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
• • 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
  • C08G59/40—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 curing agents used
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
• • 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
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/031—Organic compounds not covered by group G03F7/029
• • 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 multi-component curable resin composition, a dry film, a cured product, and an electronic component.
• solder resist has traditionally been used as a protective material for the wiring board circuit.
• a curable resin composition for example, an oxime ester photopolymerization initiator (i.e., a compound with high photosensitivity) is blended in order to form a more precise pattern (specifically, to increase the sensitivity during exposure).
• an oxime ester photopolymerization initiator i.e., a compound with high photosensitivity
• two-liquid curable resin compositions have also been proposed from the viewpoint of quality stability (for example, Patent Documents 1 and 2).
• oxime ester photopolymerization initiators mentioned above are highly reactive, so they must be handled with care.
• One area in which care must be taken is the manufacturing process of the composition.
• a two-liquid photocurable/thermosetting resin composition (invention described in Patent Document 1) has been proposed, which is composed of a liquid composition containing a photopolymerization initiator having an oxime bond and a liquid composition containing a resin having a carboxyl group or a reactive diluent.
• a two-liquid alkali-developable curable resin composition (invention described in Patent Document 2) which is composed of a liquid composition containing a photopolymerization initiator having an oxime bond and a liquid composition containing an alkali-soluble resin.
• each composition liquid was prepared at a temperature of about 40°C using a three-roll mill.
• the ability to prepare each composition liquid using another device e.g., a bead mill) instead of the conventional three-roll mill is preferable in that it allows for a wider range of preparation methods to be selected.
• a bead mill is used as the other device, each composition liquid is prepared at a higher temperature (e.g., about 60°C) than the temperature in the three-roll mill, and there is a high possibility that changes in characteristics such as sensitivity will occur when each composition liquid is mixed.
• some curable resin compositions contain a carboxyl group-containing resin and a photopolymerization initiator in the same composition liquid, and this tendency is particularly noticeable when the photopolymerization initiator is an oxime ester-based photopolymerization initiator, leaving room for improvement.
• the object of the present invention is to provide a multi-liquid curable resin composition that can exhibit stable properties such as sensitivity after mixing, even after each component liquid is prepared at a high temperature (e.g., about 60°C).
• an epoxy compound with a weight-average molecular weight of 700 or more to a liquid composition containing a resin having a carboxyl group and at least one of a primary amine, a secondary amine, and a tertiary amine (for example, an oxime ester photopolymerization initiator), and thus completed the present invention.
• a carboxyl group-containing resin At least one of a primary amine, a secondary amine, and a tertiary amine; An epoxy compound having a weight average molecular weight of 700 or more; Including, This can be achieved by a multi-component curable resin composition, which is characterized in that the carboxyl group-containing resin, at least one of the primary amine, secondary amine and tertiary amine, and the epoxy compound having a weight average molecular weight of 700 or more are blended in the same composition liquid.
• At least one of the primary amine, secondary amine, and tertiary amine includes an oxime ester photopolymerization initiator.
• the composition further contains another photopolymerization initiator different from the oxime ester photopolymerization initiator.
• the oxime ester photopolymerization initiator is blended in a larger amount than the other photopolymerization initiators.
• the composition further comprises an epoxy compound having a weight average molecular weight of less than 700, and the epoxy compound having a weight average molecular weight of less than 700 is blended in a composition liquid different from the composition liquid containing at least one of the primary amine, secondary amine, and tertiary amine.
• the present invention also relates to a dry film having a resin layer formed from the curable resin composition.
• the present invention also relates to a cured product obtained by curing the multi-component curable resin composition or the resin layer of the dry film.
• the present invention also relates to an electronic component having the cured product.
• the multi-component curable resin composition of the present invention can exhibit stable properties such as sensitivity after mixing, even after each component liquid is prepared at a high temperature (e.g., about 60°C).
• the multi-component curable resin composition of the present invention contains a carboxyl group-containing resin, at least one of a primary amine, a secondary amine, and a tertiary amine, and an epoxy compound having a weight average molecular weight of 700 or more.
• the carboxyl group-containing resin, at least one of a primary amine, a secondary amine, and a tertiary amine, and the epoxy compound having a weight average molecular weight of 700 or more are blended in the same composition liquid.
• each liquid composition containing a carboxyl group-containing resin and at least one of a primary amine, a secondary amine, and a tertiary amine
• the quality of each liquid composition can be maintained during storage, even when the carboxyl group-containing resin and at least one of a primary amine, a secondary amine, and a tertiary amine (for example, an oxime ester photopolymerization initiator) are mixed into the same liquid composition and each liquid composition is prepared and stored at a high temperature (for example, about 60°C).
