ obtained as described above, and the reaction rate of the epoxy group was measured.
- the reaction rate of the epoxy group was calculated from the peak height in the vicinity of 913 cm ⁇ 1, which is vibration derived from the epoxy group, using Microscope spotlight 200 as a measuring device.
- A Epoxy reaction rate of 98% or higher achieved at 150 ° C. for 60 min.
- Curing Epoxy reaction rate of 98% or higher achieved at 160 ° C. for 60 min.
- the film was cured by heating at 160 ° C. for 1 hour.
- the opening diameter of the evaluation substrate obtained as described above was observed, and it was confirmed whether or not halation and undercut were generated.
- Excellent opening diameter at 50 ⁇ m Good opening diameter at 70 ⁇ m Good opening diameter at 100 ⁇ m ⁇ Good opening diameter cannot be obtained at 100 ⁇ m or development is impossible
- the film was cured by heating at 160 ° C. for 1 hour. Thereafter, Au plating treatment, solder bump formation, and Si chip were mounted to obtain an evaluation substrate.
- the evaluation substrate obtained as described above was placed in a thermal cycle machine in which a temperature cycle was performed between ⁇ 65 ° C. and 150 ° C., and TCT (Thermal Cycle Test) was performed. Then, the surface of the cured film was observed at 600 cycles, 800 cycles, and 1000 cycles. Judgment criteria are as follows. (Example 16) The entire surface of the curable resin composition was applied onto an evaluation substrate for FC-BGA formed with a pad pitch of 250 ⁇ m.
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Abstract
Description
具体的には、QFP(クワッド・フラットパック・パッケージ)、SOP(スモール・アウトライン・パッケージ)等と呼ばれるICパッケージに代わって、BGA(ボール・グリッド・アレイ)、CSP(チップ・スケール・パッケージ)等と呼ばれるICパッケージが使用されている。また、近年では、さらに高密度化されたICパッケージとして、FC-BGA(フリップチップ・ボール・グリッド・アレイ)も実用化されている。
このようなICパッケージに用いられるプリント配線板(パッケージ基板ともいう。)においては、SRO(Solder Resist Opening)ピッチが狭く、互いに近接して形成されるため、SRO間でショートやクロストークノイズが生じたりするおそれが高くなる。また、SRO間に形成されるソルダーレジストは、細く薄くなるためクラックが生じやすくなる。そのため、パッケージ基板に用いられるソルダーレジスト等の永久被膜には、長期にわたる高度な信頼性、具体的には高クラック耐性および高絶縁信頼性が求められる。特に、今後のパッケージ基板の高密度化に伴い、信頼性の要求は一層高まると考えられる。 In recent years, with the rapid progress of semiconductor components, electronic devices tend to be lighter, thinner, higher performance, and multifunctional. Following this trend, miniaturization and multi-pin semiconductor packages have been put into practical use.
Specifically, instead of IC packages called QFP (Quad Flat Pack Package), SOP (Small Outline Package), etc., BGA (Ball Grid Array), CSP (Chip Scale Package), etc. IC package called is used. In recent years, FC-BGA (Flip Chip Ball Grid Array) has been put to practical use as an IC package with higher density.
A printed wiring board (also referred to as a package substrate) used in such an IC package has a narrow SRO (Solder Resist Opening) pitch and is formed close to each other, so that a short circuit or crosstalk noise occurs between the SROs. Is more likely to occur. Further, since the solder resist formed between the SROs is thin and thin, cracks are likely to occur. For this reason, permanent coatings such as solder resists used for package substrates are required to have long-term high reliability, specifically high crack resistance and high insulation reliability. In particular, it is considered that the demand for reliability will increase further as the density of package substrates increases in the future.
一方、特許文献2に記載の感光性樹脂組成物では、アクリロイル基を有するフェノールノボラックを用いているので、硬化温度を高くしなければならず、プリント配線板との密着性が低くなる。そのため、クラック耐性を得ることが困難になる。
即ち、従来のパッケージ基板に用いられるソルダーレジスト等の永久被膜では、クラック耐性および絶縁信頼性に改善の余地があった。 However, the curable resin composition described in Patent Document 1 cannot obtain high crack resistance and high insulation reliability.
On the other hand, in the photosensitive resin composition described in Patent Document 2, since a phenol novolak having an acryloyl group is used, the curing temperature must be increased, and the adhesion to the printed wiring board is lowered. Therefore, it becomes difficult to obtain crack resistance.
That is, permanent coatings such as solder resists used for conventional package substrates have room for improvement in crack resistance and insulation reliability.
(式中、R1~R4はそれぞれ独立して水素原子またはアルキル基を表し、kは0.3~10のいずれかの値を表す。) In the curable resin composition of the present invention, the (A) carboxyl group-containing resin preferably has a structure represented by the following general formula (1).
(Wherein R 1 to R 4 each independently represents a hydrogen atom or an alkyl group, and k represents any value of 0.3 to 10)
(式中、R5~R7はそれぞれ独立して水素原子またはアルキル基を表し、Zは酸無水物残基を表し、mは0.3~10のいずれかの値を表す。) In the curable resin composition of the present invention, the (A) carboxyl group-containing resin preferably has a structure represented by the following general formula (2).
(Wherein R 5 to R 7 each independently represents a hydrogen atom or an alkyl group, Z represents an acid anhydride residue, and m represents any value of 0.3 to 10)
(式中、R8~R11は、それぞれ独立して、SiO結合を有する基または有機基であり、R8~R11のうち少なくとも一つがエポキシ基を有する基である。) In the curable resin composition of the present invention, the epoxy resin (B) having a silsesquioxane skeleton preferably has a structure represented by the following general formula (3).
(Wherein R 8 to R 11 are each independently a group having a SiO bond or an organic group, and at least one of R 8 to R 11 is a group having an epoxy group.)
また、本発明の硬化性樹脂組成物はシルセスキオキサン骨格を有するエポキシ樹脂を含有することにより、硬化時の反りを抑制し、プリント配線板内部の発生応力を抑えることができる。
さらに本発明の硬化性樹脂組成物は、カルボキシル基含有樹脂とシルセスキオキサン骨格を有するエポキシ樹脂とを含有するため、低温での硬化性(反応率)が向上し、高温処理による銅回路の酸化を抑え、硬化物とプリント配線板との密着性を維持することができる。
さらに、本発明の硬化物は、高温での弾性率が高いので、架橋密度が高く、吸水率が低いと考えられる。
詳しいメカニズムは明らかではないが、このような耐熱性、低反り性、低温硬化性、低吸水性に基づき、本発明の硬化性樹脂組成物の硬化物はクラック耐性および絶縁信頼性に優れると考えられる。また、後述するように、硬化物の25~300℃の温度範囲におけるTanδの最大値が小さいため、安定したクラック耐性を得ることができると考えられる。
また、本発明の硬化性樹脂組成物によれば、解像性に優れた硬化物を得ることもできる。 Since the curable resin composition of the present invention contains a carboxyl group-containing resin and an epoxy resin having a silsesquioxane skeleton, the resulting cured product has a high glass transition temperature (Tg) and a linear expansion coefficient (CTEα1, α2) is low and the elastic modulus (E) at high temperature is high. Therefore, the fluidity of the cured product is suppressed at a high temperature, the generated stress is reduced, and the heat resistance is excellent. In other words, it can be said that the cured product of the present invention has a high crosslinking density and hardly undergoes a change in physical properties at high temperatures.
Moreover, the curable resin composition of this invention can suppress the curvature at the time of hardening by containing the epoxy resin which has silsesquioxane frame | skeleton, and can suppress the generated stress inside a printed wiring board.
Furthermore, since the curable resin composition of the present invention contains a carboxyl group-containing resin and an epoxy resin having a silsesquioxane skeleton, the curability (reaction rate) at low temperature is improved, and the copper circuit by high-temperature treatment is improved. Oxidation can be suppressed and adhesion between the cured product and the printed wiring board can be maintained.
Furthermore, since the cured product of the present invention has a high elastic modulus at high temperatures, it is considered that the crosslink density is high and the water absorption is low.
Although the detailed mechanism is not clear, based on such heat resistance, low warpage, low temperature curability, and low water absorption, the cured product of the curable resin composition of the present invention is considered to have excellent crack resistance and insulation reliability. It is done. Further, as will be described later, it is considered that stable crack resistance can be obtained because the maximum value of Tan δ in the temperature range of 25 to 300 ° C. of the cured product is small.
Moreover, according to the curable resin composition of this invention, the hardened | cured material excellent in resolution can also be obtained.
(A)カルボキシル基含有樹脂は、重合または(B)エポキシ樹脂と架橋して硬化する成分であり、カルボキシル基が含まれることによりアルカリ可溶性とすることができる。また、光硬化性や耐現像性の観点から、カルボキシル基の他に、分子内にエチレン性不飽和基を有することが好ましいが、エチレン性不飽和基を有さないカルボキシル基含有樹脂のみを使用してもよい。エチレン性不飽和基としては、アクリル酸もしくはメタアクリル酸またはそれらの誘導体由来のものが好ましい。カルボキシル基含有樹脂の中でも、共重合構造を有するカルボキシル基含有樹脂、ウレタン構造を有するカルボキシル基含有樹脂、エポキシ樹脂を出発原料とするカルボキシル基含有樹脂、フェノール化合物を出発原料とするカルボキシル基含有樹脂が好ましい。カルボキシル基含有樹脂の具体例としては、以下に列挙するような化合物(オリゴマーまたはポリマーのいずれでもよい)が挙げられる。 [(A) Carboxyl group-containing resin]
The (A) carboxyl group-containing resin is a component that is cured by polymerization or (B) crosslinking with the epoxy resin, and can be alkali-soluble by including a carboxyl group. From the viewpoint of photocurability and development resistance, it is preferable to have an ethylenically unsaturated group in the molecule in addition to the carboxyl group, but only use a carboxyl group-containing resin that does not have an ethylenically unsaturated group. May be. As the ethylenically unsaturated group, those derived from acrylic acid, methacrylic acid or derivatives thereof are preferable. Among the carboxyl group-containing resins, there are carboxyl group-containing resins having a copolymer structure, carboxyl group-containing resins having a urethane structure, carboxyl group-containing resins starting from an epoxy resin, and carboxyl group-containing resins starting from a phenol compound. preferable. Specific examples of the carboxyl group-containing resin include compounds listed below (which may be either oligomers or polymers).
(式中、R1~R4はそれぞれ独立して水素原子またはアルキル基を表し、kは0.3~10のいずれかの値を表す。) As the carboxyl group-containing resin, the carboxyl group-containing resins of the above (1), (4), (5) and (9) are preferable, and (1) from the viewpoint of improving the heat resistance (glass transition temperature) of the cured product. The carboxyl group-containing resins (4) and (5) are preferred. Among these, from the viewpoint of insulation reliability, the carboxyl group-containing resins (4) and (5) are more preferable. Furthermore, like (4) and (5), a carboxyl group-containing resin having a structure represented by the following general formula (1) can be suitably used.
(Wherein R 1 to R 4 each independently represents a hydrogen atom or an alkyl group, and k represents any value of 0.3 to 10)
(式中、R5~R7はそれぞれ独立して水素原子またはアルキル基を表し、Zは酸無水物残基を表し、mは0.3~10のいずれかの値を表す。) Moreover, the carboxyl group containing resin which has a structure represented by following General formula (2) like said (4) and (5) can be used suitably.
