Classifications

• • 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
• • 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
• • 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
• • 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
• • 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
• • 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
• • 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
• • 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
• • 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
• • 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
• • 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
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • 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
• • 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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