• a high temperature for example, about 60°C
• the multi-component curable resin composition of the present invention is composed of at least two or more kinds of composition liquids (preferably two kinds of composition liquids), and each component of the multi-component curable resin composition is contained in one of the at least two or more kinds of composition liquids so as to satisfy the condition that the carboxyl group-containing resin, at least one of a primary amine, a secondary amine and a tertiary amine, and an epoxy compound having a weight average molecular weight of 700 or more are blended in the same composition liquid.
• each component contained in the multi-component curable resin composition of the present invention will be described.
• the carboxyl group-containing resin contained in the curable resin composition of the present invention can be a known and commonly used resin compound containing a carboxyl group in the molecule. Furthermore, when preparing an alkali-developable resin composition, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is more preferable in terms of photocurability and development resistance.
• the unsaturated group is preferably derived from an acrylic acid or methacrylic acid derivative.
• a carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth)acrylate, or isobutylene.
• Carboxyl group-containing urethane resins obtained by polyaddition reaction of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and diol compounds such as polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.
• diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbut
• Carboxyl group-containing photosensitive urethane resins obtained by polyaddition reaction of diisocyanates with (meth)acrylates of bifunctional epoxy resins such as bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bixylenol type epoxy resins, and biphenol type epoxy resins, or their partial acid anhydride modifications, carboxyl group-containing dialcohol compounds, and diol compounds.
• bifunctional epoxy resins such as bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bixylenol type epoxy resins, and biphenol type epoxy resins, or their partial acid anhydride modifications, carboxyl group-containing dialcohol compounds, and diol compounds.
• a photosensitive urethane resin containing a carboxyl group which is terminated with (meth)acrylate by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as hydroxyalkyl (meth)acrylate, or (meth)acrylic acid during the synthesis of the resin (2) or (3) above.
• a photosensitive urethane resin containing carboxyl groups which is terminated with (meth)acrylation by adding a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, during the synthesis of the resin (2) or (3) above.
• a carboxyl group-containing photosensitive resin obtained by reacting a difunctional or more polyfunctional (solid) epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the hydroxyl groups present in the side chains.
• a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride
• a carboxyl group photosensitive resin obtained by reacting a polyfunctional epoxy resin in which the hydroxyl groups of a bifunctional (solid) epoxy resin have been further epoxidized with epichlorohydrin, with (meth)acrylic acid, and then adding a dibasic acid anhydride to the resulting hydroxyl groups.
• a carboxyl group-containing polyester resin obtained by reacting a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid with a bifunctional oxetane resin, and then adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the resulting primary hydroxyl groups.
• a carboxyl group-containing photosensitive resin obtained by reacting an epoxy compound having multiple epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and an unsaturated group-containing monocarboxylic acid, such as (meth)acrylic acid, and then reacting the alcoholic hydroxyl group of the resulting reaction product with a polybasic acid anhydride, such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic acid.
• a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic acid.
• a carboxyl group-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.
• an alkylene oxide such as ethylene oxide or propylene oxide
• a carboxyl group-containing photosensitive resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.
• a cyclic carbonate compound such as ethylene carbonate or propylene carbonate
• a carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins (1) to (11) above.
• carboxyl group-containing resins preferred are (X) carboxyl group-containing polyurethane resins, particularly those in which the isocyanate group of the component (including diisocyanate) having an isocyanate group of the urethane resin is not directly bonded to a benzene ring, and (Y) the polyfunctional epoxy resin used in the synthesis of the resin is a compound having a bisphenol A structure, a bisphenol F structure, a biphenol structure, a biphenyl novolac structure, a bis-xylenol structure, particularly a biphenyl novolac structure, and a hydrogenated compound thereof, which are preferred in terms of low warpage and bending resistance.
• the above-mentioned (2), (3), (4), (5), and modified products thereof such as (12) have a urethane bond in the main chain, which is preferred against warpage.
• resins other than the above-mentioned (1), (2), and (8), i.e., the resins (3), (4), (5), (6), (7), (9), (10), (11), and (12) have a photosensitive group in the molecule, and are therefore highly photoreactive and preferred.
• (meth)acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
• the above-mentioned carboxyl group-containing resin has many free carboxyl groups in the side chains of the backbone polymer, which serve as crosslinking points during thermal curing.
• the acid value of the carboxyl group-containing resin is preferably in the range of 10 to 200 mgKOH/g, more preferably in the range of 30 to 200 mgKOH/g, more preferably in the range of 40 to 200 mgKOH/g, and particularly preferably in the range of 45 to 120 mgKOH/g.