(Wherein R 5 to R 7 each independently represents a hydrogen atom or an alkyl group, Z represents an acid anhydride residue, and m represents any value of 0.3 to 10)
エステル化触媒としては、硫酸、塩酸、燐酸、フッ化ホウ素、メタンスルホン酸、ベンゼンスルホン酸、p-トルエンスルホン酸、カチオン交換樹脂等が適宜用いられる。エステル化反応は重合禁止剤の存在下で行なうのが好ましく、重合禁止剤としては、ハイドロキノン、メチルハイドロキノン、ハイドロキノンモノメチルエーテル、カテコール、ピロガロール等が好適に用いられる。 As the reaction solvent, benzene, toluene, xylene, tetramethylbenzene, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, octane, methyl isobutyl ketone, diisopropyl ether and the like are preferably used. These organic solvents can be used alone or in admixture of two or more.
As the esterification catalyst, sulfuric acid, hydrochloric acid, phosphoric acid, boron fluoride, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, cation exchange resin and the like are appropriately used. The esterification reaction is preferably performed in the presence of a polymerization inhibitor, and hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like are preferably used as the polymerization inhibitor.
(B)シルセスキオキサン骨格を有するエポキシ樹脂(以下、単に「(B)エポキシ樹脂」とも略称する)としては、シルセスキオキサン、即ち、3官能性シランを加水分解することで得られる(RSiO1.5)nの構造を持つネットワーク型ポリマーまたは多面体クラスターであって、エポキシ基を含む基を有する化合物であれば特に限定されない。シルセスキオキサンの各シリコンは平均1.5個の酸素原子と1つの炭化水素基と結合している。
ここで、(B)エポキシ樹脂は、ハロゲン原子を含まないエポキシ樹脂であることが好ましい。 [(B) Epoxy resin having silsesquioxane skeleton]
(B) An epoxy resin having a silsesquioxane skeleton (hereinafter also simply referred to as “(B) epoxy resin”) is obtained by hydrolyzing silsesquioxane, that is, trifunctional silane ( RSiO 1.5 ) Network type polymer or polyhedral cluster having a structure of n , and is not particularly limited as long as it is a compound having a group containing an epoxy group. Each silicon of silsesquioxane is bonded with an average of 1.5 oxygen atoms and one hydrocarbon group.
Here, the (B) epoxy resin is preferably an epoxy resin containing no halogen atom.
(式中、R8~R11は、それぞれ独立して、SiO結合を有する基または有機基であり、R8~R11のうち少なくとも一つがエポキシ基を有する基である。)ここで、有機基とは、炭素原子を含む基のことを言う。 (B) The epoxy resin preferably has a silsesquioxane skeleton represented by the following general formula (3).
(Wherein R 8 to R 11 are each independently a group having a SiO bond or an organic group, and at least one of R 8 to R 11 is a group having an epoxy group) A group refers to a group containing a carbon atom.
本発明の硬化性樹脂組成物は、無機フィラーを含有することが好ましく、また、無機フィラーが(C)表面処理された無機フィラー(以下、単に「(C)無機フィラー」とも略称する)であることがより好ましい。(C)無機フィラーを含むことにより、硬化物のクラック耐性がより向上する。
ここで、(C)無機フィラーの表面処理とは、(A)カルボキシル基含有樹脂または(B)エポキシ樹脂との相溶性を向上させるための処理のことを言う。
(C)無機フィラーの表面処理は特に限定されるものではなく、無機フィラーの表面に硬化性反応基を導入可能な表面処理が好ましい。 ((C) Surface-treated inorganic filler)
The curable resin composition of the present invention preferably contains an inorganic filler, and the inorganic filler is a (C) surface-treated inorganic filler (hereinafter simply referred to as “(C) inorganic filler”). It is more preferable. (C) The crack resistance of hardened | cured material improves more by including an inorganic filler.
Here, (C) the surface treatment of the inorganic filler refers to a treatment for improving compatibility with (A) a carboxyl group-containing resin or (B) an epoxy resin.
(C) The surface treatment of the inorganic filler is not particularly limited, and a surface treatment capable of introducing a curable reactive group to the surface of the inorganic filler is preferable.
本発明の硬化性樹脂組成物を、光硬化性とする場合には、光重合開始剤および光塩基発生剤の少なくとも何れか一種が好ましく用いられる。光重合開始剤としては、光重合開始剤や光ラジカル発生剤として公知の光重合開始剤であれば、いずれのものを用いることもできる。 (At least one of a photopolymerization initiator and a photobase generator)
When the curable resin composition of the present invention is photocurable, at least one of a photopolymerization initiator and a photobase generator is preferably used. Any photopolymerization initiator can be used as long as it is a known photopolymerization initiator as a photopolymerization initiator or a photoradical generator.
本発明の硬化性樹脂組成物を、光硬化性とする場合には、分子中に1個以上のエチレン性不飽和基を有する化合物が好ましく用いられる。エチレン性不飽和基を有する化合物としては、公知慣用の感光性モノマーである光重合性オリゴマー、光重合性ビニルモノマー等を用いることができる。なお、ここで言うエチレン性不飽和基を有する化合物には、エチレン性不飽和基を有する(A)カルボキシル基含有樹脂および(C)表面処理された無機フィラーは含まれないものとする。 (Compound having an ethylenically unsaturated group)
When the curable resin composition of the present invention is photocurable, a compound having one or more ethylenically unsaturated groups in the molecule is preferably used. As the compound having an ethylenically unsaturated group, a photopolymerizable oligomer, a photopolymerizable vinyl monomer, or the like that is a known and commonly used photosensitive monomer can be used. In addition, the compound which has an ethylenically unsaturated group said here shall not contain the (A) carboxyl group-containing resin which has an ethylenically unsaturated group, and the (C) surface-treated inorganic filler.
本発明の硬化性樹脂組成物は、熱硬化触媒を含有することが好ましい。そのような熱硬化触媒としては、例えば、イミダゾール、2-メチルイミダゾール、2-エチルイミダゾール、2-エチル-4-メチルイミダゾール、2-フェニルイミダゾール、4-フェニルイミダゾール、1-シアノエチル-2-フェニルイミダゾール、1-(2-シアノエチル)-2-エチル-4-メチルイミダゾール等のイミダゾール誘導体;ジシアンジアミド、ベンジルジメチルアミン、4-(ジメチルアミノ)-N,N-ジメチルベンジルアミン、4-メトキシ-N,N-ジメチルベンジルアミン、4-メチル-N,N-ジメチルベンジルアミン等のアミン化合物、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド等のヒドラジン化合物;トリフェニルホスフィン等のリン化合物等が挙げられる。また、グアナミン、アセトグアナミン、ベンゾグアナミン、メラミン、2,4-ジアミノ-6-メタクリロイルオキシエチル-S-トリアジン、2-ビニル-2,4-ジアミノ-S-トリアジン、2-ビニル-4,6-ジアミノ-S-トリアジン・イソシアヌル酸付加物、2,4-ジアミノ-6-メタクリロイルオキシエチル-S-トリアジン・イソシアヌル酸付加物等のS-トリアジン誘導体を用いることもでき、好ましくはこれら密着性付与剤としても機能する化合物を熱硬化触媒と併用する。 (Thermosetting catalyst)
The curable resin composition of the present invention preferably contains a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine / isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adducts can also be used. A compound that also functions in combination with a thermosetting catalyst.
本発明の硬化性樹脂組成物は硬化剤を含有することができる。硬化剤としては、フェノール樹脂、ポリカルボン酸およびその酸無水物、シアネートエステル樹脂、活性エステル樹脂、マレイミド化合物、脂環式オレフィン重合体等が挙げられる。硬化剤は1種を単独または2種以上を組み合わせて用いることができる。 (Curing agent)
The curable resin composition of the present invention can contain a curing agent. Examples of the curing agent include phenol resins, polycarboxylic acids and acid anhydrides thereof, cyanate ester resins, active ester resins, maleimide compounds, and alicyclic olefin polymers. A hardening | curing agent can be used individually by 1 type or in combination of 2 or more types.
本発明の硬化性樹脂組成物には、着色剤が含まれていてもよい。着色剤としては、赤、青、緑、黄、黒、白等の公知の着色剤を使用することができ、顔料、染料、色素のいずれでもよい。但し、環境負荷低減並びに人体への影響の観点からハロゲンを含有しないことが好ましい。 (Coloring agent)
The curable resin composition of the present invention may contain a colorant. As the colorant, known colorants such as red, blue, green, yellow, black, and white can be used, and any of pigments, dyes, and pigments may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.
本発明の硬化性樹脂組成物には、組成物の調製や、基板やキャリアフィルムに塗布する際の粘度調整等の目的で、有機溶剤を含有させることができる。有機溶剤としては、メチルエチルケトン、シクロヘキサノン等のケトン類;トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類;セロソルブ、メチルセロソルブ、ブチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジエチルエーテル、ジエチレングリコールモノメチルエーテルアセテート、トリプロピレングリコールモノメチルエーテル等のグリコールエーテル類;酢酸エチル、酢酸ブチル、乳酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、炭酸プロピレン等のエステル類;オクタン、デカン等の脂肪族炭化水素類;石油エーテル、石油ナフサ、ソルベントナフサ等の石油系溶剤など、公知慣用の有機溶剤が使用できる。これらの有機溶剤は、単独で、または二種類以上組み合わせて用いることができる。 (Organic solvent)
The curable resin composition of the present invention can contain an organic solvent for the purpose of preparing the composition and adjusting the viscosity when applied to a substrate or a carrier film. Examples of organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether , Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butylcarby Tall acetate, propylene glycol monomethyl ether acetate, dip Propylene glycol monomethyl ether acetate, esters such as propylene carbonate; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, and petroleum solvents such as solvent naphtha, organic solvents conventionally known can be used. These organic solvents can be used alone or in combination of two or more.
さらに、本発明の硬化性樹脂組成物には、電子材料の分野において公知慣用の他の添加剤を配合してもよい。他の添加剤としては、熱重合禁止剤、紫外線吸収剤、シランカップリング剤、可塑剤、難燃剤、帯電防止剤、老化防止剤、抗菌・防黴剤、消泡剤、レベリング剤、増粘剤、密着性付与剤、チキソ性付与剤、光開始助剤、増感剤、熱可塑性樹脂、有機フィラー、離型剤、表面処理剤、分散剤、分散助剤、表面改質剤、安定剤、蛍光体等が挙げられる。 (Other optional ingredients)
Furthermore, you may mix | blend the other well-known and usual additive in the field | area of an electronic material with the curable resin composition of this invention. Other additives include thermal polymerization inhibitors, UV absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial / antifungal agents, antifoaming agents, leveling agents, thickening agents Agent, adhesion imparting agent, thixotropic agent, photoinitiator aid, sensitizer, thermoplastic resin, organic filler, mold release agent, surface treatment agent, dispersant, dispersion aid, surface modifier, stabilizer And phosphors.
多官能エポキシ化合物としては、エポキシ化植物油;ビスフェノールA型エポキシ樹脂;ハイドロキノン型エポキシ樹脂;ビスフェノール型エポキシ樹脂;チオエーテル型エポキシ樹脂;ブロム化エポキシ樹脂;ノボラック型エポキシ樹脂;ビフェノールノボラック型エポキシ樹脂;ビスフェノールF型エポキシ樹脂;水添ビスフェノールA型エポキシ樹脂;グリシジルアミン型エポキシ樹脂;ヒダントイン型エポキシ樹脂;脂環式エポキシ樹脂;トリヒドロキシフェニルメタン型エポキシ樹脂;アルキルフェノール型エポキシ樹脂(例えば、ビキシレノール型エポキシ樹脂);ビフェノール型エポキシ樹脂;ビスフェノールS型エポキシ樹脂;ビスフェノールAノボラック型エポキシ樹脂;テトラフェニロールエタン型エポキシ樹脂;複素環式エポキシ樹脂;ジグリシジルフタレート樹脂;テトラグリシジルキシレノイルエタン樹脂;ナフタレン基含有エポキシ樹脂;ジシクロペンタジエン骨格を有するエポキシ樹脂;トリフェニルメタン型エポキシ樹脂;シルセスキオキサン骨格を有するエポキシ樹脂;グリシジルメタアクリレート共重合系エポキシ樹脂;シクロヘキシルマレイミドとグリシジルメタアクリレートの共重合エポキシ樹脂;エポキシ変性のポリブタジエンゴム誘導体;CTBN変性エポキシ樹脂等が挙げられるが、これらに限られるものではない。これらのエポキシ樹脂は、1種を単独または2種以上を組み合わせて用いることができる。これらの中でも特にトリフェニルメタン型エポキシ樹脂、ノボラック型エポキシ樹脂、ビスフェノール型エポキシ樹脂、ビキシレノール型エポキシ樹脂、ビフェノール型エポキシ樹脂、ビフェノールノボラック型エポキシ樹脂、ナフタレン型エポキシ樹脂、またはそれらの混合物が好ましい。(B)シルセスキオキサン骨格を有するエポキシ樹脂と、他のエポキシ樹脂を併用することで、硬化物のガラス転移温度を高くすることができる。 As the thermosetting resin other than the (B) epoxy resin, a compound having a plurality of cyclic (thio) ether groups in the molecule is preferable. The compound having a plurality of cyclic (thio) ether groups in the molecule is a compound having a plurality of 3, 4 or 5-membered cyclic (thio) ether groups in the molecule. A compound having a group, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, that is, a polyfunctional episulfide resin.
Polyfunctional epoxy compounds include epoxidized vegetable oils; bisphenol A type epoxy resins; hydroquinone type epoxy resins; bisphenol type epoxy resins; thioether type epoxy resins; brominated epoxy resins; novolac type epoxy resins; biphenol novolac type epoxy resins; Type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; trihydroxyphenylmethane type epoxy resin; alkylphenol type epoxy resin (for example, bixylenol type epoxy resin) Biphenol type epoxy resin; Bisphenol S type epoxy resin; Bisphenol A novolac type epoxy resin; Tetraphenylolethane type epoxy resin; Complex Diglycidyl phthalate resin; Tetraglycidyl xylenoyl ethane resin; Naphthalene group-containing epoxy resin; Epoxy resin having dicyclopentadiene skeleton; Triphenylmethane type epoxy resin; Epoxy resin having silsesquioxane skeleton; Glycidyl Examples thereof include, but are not limited to, a methacrylate copolymer epoxy resin; a copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; an epoxy-modified polybutadiene rubber derivative; a CTBN-modified epoxy resin. These epoxy resins can be used alone or in combination of two or more. Among these, triphenylmethane type epoxy resin, novolak type epoxy resin, bisphenol type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, biphenol novolak type epoxy resin, naphthalene type epoxy resin, or a mixture thereof is particularly preferable. (B) The glass transition temperature of hardened | cured material can be made high by using together the epoxy resin which has silsesquioxane frame | skeleton, and another epoxy resin.
尚、本明細書において、Tanδは、特に断りが無い限り、樹脂組成物の乾燥後の樹脂層に対し、約500mJ/cm2で紫外線を照射後、さらに高圧水銀灯を備えたUVコンベア炉にて1J/cm2の露光量で照射した後、160℃で60分加熱して樹脂層を完全硬化させて得られる厚さ40μmの硬化物の物性を意味する。また、紫外線とは波長が10~400nmの電磁波である。Tanδは、動的粘弾性測定で測定した損失弾性率を貯蔵弾性率で除した値、即ち、損失正接(=損失弾性率/貯蔵弾性率)であり、本明細書においてTanδは、周波数1Hz、昇温速度5℃/minの条件下で25℃~300℃まで測定して得られるチャート図に基づくものである。 In the curable resin composition of the present invention, the maximum value of Tan δ in the temperature range of 25 to 300 ° C. of the cured product is preferably less than 0.25. With such physical properties, stable crack resistance can be obtained even when the temperature of the cured film is near Tg or above Tg.
In the present specification, unless otherwise specified, Tan δ is measured with a UV conveyor furnace equipped with a high-pressure mercury lamp after irradiation of the resin layer after drying the resin composition with ultraviolet rays at about 500 mJ / cm 2 . It means the physical properties of a cured product having a thickness of 40 μm obtained by irradiation at an exposure amount of 1 J / cm 2 and then heating at 160 ° C. for 60 minutes to completely cure the resin layer. Ultraviolet rays are electromagnetic waves having a wavelength of 10 to 400 nm. Tan δ is a value obtained by dividing the loss elastic modulus measured by dynamic viscoelasticity measurement by the storage elastic modulus, that is, loss tangent (= loss elastic modulus / storage elastic modulus). In this specification, Tan δ is a frequency of 1 Hz, This is based on a chart obtained by measuring from 25 ° C. to 300 ° C. under a temperature rising rate of 5 ° C./min.
Tanδの最大値を0.25未満とするための手段は特に限定されない。 In order to obtain a cured product having a small Tan δ (= loss elastic modulus / storage elastic modulus), the loss elastic modulus (viscous component) is decreased, the storage elastic modulus (elastic component) is increased, or both are performed. In other words, the elastic component may be increased as much as possible in the cured product rather than the viscous component.
The means for setting the maximum value of Tan δ to less than 0.25 is not particularly limited.
なお、本発明の硬化性樹脂組成物が、光塩基発生剤を含む場合、露光後現像前に加熱することが好ましく、露光後現像前の加熱条件としては、例えば、60~150℃で1~60分加熱することが好ましい。 When the curable resin composition of the present invention is light-hardened, after forming a resin layer on a printed wiring board, it is selectively exposed with active energy rays through a photomask having a predetermined pattern, and unexposed portions are diluted. Development with an alkaline aqueous solution (for example, 0.3 to 3% by mass aqueous sodium carbonate solution) forms a pattern of a cured product. Further, the cured product is irradiated with active energy rays and then heat-cured (for example, 100 to 220 ° C.), irradiated with active energy rays after heat-curing, or is subjected to final finish curing (main curing) only by heat-curing. A cured film having excellent properties such as properties and hardness is formed.
When the curable resin composition of the present invention contains a photobase generator, it is preferably heated after exposure and before development. The heating conditions before development after exposure are, for example, 1 to 1 at 60 to 150 ° C. It is preferable to heat for 60 minutes.
温度計、窒素導入装置兼アルキレンオキシド導入装置および撹拌装置を備えたオートクレーブに、ノボラック型クレゾール樹脂(昭和電工社製ショーノールCRG95、OH当量:119.4)119.4部、水酸化カリウム1.19部およびトルエン119.4部を導入し、撹拌しつつ系内を窒素置換し、加熱昇温した。次に、プロピレンオキシド63.8部を徐々に滴下し、125~132℃、0~4.8kg/cm2で16時間反応させた。その後、室温まで冷却し、この反応溶液に89%リン酸1.56部を添加混合して水酸化カリウムを中和し、不揮発分62.1%、水酸基価が182.2mgKOH/g(307.9g/eq.)であるノボラック型クレゾール樹脂のプロピレンオキシド反応溶液を得た。これは、フェノール性水酸基1当量当りプロピレンオキシドが平均1.08モル付加したものであった。
得られたノボラック型クレゾール樹脂のプロピレンオキシド反応溶液293.0部、アクリル酸43.2部、メタンスルホン酸11.53部、メチルハイドロキノン0.18部およびトルエン252.9部を、撹拌機、温度計および空気吹き込み管を備えた反応器に導入し、空気を10ml/分の速度で吹き込み、撹拌しながら、110℃で12時間反応させた。反応により生成した水は、トルエンとの共沸混合物として、12.6部の水が留出した。その後、室温まで冷却し、得られた反応溶液を15%水酸化ナトリウム水溶液35.35部で中和し、次いで水洗した。その後、エバポレーターにてトルエンをジエチレングリコールモノエチルエーテルアセテート118.1部で置換しつつ留去し、ノボラック型アクリレート樹脂溶液を得た。次に、得られたノボラック型アクリレート樹脂溶液332.5部およびトリフェニルホスフィン1.22部を、撹拌器、温度計および空気吹き込み管を備えた反応器に導入し、空気を10ml/分の速度で吹き込み、撹拌しながら、テトラヒドロフタル酸無水物60.8部を徐々に加え、95~101℃で6時間反応させ、冷却後、取り出した。このようにして、固形分65%、固形分の酸価87.7mgKOH/gの感光性のカルボキシル基含有樹脂A-1の溶液を得た。以下、このカルボキシル基含有感光性樹脂の溶液を樹脂溶液A-1と称す。 [Synthesis of carboxyl group-containing resin A-1]
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device, 119.4 parts of a novolac-type cresol resin (Shornol CRG95, OH equivalent: 119.4, manufactured by Showa Denko KK), potassium hydroxide 1. 19 parts and 119.4 parts of toluene were introduced, the inside of the system was replaced with nitrogen while stirring, and the temperature was increased by heating. Next, 63.8 parts of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm 2 for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1%, and the hydroxyl value was 182.2 mgKOH / g (307. 9 g / eq.) Of a novolak-type cresol resin propylene oxide reaction solution. This was an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
293.0 parts of a propylene oxide reaction solution of the obtained novolac-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 part of methylhydroquinone and 252.9 parts of toluene were mixed with a stirrer and a temperature. It was introduced into a reactor equipped with a meter and an air blowing tube, and air was blown at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours while stirring. 12.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 parts of the obtained novolak acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was supplied at a rate of 10 ml / min. With stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added, reacted at 95 to 101 ° C. for 6 hours, cooled and taken out. Thus, a solution of photosensitive carboxyl group-containing resin A-1 having a solid content of 65% and a solid content acid value of 87.7 mgKOH / g was obtained. Hereinafter, this carboxyl group-containing photosensitive resin solution is referred to as Resin Solution A-1.
冷却管、攪拌機を備えたフラスコに、ビスフェノールA456部、水228部、37%ホルマリン649部を仕込み、40℃以下の温度を保ち、25%水酸化ナトリウム水溶液228部を添加した、添加終了後50℃で10時間反応した。反応終了後40℃まで冷却し、40℃以下を保ちながら37.5%リン酸水溶液でpH4まで中和した。その後静置し水層を分離した。分離後メチルイソブチルケトン300部を添加し均一に溶解した後、蒸留水500部で3回洗浄し、50℃以下の温度で減圧下、水、溶媒等を除去した。得られたポリメチロール化合物をメタノール550部に溶解し、ポリメチロール化合物のメタノール溶液1230部を得た。
得られたポリメチロール化合物のメタノール溶液の一部を真空乾燥機中室温で乾燥したところ、固形分が55.2%であった。
冷却管、攪拌機を備えたフラスコに、得られたポリメチロール化合物のメタノール溶液500部、2,6-キシレノール440部を仕込み、50℃で均一に溶解した。均一に溶解した後50℃以下の温度で減圧下メタノールを除去した。その後シュウ酸8部を加え、100℃で10時間反応した。反応終了後180℃、50mmHgの減圧下で溜出分を除去し、ノボラック樹脂Aを550部を得た。
温度計、窒素導入装置兼アルキレンオキシド導入装置および撹拌装置を備えたオートクレーブに、ノボラック樹脂A 130部、50%水酸化ナトリウム水溶液2.6部、トルエン/メチルイソブチルケトン(質量比=2/1)100部を仕込み、撹拌しつつ系内を窒素置換し、次に加熱昇温し、150℃、8kg/cm2でプロピレンオキシド60部を徐々に導入し反応させた。反応はゲージ圧0.0kg/cm2となるまで約4時間を続けた後、室温まで冷却した。この反応溶液に3.3部の36%塩酸水溶液を添加混合し、水酸化ナトリウムを中和した。この中和反応生成物をトルエンで希釈し、3回水洗し、エバポレーターにて脱溶剤して、水酸基価が189g/eq.であるノボラック樹脂Aのプロピレンオキシド付加物を得た。これは、フェノール性水酸基1当量当りプロピレンオキシドが平均1モル付加しているものであった。
得られたノボラック樹脂Aのプロピレンオキシド付加物189部、アクリル酸36部、p-トルエンスルホン酸3.0部、ハイドロキノンモノメチルエーテル0.1部、トルエン140部を撹拌機、温度計、空気吹き込み管を備えた反応器に仕込み、空気を吹き込みながら攪拌して、115℃に昇温し、反応により生成した水をトルエンと共沸混合物として留去しながら、さらに4時間反応させたのち、室温まで冷却した。得られた反応溶液を5%NaCl水溶液を用いて水洗し、減圧留去にてトルエンを除去したのち、ジエチレングリコールモノエチルエーテルアセテートを加えて、固形分67%のアクリレート樹脂溶液を得た。
次に、撹拌器および還流冷却器の付いた4つ口フラスコに、得られたアクリレート樹脂溶液322部、ハイドロキノンモノメチルエーテル0.1部、トリフェニルホスフィン0.3部を仕込み、この混合物を110℃に加熱し、テトラヒドロ無水フタル酸60部を加え、4時間反応させ、冷却後、取り出した。このようにして得られた感光性のカルボキシル基含有樹脂溶液は、固形分70%、固形分酸価81mgKOH/gであった。以下、このカルボキシル基含有感光性樹脂の溶液を樹脂溶液A-2と称す。 [Synthesis of carboxyl group-containing resin A-2]
A flask equipped with a condenser and a stirrer was charged with 456 parts of bisphenol A, 228 parts of water, and 649 parts of 37% formalin, and kept at a temperature of 40 ° C. or lower, and 228 parts of 25% aqueous sodium hydroxide solution was added. The reaction was carried out at 0 ° C. for 10 hours. After completion of the reaction, the reaction mixture was cooled to 40 ° C. and neutralized to pH 4 with a 37.5% phosphoric acid aqueous solution while maintaining the temperature at 40 ° C. or lower. Thereafter, the mixture was allowed to stand to separate the aqueous layer. After separation, 300 parts of methyl isobutyl ketone was added and dissolved uniformly, and then washed three times with 500 parts of distilled water, and water, solvent, and the like were removed under reduced pressure at a temperature of 50 ° C. or lower. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanol solution of the polymethylol compound.
When a part of the methanol solution of the obtained polymethylol compound was dried at room temperature in a vacuum dryer, the solid content was 55.2%.
In a flask equipped with a condenser and a stirrer, 500 parts of a methanol solution of the obtained polymethylol compound and 440 parts of 2,6-xylenol were charged and uniformly dissolved at 50 ° C. After dissolving uniformly, methanol was removed under reduced pressure at a temperature of 50 ° C. or lower. Thereafter, 8 parts of oxalic acid was added and reacted at 100 ° C. for 10 hours. After completion of the reaction, the distillate was removed under reduced pressure at 180 ° C. and 50 mmHg to obtain 550 parts of novolak resin A.
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device, 130 parts of novolak resin A, 2.6 parts of 50% aqueous sodium hydroxide, toluene / methyl isobutyl ketone (mass ratio = 2/1) 100 parts were charged, and the system was purged with nitrogen while stirring. Next, the temperature was raised by heating, and 60 parts of propylene oxide was gradually introduced and reacted at 150 ° C. and 8 kg / cm 2 . The reaction was continued for about 4 hours until the gauge pressure reached 0.0 kg / cm 2, and then cooled to room temperature. To this reaction solution, 3.3 parts of 36% aqueous hydrochloric acid was added and mixed to neutralize sodium hydroxide. The neutralized reaction product was diluted with toluene, washed with water three times, and the solvent was removed with an evaporator. The hydroxyl value was 189 g / eq. A propylene oxide adduct of novolak resin A was obtained. This was an average of 1 mole of propylene oxide added per equivalent of phenolic hydroxyl group.
189 parts of propylene oxide adduct of the obtained novolak resin A, 36 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 part of hydroquinone monomethyl ether and 140 parts of toluene were stirred, a thermometer, and an air blowing tube. Was stirred while blowing air, heated to 115 ° C., reacted for an additional 4 hours while distilling off the water produced by the reaction as an azeotrope with toluene, and then brought to room temperature. Cooled down. The obtained reaction solution was washed with 5% NaCl aqueous solution, and toluene was removed by distillation under reduced pressure. Diethylene glycol monoethyl ether acetate was added to obtain an acrylate resin solution having a solid content of 67%.
Next, in a four-necked flask equipped with a stirrer and a reflux condenser, 322 parts of the obtained acrylate resin solution, 0.1 part of hydroquinone monomethyl ether, and 0.3 part of triphenylphosphine were charged. Then, 60 parts of tetrahydrophthalic anhydride was added, reacted for 4 hours, cooled and taken out. The photosensitive carboxyl group-containing resin solution thus obtained had a solid content of 70% and a solid content acid value of 81 mgKOH / g. Hereinafter, this carboxyl group-containing photosensitive resin solution is referred to as Resin Solution A-2.
ジエチレングリコールモノエチルエーテルアセテート600gにオルソクレゾールノボラック型エポキシ樹脂(DIC社製EPICLON N-695、軟化点95℃、エポキシ当量214、平均官能基数7.6)1070g(グリシジル基数(芳香環総数):5.0モル)、アクリル酸360g(5.0モル)、およびハイドロキノン1.5gを仕込み、100℃に加熱攪拌し、均一溶解した。
次いで、トリフェニルホスフィン4.3gを仕込み、110℃に加熱して2時間反応後、120℃に昇温してさらに12時間反応を行った。得られた反応液に、芳香族系炭化水素(ソルベッソ150)415g、テトラヒドロ無水フタル酸456.0g(3.0モル)を仕込み、110℃で4時間反応を行い、冷却し、感光性のカルボキシル基含有樹脂溶液を得た。このようにして得られた樹脂溶液の固形分は65%、固形分の酸価は89mgKOH/gであった。以下、このカルボキシル基含有感光性樹脂の溶液を樹脂溶液A-3と称す。 [Synthesis of carboxyl group-containing resin A-3]
Orthocresol novolak type epoxy resin (DICICLON N-695 manufactured by DIC, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) to 1070 g (number of glycidyl groups (total number of aromatic rings)): 600 g of diethylene glycol monoethyl ether acetate 0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved.
Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. Into the obtained reaction liquid, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added, reacted at 110 ° C. for 4 hours, cooled, and photosensitive carboxyl A group-containing resin solution was obtained. The resin solution thus obtained had a solid content of 65% and an acid value of the solid content of 89 mgKOH / g. Hereinafter, this carboxyl group-containing photosensitive resin solution is referred to as Resin Solution A-3.
温度計、撹拌機、滴下ロート、および還流冷却器を備えたフラスコに、溶媒としてジプロピレングリコールモノメチルエーテル325.0部を110℃まで加熱し、メタクリル酸174.0部、ε-カプロラクトン変性メタクリル酸(平均分子量314)174.0部、メタクリル酸メチル77.0部、ジプロピレングリコールモノメチルエーテル222.0部、および重合触媒としてt-ブチルパーオキシ2-エチルヘキサノエート(日油社製パーブチルO)12.0部の混合物を、3時間かけて滴下し、さらに110℃で3時間攪拌し、重合触媒を失活させて、樹脂溶液を得た。
この樹脂溶液を冷却後、ダイセル化学工業社製サイクロマーA200を289.0部、トリフェニルホスフィン3.0部、ハイドロキノンモノメチルエーテル1.3部を加え、100℃に昇温し、攪拌することによってエポキシ基の開環付加反応を行い、感光性のカルボキシル基含有樹脂溶液を得た。
このようにして得られた樹脂溶液は、重量平均分子量(Mw)が15,000で、かつ、固形分が57%、固形物の酸価が79.8mgKOH/gであった。以下、このカルボキシル基含有感光性樹脂の溶液を樹脂溶液A-4と称す。 [Synthesis of carboxyl group-containing resin A-4]
In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, 325.0 parts of dipropylene glycol monomethyl ether as a solvent was heated to 110 ° C., and 174.0 parts of methacrylic acid, ε-caprolactone-modified methacrylic acid (Average molecular weight 314) 174.0 parts, methyl methacrylate 77.0 parts, dipropylene glycol monomethyl ether 222.0 parts, and t-butyl peroxy 2-ethylhexanoate (Perbutyl O. ) 12.0 parts of the mixture was added dropwise over 3 hours and further stirred at 110 ° C. for 3 hours to deactivate the polymerization catalyst to obtain a resin solution.
After cooling this resin solution, 289.0 parts of Cyclomer A200 manufactured by Daicel Chemical Industries, Ltd., 3.0 parts of triphenylphosphine and 1.3 parts of hydroquinone monomethyl ether were added, and the mixture was heated to 100 ° C. and stirred. A ring-opening addition reaction of an epoxy group was performed to obtain a photosensitive carboxyl group-containing resin solution.
The resin solution thus obtained had a weight average molecular weight (Mw) of 15,000, a solid content of 57%, and a solid acid value of 79.8 mgKOH / g. Hereinafter, this carboxyl group-containing photosensitive resin solution is referred to as Resin Solution A-4.
γ-グリシドキシプロピルトリメトキシシラン90.0部、メチルイソブチルケトン93部を反応容器に仕込み、80℃に昇温した。昇温後、0.1重量%水酸化カリウム水溶液21.6部を30分間かけて連続的に滴下した。滴下終了後、生成するメタノールを除去しながら80℃にて5時間反応させた。反応終了後、洗浄液が中性になるまで水洗を繰り返した。次いで減圧下で溶媒を除去することによりシルセスキオキサン骨格を有するエポキシ樹脂69部を得た。得られたエポキシ樹脂のエポキシ当量は165g/eq.、重量平均分子量は2000であった。 [Synthesis of epoxy resin B-1 having silsesquioxane skeleton]
90.0 parts of γ-glycidoxypropyltrimethoxysilane and 93 parts of methyl isobutyl ketone were charged into a reaction vessel and heated to 80 ° C. After the temperature increase, 21.6 parts of a 0.1 wt% aqueous potassium hydroxide solution was continuously added dropwise over 30 minutes. After completion of the dropping, the reaction was carried out at 80 ° C. for 5 hours while removing the produced methanol. After completion of the reaction, washing with water was repeated until the washing solution became neutral. Next, 69 parts of an epoxy resin having a silsesquioxane skeleton was obtained by removing the solvent under reduced pressure. The epoxy equivalent of the obtained epoxy resin is 165 g / eq. The weight average molecular weight was 2000.
γ-グリシドキシプロピルトリメトキシシラン90.0部、フェニルトリメトキシシラン3.0部、メチルトリメトキシシラン2.0部、メチルイソブチルケトン93部を反応容器に仕込み、80℃に昇温した。昇温後、0.1重量%水酸化カリウム水溶液21.6部を30分間かけて連続的に滴下した。滴下終了後、生成するメタノールを除去しながら80℃にて5時間反応させた。反応終了後、洗浄液が中性になるまで水洗を繰り返した。次いで減圧下で溶媒を除去することによりシルセスキオキサン骨格を有するエポキシ樹脂69部を得た。得られたエポキシ樹脂のエポキシ当量は176g/eq.、重量平均分子量は2200であった。 [Synthesis of epoxy resin B-2 having silsesquioxane skeleton]
90.0 parts of γ-glycidoxypropyltrimethoxysilane, 3.0 parts of phenyltrimethoxysilane, 2.0 parts of methyltrimethoxysilane, and 93 parts of methyl isobutyl ketone were charged into a reaction vessel, and the temperature was raised to 80 ° C. After the temperature increase, 21.6 parts of a 0.1 wt% aqueous potassium hydroxide solution was continuously added dropwise over 30 minutes. After completion of the dropping, the reaction was carried out at 80 ° C. for 5 hours while removing the produced methanol. After completion of the reaction, washing with water was repeated until the washing solution became neutral. Next, 69 parts of an epoxy resin having a silsesquioxane skeleton was obtained by removing the solvent under reduced pressure. The epoxy equivalent of the obtained epoxy resin is 176 g / eq. The weight average molecular weight was 2200.
γ-グリシドキシプロピルトリメトキシシラン65.0部、フェニルトリメトキシシラン12.0部、メチルトリメトキシシラン8.0部、メチルイソブチルケトン93部を反応容器に仕込み、80℃に昇温した。昇温後、0.1重量%水酸化カリウム水溶液21.6部を30分間かけて連続的に滴下した。滴下終了後、生成するメタノールを除去しながら80℃にて5時間反応させた。反応終了後、洗浄液が中性になるまで水洗を繰り返した。次いで減圧下で溶媒を除去することによりシルセスキオキサン骨格を有するエポキシ樹脂69部を得た。得られたエポキシ樹脂のエポキシ当量は236g/eq.、重量平均分子量は2200であった。 [Synthesis of Epoxy Resin B-3 Having Silsesquioxane Skeleton]
A reaction vessel was charged with 65.0 parts of γ-glycidoxypropyltrimethoxysilane, 12.0 parts of phenyltrimethoxysilane, 8.0 parts of methyltrimethoxysilane, and 93 parts of methylisobutylketone, and the temperature was raised to 80 ° C. After the temperature increase, 21.6 parts of a 0.1 wt% aqueous potassium hydroxide solution was continuously added dropwise over 30 minutes. After completion of the dropping, the reaction was carried out at 80 ° C. for 5 hours while removing the produced methanol. After completion of the reaction, washing with water was repeated until the washing solution became neutral. Next, 69 parts of an epoxy resin having a silsesquioxane skeleton was obtained by removing the solvent under reduced pressure. The epoxy equivalent of the obtained epoxy resin is 236 g / eq. The weight average molecular weight was 2200.
γ-グリシドキシプロピルトリメトキシシラン40.0部、フェニルトリメトキシシラン25.0部、メチルトリメトキシシラン15.0部、メチルイソブチルケトン93部を反応容器に仕込み、80℃に昇温した。昇温後、0.1重量%水酸化カリウム水溶液21.6部を30分間かけて連続的に滴下した。滴下終了後、生成するメタノールを除去しながら80℃にて5時間反応させた。反応終了後、洗浄液が中性になるまで水洗を繰り返した。次いで減圧下で溶媒を除去することによりシルセスキオキサン骨格を有するエポキシ樹脂69部を得た。得られたエポキシ樹脂のエポキシ当量は400g/eq.、重量平均分子量は2200であった。 [Synthesis of Epoxy Resin B-4 Having Silsesquioxane Skeleton]
A reaction vessel was charged with 40.0 parts of γ-glycidoxypropyltrimethoxysilane, 25.0 parts of phenyltrimethoxysilane, 15.0 parts of methyltrimethoxysilane, and 93 parts of methylisobutylketone, and the temperature was raised to 80 ° C. After the temperature increase, 21.6 parts of a 0.1 wt% aqueous potassium hydroxide solution was continuously added dropwise over 30 minutes. After completion of the dropping, the reaction was carried out at 80 ° C. for 5 hours while removing the produced methanol. After completion of the reaction, washing with water was repeated until the washing solution became neutral. Next, 69 parts of an epoxy resin having a silsesquioxane skeleton was obtained by removing the solvent under reduced pressure. The epoxy equivalent of the obtained epoxy resin is 400 g / eq. The weight average molecular weight was 2200.
球状シリカ(デンカ社製SFP-20M)70gと、溶剤としてPMA(プロピレングリコールモノメチルエーテルアセテート)28gと、シランカップリング剤(信越化学工業社製KBM-503)2gとを均一分散させて、シリカ溶剤分散品D-1を得た。 [Preparation of surface-treated inorganic filler (silica) C-1]
70 g of spherical silica (SFP-20M manufactured by Denka), 28 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 2 g of a silane coupling agent (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) are uniformly dispersed to obtain a silica solvent. Dispersion D-1 was obtained.
硫酸バリウム(堺化学工業社製B-30(アルミナ表面処理硫酸バリウム))を70gと、溶剤としてPMA(プロピレングリコールモノメチルエーテルアセテート)を28gと、分散剤(BYK社製BYK-111)2gとを均一分散させて、硫酸バリウム溶剤分散品D-2を得た。 [Preparation of surface-treated inorganic filler (barium sulfate) C-2]
70 g of barium sulfate (B-30 manufactured by Sakai Chemical Industry Co., Ltd.), 28 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 2 g of a dispersant (BYK-111 manufactured by BYK) By uniformly dispersing, a barium sulfate solvent dispersion D-2 was obtained.
球状シリカ(デンカ社製SFP-20M)70gと、溶剤としてPMA(プロピレングリコールモノメチルエーテルアセテート)28gと、分散剤(BYK社製BYK-111)2gとを均一分散させて、シリカ溶剤分散品を得た。 [Preparation of untreated surface silica]
70 g of spherical silica (SFP-20M manufactured by Denka), 28 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 2 g of a dispersant (BYK-111 manufactured by BYK) are uniformly dispersed to obtain a silica solvent dispersion product. It was.
上記の樹脂溶液(ワニス)を、表1に示す種々の成分とともに表1に示す割合(質量部)にて配合し、攪拌機にて予備混合した後、3本ロールミルで混練し、硬化性樹脂組成物を調製した。 [Examples 1 to 16, Comparative Examples 1 to 5]
The above resin solution (varnish) is blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and curable resin composition A product was prepared.
(実施例1~15,比較例1~5)
銅箔基板上に、硬化性樹脂組成物をスクリーン印刷により乾燥膜厚約40μmになるように全面塗布した。これを、80℃で乾燥し、室温まで放冷することにより、硬化性樹脂組成物からなる樹脂層を形成し、各実施例および比較例ごとの未硬化サンプルを有する評価基板を得た。これに対して、ORC社製HMW680GW(メタルハライドランプ、散乱光)により、最適露光量:800mJにて50mm×3mmの短冊状のネガマスクを通して露光を行った。その後、30℃の1wt.%炭酸ナトリウム水溶液で現像を行い、硬化膜のパターンを得た。更に積算露光量を1000mJとして紫外線を照射した後、160℃で1時間加熱して硬化した。
上記により得られた評価基板の硬化膜を銅箔より剥離し、評価を実施した。測定は、TMA測定装置(島津製作所社製、機種名:TMA6000)を用いて行い、TgとCTEα1(0℃-50℃)、CTEα2(200℃-250℃)ついて評価を行った。評価基準は以下の通りである。
(実施例16)
銅箔基板上に、硬化性樹脂組成物をスクリーン印刷により乾燥膜厚約40μmになるように全面塗布した。これを、80℃で乾燥し、室温まで放冷することにより、硬化性樹脂組成物からなる樹脂層を形成した。これを160℃で1時間加熱して硬化させて硬化膜を有する評価基板を得た。
上記により得られた評価基板の硬化膜を銅箔より剥離し、50mm×3mmの短冊状に切り出して評価を実施した。測定は、TMA測定装置(島津製作所社製、機種名:TMA6000)を用いて行い、TgとCTEα1(0℃-50℃)、CTEα2(200℃-250℃)ついて評価を行った。評価基準は以下の通りである。
(Tg)
◎…150℃以上
○…145℃以上150℃未満
△…140℃以上145℃未満
×…140℃未満
(CTEα1)
◎…40ppm未満
○…40ppm以上50ppm未満
△…50ppm以上60ppm未満
×…60ppm以上
(CTEα2)
◎…110ppm未満
○…110ppm以上120ppm未満
△…120ppm以上130ppm未満
×…130ppm以上 <Glass transition temperature Tg and thermal expansion coefficient CTE>
(Examples 1 to 15, Comparative Examples 1 to 5)
On the copper foil substrate, the entire surface of the curable resin composition was applied by screen printing to a dry film thickness of about 40 μm. This was dried at 80 ° C. and allowed to cool to room temperature, thereby forming a resin layer made of a curable resin composition, and obtaining an evaluation substrate having an uncured sample for each example and comparative example. On the other hand, exposure was performed through a strip-shaped negative mask of 50 mm × 3 mm at an optimum exposure amount: 800 mJ with ORC HMW680GW (metal halide lamp, scattered light). Thereafter, 1 wt. Development was performed with an aqueous sodium carbonate solution to obtain a cured film pattern. Furthermore, after irradiating with ultraviolet rays with an integrated exposure amount of 1000 mJ, the film was cured by heating at 160 ° C. for 1 hour.
The cured film of the evaluation board | substrate obtained by the above was peeled off from copper foil, and evaluation was implemented. The measurement was performed using a TMA measuring apparatus (manufactured by Shimadzu Corporation, model name: TMA6000), and Tg, CTEα1 (0 ° C.-50 ° C.), and CTEα2 (200 ° C.-250 ° C.) were evaluated. The evaluation criteria are as follows.
(Example 16)
On the copper foil substrate, the entire surface of the curable resin composition was applied by screen printing to a dry film thickness of about 40 μm. This was dried at 80 ° C. and allowed to cool to room temperature, thereby forming a resin layer made of a curable resin composition. This was heated and cured at 160 ° C. for 1 hour to obtain an evaluation substrate having a cured film.
The cured film of the evaluation board | substrate obtained by the above was peeled off from copper foil, and it cut out to 50 mm x 3 mm strip shape, and evaluated. The measurement was performed using a TMA measuring apparatus (manufactured by Shimadzu Corporation, model name: TMA6000), and Tg, CTEα1 (0 ° C.-50 ° C.), and CTEα2 (200 ° C.-250 ° C.) were evaluated. The evaluation criteria are as follows.
(Tg)
◎… 150 ° C. or higher ○… 145 ° C. or higher and lower than 150 ° C. Δ ... 140 ° C. or higher and lower than 145 ° C.
◎ ... less than 40 ppm ○ ... 40 ppm or more and less than 50 ppm Δ ... 50 ppm or more and less than 60 ppm × ... 60 ppm or more (CTEα2)
◎ ... less than 110 ppm ○ ... 110 ppm or more and less than 120 ppm Δ ... 120 ppm or more and less than 130 ppm × ... 130 ppm or more
(実施例1~15,比較例1~5)
銅箔基板上に、硬化性樹脂組成物をスクリーン印刷により乾燥膜厚約40μmになるように全面塗布した。これを、80℃で乾燥し、室温まで放冷することにより、硬化性樹脂組成物からなる樹脂層を形成し、各実施例及び比較例ごとの未硬化サンプルを有する評価基板を得た。これに対して、ORC社製HMW680GW(メタルハライドランプ、散乱光)により、800mJにて50mm×5mmの短冊状のネガマスクを通して露光を行った。その後、30℃の1wt.%炭酸ナトリウム水溶液で現像を行い、硬化被膜のパターンを得た。更に積算露光量を1000mJとして紫外線を照射した後、160℃で1時間加熱硬化して硬化膜を有する評価基板を得た。
上記により得られた評価基板の硬化被膜を銅箔より剥離し、評価を実施した。測定は、DMA測定装置(島津製作所社製 機種名:DMS6100)を用いて行い、260℃におけるEについて評価を行った。Tanδについては、日立ハイテック社製DMS6100にて25℃から300℃まで昇温5℃/分、周波数1Hz、引張り正弦波モードで測定し、温度測定領域での最大値をとった。
(実施例16)
銅箔基板上に、硬化性樹脂組成物をスクリーン印刷により乾燥膜厚約40μmになるように全面塗布した。これを160℃で1時間加熱硬化させて硬化膜を有する評価基板を得た。
上記により得られた評価基板の硬化被膜を銅箔より剥離し、評価を実施した。測定は、DMA測定装置(島津製作所社製 機種名:DMS6100)を用いて行い、260℃におけるEについて評価を行った。Tanδについては、日立ハイテック社製DMS6100にて25℃から300℃まで昇温5℃/分、周波数1Hz、引張り正弦波モードで測定し、温度測定領域での最大値をとった。
評価基準は以下の通りである。
(弾性率E)
◎…1×109Pa以上
○…5×108Pa以上1×109Pa未満
△…1×108Pa以上5×108Pa未満
×…1×108Pa未満
(Tanδ)
◎…0.20未満
○…0.20以上0.25未満
△…0.25以上0.30未満
×…0.30以上 <Elastic modulus E and Tanδ>
(Examples 1 to 15, Comparative Examples 1 to 5)
On the copper foil substrate, the entire surface of the curable resin composition was applied by screen printing to a dry film thickness of about 40 μm. This was dried at 80 ° C. and allowed to cool to room temperature, thereby forming a resin layer made of a curable resin composition, thereby obtaining an evaluation substrate having uncured samples for each example and comparative example. On the other hand, exposure was performed through a negative mask of 50 mm × 5 mm at 800 mJ with ORC HMW680GW (metal halide lamp, scattered light). Thereafter, 1 wt. Development was performed with an aqueous sodium carbonate solution to obtain a cured film pattern. Furthermore, after irradiating ultraviolet rays with an integrated exposure amount of 1000 mJ, the substrate was heat cured at 160 ° C. for 1 hour to obtain an evaluation substrate having a cured film.
The cured film of the evaluation board | substrate obtained by the above was peeled off from copper foil, and evaluation was implemented. The measurement was performed using a DMA measuring device (model name: DMS6100, manufactured by Shimadzu Corporation), and E at 260 ° C. was evaluated. Tan δ was measured with a DMS6100 manufactured by Hitachi High-Tech Co., Ltd. from 25 ° C. to 300 ° C. at a rate of 5 ° C./min, a frequency of 1 Hz, and a tensile sine wave mode, and the maximum value in the temperature measurement region was taken.
(Example 16)
On the copper foil substrate, the entire surface of the curable resin composition was applied by screen printing to a dry film thickness of about 40 μm. This was heat-cured at 160 ° C. for 1 hour to obtain an evaluation substrate having a cured film.
The cured film of the evaluation board | substrate obtained by the above was peeled off from copper foil, and evaluation was implemented. The measurement was performed using a DMA measuring device (model name: DMS6100, manufactured by Shimadzu Corporation), and E at 260 ° C. was evaluated. Tan δ was measured with a DMS6100 manufactured by Hitachi High-Tech Co., Ltd. from 25 ° C. to 300 ° C. at a rate of 5 ° C./min, a frequency of 1 Hz, and a tensile sine wave mode, and the maximum value in the temperature measurement region was taken.
The evaluation criteria are as follows.
(Elastic modulus E)
◎… 1 × 10 9 Pa or more ○… 5 × 10 8 Pa or more and less than 1 × 10 9 Pa Δ… 1 × 10 8 Pa or more and less than 5 × 10 8 Pa ×… 1 × 10 8 Pa or less (Tan δ)
◎ ... less than 0.20 ○ ... 0.20 or more and less than 0.25 Δ ... 0.25 or more and less than 0.30 × ... 0.30 or more
(実施例1~15、比較例1~5)
CZ処理された35μm銅箔基板上に、硬化性樹脂組成物をスクリーン印刷により乾燥膜厚20μmになるように全面塗布した。これを、80℃で乾燥し、室温まで放冷することにより、硬化性樹脂組成物からなる樹脂層を形成し、各実施例および比較例ごとの未硬化サンプルを有する評価基板を得た。これに対して、ORC社製HMW680GW(メタルハライドランプ、散乱光)により、最適露光量:800mJにて全面露光を行った。その後、30℃の1wt.%炭酸ナトリウム水溶液で現像処理を行い、硬化膜のパターンを得た。更に積算露光量を1000mJとして紫外線を照射した後、160℃で1時間加熱して硬化した。
上記により得られた評価基板の硬化膜を50mm×50mmに切り出し、硬化膜面を下に向け水平な台に静置した。静置後、切り出した硬化膜の4角について水平な台からCu箔までの距離をそれぞれ測定して平均値を求め下記の通り評価した。
(実施例16)
CZ処理された35μm銅箔基板上に、硬化性樹脂組成物をスクリーン印刷により乾燥膜厚20μmになるように全面塗布した。これを、80℃で乾燥し、室温まで放冷することにより、硬化性樹脂組成物からなる樹脂層を形成した。これを160℃で1時間加熱して硬化させ、硬化膜を有する評価基板を得た。
上記により得られた評価基板の硬化膜を50mm×50mmに切り出し、硬化膜面を下に向け水平な台に静置した。静置後、切り出した硬化膜の4角について水平な台からCu箔までの距離をそれぞれ測定して平均値を求め下記の通り評価した。
◎…10mm未満
○…10mm以上15mm未満
△…15mm以上20mm未満
×…20mm以上 <Warpage>
(Examples 1 to 15 and Comparative Examples 1 to 5)
The entire surface of the curable resin composition was applied to a dry film thickness of 20 μm by screen printing on a CZ-treated 35 μm copper foil substrate. This was dried at 80 ° C. and allowed to cool to room temperature, thereby forming a resin layer made of a curable resin composition, and obtaining an evaluation substrate having an uncured sample for each example and comparative example. On the other hand, whole surface exposure was performed with an optimum exposure amount of 800 mJ using an HMW680GW (metal halide lamp, scattered light) manufactured by ORC. Thereafter, 1 wt. Development processing was carried out with an aqueous sodium carbonate solution to obtain a cured film pattern. Furthermore, after irradiating with ultraviolet rays with an integrated exposure amount of 1000 mJ, the film was cured by heating at 160 ° C. for 1 hour.
The cured film of the evaluation substrate obtained as described above was cut out to 50 mm × 50 mm, and left on a horizontal table with the cured film surface facing down. After standing, the distance from the horizontal base to the Cu foil was measured for each of the four corners of the cut out cured film, and the average value was obtained and evaluated as follows.
(Example 16)
The entire surface of the curable resin composition was applied to a dry film thickness of 20 μm by screen printing on a CZ-treated 35 μm copper foil substrate. This was dried at 80 ° C. and allowed to cool to room temperature, thereby forming a resin layer made of a curable resin composition. This was heated and cured at 160 ° C. for 1 hour to obtain an evaluation substrate having a cured film.
The cured film of the evaluation substrate obtained as described above was cut out to 50 mm × 50 mm, and left on a horizontal table with the cured film surface facing down. After standing, the distance from the horizontal base to the Cu foil was measured for each of the four corners of the cut out cured film, and the average value was obtained and evaluated as follows.
◎ ... Less than 10 mm ○ ... 10 mm or more and less than 15 mm △… 15 mm or more and less than 20 mm x ... 20 mm or more
(実施例1~15、比較例1~5)
めっき銅基板をCZ8101でエッチングレート1μm/m2で処理し、その面に硬化性樹脂組成物をスクリーン印刷により乾燥膜厚約20μmになるように全面塗布した。これを、80℃で乾燥し、室温まで放冷することにより、硬化性樹脂組成物からなる樹脂層を形成し、評価基板αを得た。これに対して、ORC社製HMW680GW(メタルハライドランプ、散乱光)により、最適露光量:800mJにて全面露光を行った。その後、30℃の1wt.%炭酸ナトリウム水溶液で処理し、硬化膜を得た。更に積算露光量を1000mJとして紫外線を照射した後、下記条件で加熱して硬化し、評価基板βを得た。
上記により得られた評価基板α、βのFT-IR測定を行い、エポキシ基の反応率を測定した。
エポキシ基の反応率は、測定装置としてMicroscope spotlight200を使用し、エポキシ基由来の振動である913cm-1付近のピーク高さから算出した。
(実施例16)
めっき銅基板をCZ8101でエッチングレート1μm/m2で処理し、その面に硬化性樹脂組成物をスクリーン印刷により乾燥膜厚約20μmになるように全面塗布した。これを、80℃で乾燥し、室温まで放冷することにより、硬化性樹脂組成物からなる樹脂層を形成し、評価基板αを得た。これを下記条件で加熱して硬化し評価基板βを得た。
上記により得られた評価基板α、βのFT-IR測定を行い、エポキシ基の反応率を測定した。
エポキシ基の反応率は、測定装置としてMicroscope spotlight200を使用し、エポキシ基由来の振動である913cm-1付近のピーク高さから算出した。
◎…150℃60min硬化にてエポキシの反応率98%以上達成
○…160℃60min硬化にてエポキシの反応率98%以上達成
△…170℃60min硬化にてエポキシの反応率98%以上達成
×…170℃60min硬化にてエポキシの反応率98%未満 <Reaction rate>
(Examples 1 to 15 and Comparative Examples 1 to 5)
The plated copper substrate was treated with CZ8101 at an etching rate of 1 μm / m 2 , and the entire surface of the curable resin composition was applied by screen printing to a dry film thickness of about 20 μm. This was dried at 80 ° C. and allowed to cool to room temperature, whereby a resin layer made of a curable resin composition was formed, and an evaluation substrate α was obtained. On the other hand, whole surface exposure was performed with an optimum exposure amount of 800 mJ using an HMW680GW (metal halide lamp, scattered light) manufactured by ORC. Thereafter, 1 wt. A cured film was obtained by treatment with an aqueous sodium carbonate solution. Furthermore, after irradiating with ultraviolet rays with an integrated exposure amount of 1000 mJ, the substrate was heated and cured under the following conditions to obtain an evaluation substrate β.
FT-IR measurement was performed on the evaluation substrates α and β obtained as described above, and the reaction rate of the epoxy group was measured.
The reaction rate of the epoxy group was calculated from the peak height in the vicinity of 913 cm −1, which is vibration derived from the epoxy group, using Microscope spotlight 200 as a measuring device.
(Example 16)
The plated copper substrate was treated with CZ8101 at an etching rate of 1 μm / m 2 , and the entire surface of the curable resin composition was applied by screen printing to a dry film thickness of about 20 μm. This was dried at 80 ° C. and allowed to cool to room temperature, whereby a resin layer made of a curable resin composition was formed, and an evaluation substrate α was obtained. This was heated and cured under the following conditions to obtain an evaluation substrate β.
FT-IR measurement was performed on the evaluation substrates α and β obtained as described above, and the reaction rate of the epoxy group was measured.
The reaction rate of the epoxy group was calculated from the peak height in the vicinity of 913 cm −1, which is vibration derived from the epoxy group, using Microscope spotlight 200 as a measuring device.
A: Epoxy reaction rate of 98% or higher achieved at 150 ° C. for 60 min. Curing: Epoxy reaction rate of 98% or higher achieved at 160 ° C. for 60 min. Epoxy reaction rate of less than 98% after curing at 170 ° C for 60 minutes
(実施例1~15、比較例1~5)
めっき銅基板をCZ8101でエッチングレート1μm/m2で処理し、その面に硬化性樹脂組成物をスクリーン印刷により乾燥膜厚約20μmになるように全面塗布した。これを、80℃で乾燥し、室温まで放冷することにより、硬化性樹脂組成物からなる樹脂層を形成した。これに対して、ORC社製HMW680GW(メタルハライドランプ、散乱光)により、最適露光量:800mJにてパターン露光を行った。その後、30℃の1wt.%炭酸ナトリウム水溶液で現像を行い、硬化膜のパターンを得た。更に積算露光量を1000mJとして紫外線を照射した後、160℃で1時間加熱して硬化した。
上記により得られた評価基板の開口径を観測し、ハレーション、アンダーカットの発生がないかを確認し評価を行った。
◎…50μmにて良好な開口径
○…70μmにて良好な開口径
△…100μmにて良好な開口径
×…100μmにて良好な開口径が得られない、または現像不可 <Resolution evaluation>
(Examples 1 to 15 and Comparative Examples 1 to 5)
The plated copper substrate was treated with CZ8101 at an etching rate of 1 μm / m 2 , and the entire surface of the curable resin composition was applied by screen printing to a dry film thickness of about 20 μm. This was dried at 80 ° C. and allowed to cool to room temperature, thereby forming a resin layer made of a curable resin composition. On the other hand, pattern exposure was performed at an optimum exposure amount of 800 mJ using ORC HMW680GW (metal halide lamp, scattered light). Thereafter, 1 wt. Development was performed with an aqueous sodium carbonate solution to obtain a cured film pattern. Furthermore, after irradiating with ultraviolet rays with an integrated exposure amount of 1000 mJ, the film was cured by heating at 160 ° C. for 1 hour.
The opening diameter of the evaluation substrate obtained as described above was observed, and it was confirmed whether or not halation and undercut were generated.
Excellent opening diameter at 50 μm Good opening diameter at 70 μm Good opening diameter at 100 μm × Good opening diameter cannot be obtained at 100 μm or development is impossible
(実施例1~15、比較例1~5)
L/S=20/20の櫛形パターンが形成された基板を用い、硬化性樹脂組成物をスクリーン印刷により乾燥膜厚約20μmになるように全面塗布した。これを、80℃で乾燥し、室温まで放冷することにより、硬化性樹脂組成物からなる樹脂層を形成し、各実施例および比較例ごとの未硬化サンプルを有する評価基板を得た。これに対して、ORC社製HMW680GW(メタルハライドランプ、散乱光)により、最適露光量:800mJにて全面露光を行った。その後、30℃の1wt.%炭酸ナトリウム水溶液で現像を行い、硬化膜のパターンを得た。更に積算露光量を1000mJとして紫外線を照射した後、160℃で1時間加熱して硬化した。
その後得られた評価基板に電極をつなぎ130℃、湿度85%の雰囲気下の高温高湿槽に入れ、電圧5Vの条件でHAST試験を実施し、電気絶縁性が1×106Ω以下になったときの時間を測定した。
(実施例16)
L/S=20/20の櫛形パターンが形成された基板を用い、硬化性樹脂組成物をスクリーン印刷により乾燥膜厚約20μmになるように全面塗布した。これを、80℃で乾燥し、室温まで放冷することにより、硬化性樹脂組成物からなる樹脂層を形成した。これを160℃で1時間加熱して硬化させて、硬化膜を有する評価基板を得た。
その後得られた評価基板に電極をつなぎ130℃、湿度85%の雰囲気下の高温高湿槽に入れ、電圧5Vの条件でHAST試験を実施し、電気絶縁性が1×106Ω以下になったときの時間を測定した。
◎…300h pass
○…200h pass
△…150h pass
×…150h以内でNG <Insulation reliability (HAST resistance)>
(Examples 1 to 15 and Comparative Examples 1 to 5)
Using the substrate on which the comb pattern of L / S = 20/20 was formed, the entire surface of the curable resin composition was applied by screen printing so as to have a dry film thickness of about 20 μm. This was dried at 80 ° C. and allowed to cool to room temperature, thereby forming a resin layer made of a curable resin composition, and obtaining an evaluation substrate having an uncured sample for each example and comparative example. On the other hand, whole surface exposure was performed with an optimum exposure amount of 800 mJ using an HMW680GW (metal halide lamp, scattered light) manufactured by ORC. Thereafter, 1 wt. Development was performed with an aqueous sodium carbonate solution to obtain a cured film pattern. Furthermore, after irradiating with ultraviolet rays with an integrated exposure amount of 1000 mJ, the film was cured by heating at 160 ° C. for 1 hour.
After that, an electrode was connected to the obtained evaluation substrate, placed in a high-temperature and high-humidity tank under an atmosphere of 130 ° C. and 85% humidity, and a HAST test was conducted under the condition of a voltage of 5 V, and the electrical insulation became 1 × 10 6 Ω or less. The time was measured.
(Example 16)
Using the substrate on which the comb pattern of L / S = 20/20 was formed, the entire surface of the curable resin composition was applied by screen printing so as to have a dry film thickness of about 20 μm. This was dried at 80 ° C. and allowed to cool to room temperature, thereby forming a resin layer made of a curable resin composition. This was heated and cured at 160 ° C. for 1 hour to obtain an evaluation substrate having a cured film.
After that, an electrode was connected to the obtained evaluation substrate, placed in a high-temperature and high-humidity tank under an atmosphere of 130 ° C. and 85% humidity, and a HAST test was conducted under the condition of a voltage of 5 V, and the electrical insulation became 1 × 10 6 Ω or less. The time was measured.
◎… 300h pass
○ ... 200h pass
△ ... 150h pass
× NG within 150h
(実施例1~15、比較例1~5)
パッドピッチが250μmピッチで形成されたFC-BGA用評価基板上に、硬化性樹脂組成物を全面塗布した。これを乾燥し、室温まで放冷することにより、硬化性樹脂組成物からなる樹脂層を形成した。これに対して、最適露光量:800mJにて、銅パッド上にSRO(Solder Resist Opening)80μmの開口サイズでダイレクトイメージング露光を行った。その後、30℃の1wt%炭酸ナトリウム水溶液を噴射することにより現像を行い、硬化膜のパターンを得た。更に積算露光量を1000mJとして紫外線を照射した後、160℃で1時間加熱して硬化した。その後、Auめっき処理、はんだバンプ形成、Siチップを実装し、評価基板を得た。
上記により得られた評価基板を、-65℃と150℃の間で温度サイクルが行われる冷熱サイクル機に入れ、TCT(Thermal Cycle Test)を行った。そして、600サイクル時、800サイクル時および1000サイクル時の硬化膜の表面を観察した。判定基準は以下の通りである。
(実施例16)
パッドピッチが250μmピッチで形成されたFC-BGA用評価基板上に、硬化性樹脂組成物を全面塗布した。これを乾燥し、室温まで放冷することにより、硬化性樹脂組成物からなる樹脂層を形成した。これを160℃で1時間加熱して硬化させて、硬化膜を有する基板を得た。これに対しCO2レーザー加工機(日立ビアメカニクス社製)にてトップ径が80μmとなるように硬化膜にビアを形成した。その後、Auめっき処理、はんだバンプ形成、Siチップを実装し、評価基板を得た。
上記により得られた評価基板を、-65℃と150℃の間で温度サイクルが行われる冷熱サイクル機に入れ、TCT(Thermal Cycle Test)を行った。そして、600サイクル時、800サイクル時および1000サイクル時の硬化膜の表面を観察した。判定基準は以下の通りである。
◎…1000サイクルで異常なし
○…800サイクルで異常なし、1000サイクルでクラック発生
△…600サイクルで異常なし、800サイクルでクラック発生
×…600サイクルでクラック発生 <Crack resistance (TCT resistance)>
(Examples 1 to 15 and Comparative Examples 1 to 5)
The entire surface of the curable resin composition was applied onto an evaluation substrate for FC-BGA formed with a pad pitch of 250 μm. This was dried and allowed to cool to room temperature to form a resin layer made of a curable resin composition. On the other hand, direct imaging exposure was performed with an optimal exposure amount of 800 mJ and an opening size of 80 μm of SRO (Solder Resist Opening) on the copper pad. Thereafter, development was carried out by spraying a 1 wt% sodium carbonate aqueous solution at 30 ° C. to obtain a cured film pattern. Furthermore, after irradiating with ultraviolet rays with an integrated exposure amount of 1000 mJ, the film was cured by heating at 160 ° C. for 1 hour. Thereafter, Au plating treatment, solder bump formation, and Si chip were mounted to obtain an evaluation substrate.
The evaluation substrate obtained as described above was placed in a thermal cycle machine in which a temperature cycle was performed between −65 ° C. and 150 ° C., and TCT (Thermal Cycle Test) was performed. Then, the surface of the cured film was observed at 600 cycles, 800 cycles, and 1000 cycles. Judgment criteria are as follows.
(Example 16)
The entire surface of the curable resin composition was applied onto an evaluation substrate for FC-BGA formed with a pad pitch of 250 μm. This was dried and allowed to cool to room temperature to form a resin layer made of a curable resin composition. This was heated and cured at 160 ° C. for 1 hour to obtain a substrate having a cured film. On the other hand, vias were formed in the cured film with a CO 2 laser processing machine (manufactured by Hitachi Via Mechanics) so that the top diameter was 80 μm. Thereafter, Au plating treatment, solder bump formation, and Si chip were mounted to obtain an evaluation substrate.
The evaluation substrate obtained as described above was placed in a thermal cycle machine in which a temperature cycle was performed between −65 ° C. and 150 ° C., and TCT (Thermal Cycle Test) was performed. Then, the surface of the cured film was observed at 600 cycles, 800 cycles, and 1000 cycles. Judgment criteria are as follows.
◎… No abnormalities at 1000 cycles ○… No abnormalities at 800 cycles, cracks generated at 1000 cycles Δ… No abnormalities at 600 cycles, cracks generated at 800 cycles ×… cracks generated at 600 cycles
*2:上記で合成したカルボキシル基含有樹脂溶液A-2
*3:上記で合成したカルボキシル基含有樹脂溶液A-3
*4:上記で合成したカルボキシル基含有樹脂溶液A-4
*5:BASFジャパン社製イルガキュアTPO(2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド)
*6:BASFジャパン社製イルガキュア907(2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン)
*7:BASFジャパン社製イルガキュアOXE02(エタノン,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]-1-(o-アセチルオキシム)
*8:上記で合成したシルセスキオキサン骨格を有するエポキシ樹脂B-1
*9:上記で合成したシルセスキオキサン骨格を有するエポキシ樹脂B-2
*10:上記で合成したシルセスキオキサン骨格を有するエポキシ樹脂B-3
*11:上記で合成したシルセスキオキサン骨格を有するエポキシ樹脂B-4
*12:三菱化学社製jER828(ビスフェノールA型エポキシ樹脂)
*13:ダウケミカル社製DEN431(フェノールノボラックエポキシ樹脂)
*14:DIC社製N-870 75EA(ビスフェノールAノボラック型エポキシ樹脂)
*15:DIC社製EXA-724(トリフェニルメタン型エポキシ樹脂))
*16:上記で調整した表面処理されたシリカ溶剤分散品C-1(球状シリカをPMAに均一分散。メタクリル表面処理。シリカ含有量70wt%(固形分)。シリカ平均粒径0.8μm)
*17:上記で調整した表面処理された硫酸バリウム溶剤分散品C-2(硫酸バリウムをPMAに均一分散。アルミナ表面処理。硫酸バリウム含有量70wt%(固形分)。硫酸バリウム平均粒径(0.5μm))
*18:上記で調整した表面処理されていないシリカ溶剤分散品(球状シリカをPMAに均一分散。表面処理無。シリカ含有量70wt%(固形分)。シリカ平均粒径0.8μm)
*19:沈降性硫酸バリウムをPMAに均一分散させたもの。硫酸バリウム含有量70wt%(固形分)。表面処理していない。
*20:日本化薬社製DPHA(ジペンタエリスリトールヘキサアクリレート)
*21:青色着色剤、着色剤含有量12質量%
*22:黄色着色剤、着色剤含有量10質量%
*23:DICY(ジシアンジアミド)
*24:評価せず
* 2: Carboxyl group-containing resin solution A-2 synthesized above
* 3: Carboxyl group-containing resin solution A-3 synthesized above
* 4: Carboxyl group-containing resin solution A-4 synthesized above
* 5: Irgacure TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by BASF Japan
* 6: Irgacure 907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one) manufactured by BASF Japan
* 7: Irgacure OXE02 manufactured by BASF Japan (Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime)
* 8: Epoxy resin B-1 having a silsesquioxane skeleton synthesized above
* 9: Epoxy resin B-2 having silsesquioxane skeleton synthesized above
* 10: Epoxy resin B-3 having a silsesquioxane skeleton synthesized above
* 11: Epoxy resin B-4 having a silsesquioxane skeleton synthesized above
* 12: jER828 (bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation
* 13: DEN431 (phenol novolac epoxy resin) manufactured by Dow Chemical Company
* 14: N-870 75EA (bisphenol A novolac type epoxy resin) manufactured by DIC
* 15: EXA-724 manufactured by DIC (triphenylmethane type epoxy resin))
* 16: Surface-treated silica solvent dispersion C-1 prepared as described above (spherical silica is uniformly dispersed in PMA. Methacrylic surface treatment. Silica content 70 wt% (solid content). Silica average particle diameter 0.8 μm)
* 17: Surface-treated barium sulfate solvent dispersion C-2 prepared above (barium sulfate is uniformly dispersed in PMA. Alumina surface treatment. Barium sulfate content 70 wt% (solid content). Barium sulfate average particle diameter (0 .5 μm))
* 18: Silica solvent dispersion without surface treatment prepared as described above (spherical silica is uniformly dispersed in PMA. No surface treatment. Silica content 70 wt% (solid content). Silica average particle size 0.8 μm)
* 19: Precipitated barium sulfate uniformly dispersed in PMA. Barium sulfate content 70 wt% (solid content). No surface treatment.
* 20: Nippon Kayaku DPHA (dipentaerythritol hexaacrylate)
* 21: Blue colorant, colorant content 12% by mass
* 22: Yellow colorant, colorant content 10% by mass
* 23: DICY (dicyandiamide)
* 24: Not evaluated
From the results shown in the above table, it can be seen that the cured products of the curable resin compositions of Examples 1 to 16 of the present invention are excellent in crack resistance and insulation reliability. On the other hand, when the curable resin compositions of Comparative Examples 1 to 5 were used, the elastic modulus (E) particularly at high temperatures was low, and it was difficult to obtain high crack resistance and insulation reliability.
Claims (8)
- (A)カルボキシル基含有樹脂と、(B)シルセスキオキサン骨格を有するエポキシ樹脂と、
を含有することを特徴とする硬化性樹脂組成物。 (A) a carboxyl group-containing resin, (B) an epoxy resin having a silsesquioxane skeleton,
A curable resin composition comprising: - さらに(C)表面処理された無機フィラーを含有することを特徴とする請求項1記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, further comprising (C) a surface-treated inorganic filler.
- 前記(A)カルボキシル基含有樹脂が、下記一般式(1)で表される構造を有することを特徴とする請求項1記載の硬化性樹脂組成物。
(式中、R1~R4はそれぞれ独立して水素原子またはアルキル基を表し、kは0.3~10のいずれかの値を表す。) The curable resin composition according to claim 1, wherein the (A) carboxyl group-containing resin has a structure represented by the following general formula (1).
(Wherein R 1 to R 4 each independently represents a hydrogen atom or an alkyl group, and k represents any value of 0.3 to 10) - 前記(A)カルボキシル基含有樹脂が、下記一般式(2)で表される構造を有することを特徴とする請求項1記載の硬化性樹脂組成物。
(式中、R5~R7はそれぞれ独立して水素原子またはアルキル基を表し、Zは酸無水物残基を表し、mは0.3~10のいずれかの値を表す。) The curable resin composition according to claim 1, wherein the (A) carboxyl group-containing resin has a structure represented by the following general formula (2).
(Wherein R 5 to R 7 each independently represents a hydrogen atom or an alkyl group, Z represents an acid anhydride residue, and m represents any value of 0.3 to 10) - 前記(B)シルセスキオキサン骨格を有するエポキシ樹脂が、下記一般式(3)で表される構造を有することを特徴とする請求項1記載の硬化性樹脂組成物。
(式中、R8~R11は、それぞれ独立して、SiO結合を有する基または有機基であり、R8~R11のうち少なくとも一つがエポキシ基を有する基である。) The curable resin composition according to claim 1, wherein the (B) epoxy resin having a silsesquioxane skeleton has a structure represented by the following general formula (3).
(Wherein R 8 to R 11 are each independently a group having a SiO bond or an organic group, and at least one of R 8 to R 11 is a group having an epoxy group.) - 請求項1記載の硬化性樹脂組成物をフィルムに塗布、乾燥して得られる樹脂層を有することを特徴とするドライフィルム。 A dry film comprising a resin layer obtained by applying the curable resin composition according to claim 1 to a film and drying the film.
- 請求項1~5のいずれか一項に記載の硬化性樹脂組成物、または、請求項6記載のドライフィルムの樹脂層を硬化して得られることを特徴とする硬化物。 A curable resin composition according to any one of claims 1 to 5, or a cured product obtained by curing the resin layer of the dry film according to claim 6.
- 請求項7記載の硬化物を有することを特徴とするプリント配線板。
A printed wiring board comprising the cured product according to claim 7.
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JP2018509483A JP6951323B2 (en) | 2016-03-31 | 2017-03-30 | Curable resin composition, dry film, cured product and printed wiring board |
CN201780018516.0A CN108885400A (en) | 2016-03-31 | 2017-03-30 | Hardening resin composition, dry film, solidfied material and printed circuit board |
KR1020187031078A KR20180129867A (en) | 2016-03-31 | 2017-03-30 | Curable resin composition, dry film, cured product and printed wiring board |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018172632A (en) * | 2017-03-31 | 2018-11-08 | 太陽インキ製造株式会社 | Curable composition, dry film, cured material and print circuit board |
JP2019077856A (en) * | 2017-10-19 | 2019-05-23 | サムソン エレクトロ−メカニックス カンパニーリミテッド. | Photocurable and thermosetting resin composition and cured product of the same |
CN111295289A (en) * | 2018-01-31 | 2020-06-16 | 大日本印刷株式会社 | Thermal transfer sheet, coating liquid for release layer, and method for producing thermal transfer sheet |
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---|---|---|---|---|
KR20190095128A (en) * | 2018-02-05 | 2019-08-14 | 제이에스알 가부시끼가이샤 | Wiring member |
JP6987011B2 (en) * | 2018-03-30 | 2021-12-22 | 太陽インキ製造株式会社 | Curable resin composition, dry film, cured product and printed wiring board |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000281790A (en) * | 1999-03-30 | 2000-10-10 | Nippon Steel Chem Co Ltd | Silicon resin and photosensitive resin composition containing same |
JP2009126901A (en) * | 2007-11-21 | 2009-06-11 | Nof Corp | Thermosetting resin composition for sealing optical semiconductor |
JP2010106205A (en) * | 2008-10-31 | 2010-05-13 | Nof Corp | Thermosetting resin composition |
WO2011155613A1 (en) * | 2010-06-11 | 2011-12-15 | 日本化薬株式会社 | Curable resin composition and substance obtained by curing same |
JP2013541733A (en) * | 2010-09-30 | 2013-11-14 | コーロン インダストリーズ インク | Photosensitive resin composition for organic insulating film |
JP2014081611A (en) * | 2012-09-28 | 2014-05-08 | Taiyo Ink Mfg Ltd | Photocurable resin composition, print circuit board, and production method of photocurable composition |
JP2015227441A (en) * | 2014-05-09 | 2015-12-17 | 太陽インキ製造株式会社 | Curable resin composition, dry film, and printed wiring board |
JP2016160420A (en) * | 2015-03-05 | 2016-09-05 | Jnc株式会社 | Thermosetting composition, cured film, substrate with cured film, electronic component, and display device |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100379780C (en) * | 2002-03-15 | 2008-04-09 | 太阳油墨制造株式会社 | Curable resins and curable resin compositions containing the same |
TWI475050B (en) * | 2011-03-30 | 2015-03-01 | Asahi Kasei Chemicals Corp | Organopolysiloxane, method for producing the same and curable resin composition containing the same |
JP6021605B2 (en) * | 2012-11-19 | 2016-11-09 | 新日鉄住金化学株式会社 | Cage type silsesquioxane compound, curable resin composition and resin cured product using the same |
-
2017
- 2017-03-30 KR KR1020187031078A patent/KR20180129867A/en unknown
- 2017-03-30 WO PCT/JP2017/013454 patent/WO2017170959A1/en active Application Filing
- 2017-03-30 CN CN201780018516.0A patent/CN108885400A/en active Pending
- 2017-03-30 JP JP2018509483A patent/JP6951323B2/en active Active
- 2017-03-31 TW TW106111184A patent/TWI731956B/en active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000281790A (en) * | 1999-03-30 | 2000-10-10 | Nippon Steel Chem Co Ltd | Silicon resin and photosensitive resin composition containing same |
JP2009126901A (en) * | 2007-11-21 | 2009-06-11 | Nof Corp | Thermosetting resin composition for sealing optical semiconductor |
JP2010106205A (en) * | 2008-10-31 | 2010-05-13 | Nof Corp | Thermosetting resin composition |
WO2011155613A1 (en) * | 2010-06-11 | 2011-12-15 | 日本化薬株式会社 | Curable resin composition and substance obtained by curing same |
JP2013541733A (en) * | 2010-09-30 | 2013-11-14 | コーロン インダストリーズ インク | Photosensitive resin composition for organic insulating film |
JP2014081611A (en) * | 2012-09-28 | 2014-05-08 | Taiyo Ink Mfg Ltd | Photocurable resin composition, print circuit board, and production method of photocurable composition |
JP2015227441A (en) * | 2014-05-09 | 2015-12-17 | 太陽インキ製造株式会社 | Curable resin composition, dry film, and printed wiring board |
JP2016160420A (en) * | 2015-03-05 | 2016-09-05 | Jnc株式会社 | Thermosetting composition, cured film, substrate with cured film, electronic component, and display device |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018172632A (en) * | 2017-03-31 | 2018-11-08 | 太陽インキ製造株式会社 | Curable composition, dry film, cured material and print circuit board |
JP2019077856A (en) * | 2017-10-19 | 2019-05-23 | サムソン エレクトロ−メカニックス カンパニーリミテッド. | Photocurable and thermosetting resin composition and cured product of the same |
JP7193074B2 (en) | 2017-10-19 | 2022-12-20 | サムソン エレクトロ-メカニックス カンパニーリミテッド. | Photocurable and thermosetting resin composition, and cured product thereof |
CN111295289A (en) * | 2018-01-31 | 2020-06-16 | 大日本印刷株式会社 | Thermal transfer sheet, coating liquid for release layer, and method for producing thermal transfer sheet |
EP3702167A4 (en) * | 2018-01-31 | 2021-08-25 | Dai Nippon Printing Co., Ltd. | Heat transfer sheet, coating liquid for release layer, and method for manufacturing heat transfer sheet |
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JP6951323B2 (en) | 2021-10-20 |
TW201742888A (en) | 2017-12-16 |
TWI731956B (en) | 2021-07-01 |
KR20180129867A (en) | 2018-12-05 |
JPWO2017170959A1 (en) | 2019-02-14 |
CN108885400A (en) | 2018-11-23 |
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