• the acid value of the carboxyl group-containing resin is 30 mgKOH/g or more, the alkali developability of the curable resin composition is improved.
• the acid value is less than 200 mgKOH/g, it is easy to draw a good resist pattern.
• the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, and preferably 5,000 to 100,000. A weight average molecular weight of 2,000 or more can improve tack-free performance and resolution. A weight average molecular weight of 150,000 or less can improve the developability and storage stability of the curable resin composition.
• the amount of the carboxyl group-containing resin is preferably 10 to 60% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 60% by mass, calculated as solid content, in the total composition. If it is less than the above range, the coating strength decreases, which is not preferred. On the other hand, if it is more than the above range, the viscosity of the composition increases and the coatability decreases, which is not preferred.
• carboxyl group-containing resins can be used alone or in combination of two or more.
• At least one of primary amine, secondary amine and tertiary amine may be, for example, an oxime ester photopolymerization initiator having a group represented by the following general formula (I).
• R 1 represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups and which may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group), R2 represents a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups and may have one
• oxime ester photopolymerization initiator having a group represented by the above general formula (I) include 2-(acetyloxyiminomethyl)thioxanthen-9-one represented by the following general formula (II), a compound represented by the following general formula (III), and a compound represented by the following general formula (IV).
• R 3 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain), or a phenoxycarbonyl group;
• R 4 and R 6 each independently represent a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which may be substituted
• R 7 , R 8 and R 13 each independently represent an alkyl group having 1 to 12 carbon atoms
• R 9 , R 10 , R 11 and R 12 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
• M represents O, S or NH
• p and q each independently represent an integer of 0 to 5.
• Oxime ester photopolymerization initiators having a group represented by the above general formula (II) are preferred because they have good initiator efficiency and are effective in improving sensitivity in small amounts, so they produce less outgassing during heat treatment after resist film formation and are effective in reducing warping of the film.
• 2-(acetyloxyiminomethyl)thioxanthen-9-one represented by the above general formula (II), ethanone represented by the above general formula (III), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), and the compound represented by the general formula (IV) are more preferred.
• Commercially available products include IrgacureOXE02 and IrgacureOXE04 manufactured by BASF Japan Ltd.
• the amount of the oxime ester photopolymerization initiator to be blended is preferably 0.01 to 30 parts by mass, preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin, calculated as solid content. From the viewpoint of sensitivity and resolution, it is preferable that the oxime ester photopolymerization initiator is blended in an amount greater than other photopolymerization initiators different from the oxime ester photopolymerization initiator (specifically, photopolymerization initiators containing a nucleophilic group and photopolymerization initiators not containing a nucleophilic group, which will be described later).
• the ratio of the oxime photopolymerization initiator to the other photopolymerization initiator is preferably 1:0.01 to 1:20, more preferably 1:0.02 to 1:10, even more preferably 1:0.02 to 1:1, and particularly preferably 1:0.02 to 1:0.7.
• At least one of the primary amine, secondary amine, and tertiary amine can be, for example, a photopolymerization initiator containing a nucleophilic group different from the above-mentioned oxime ester-based photopolymerization initiator (for example, an ⁇ -aminoacetophenone-based photopolymerization initiator having a group represented by the following general formula (V)).
• a photopolymerization initiator containing a nucleophilic group different from the above-mentioned oxime ester-based photopolymerization initiator for example, an ⁇ -aminoacetophenone-based photopolymerization initiator having a group represented by the following general formula (V)).
• R 14 and R 15 each independently represent an alkyl group or an arylalkyl group having 1 to 12 carbon atoms
• R 16 and R 17 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two of them are bonded together.
• Examples of the ⁇ -aminoacetophenone-based photopolymerization initiator having a group represented by the general formula (V) include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and N,N-dimethylaminoacetophenone.
• Commercially available products include Omnirad 369 and Omnirad 379 manufactured by IGM Resins.
• the amount of the ⁇ -aminoacetophenone-based photopolymerization initiator is preferably 0.1 to 80 parts by mass, preferably 2 to 50 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin, calculated as solid content.
• the above photopolymerization initiators may be used alone or in combination of two or more kinds.
• Oxime ester photopolymerization initiators having a group represented by the above general formula (V) are preferred because they have good initiator efficiency and are effective in improving sensitivity even in small amounts, so they produce less outgassing during heat treatment after resist film formation and are effective in reducing warping of the film.
• At least one of the primary amine, secondary amine, and tertiary amine may be, for example, a catalyst containing a nucleophilic group.
• the catalyst containing a nucleophilic group include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine; and hydrazine compounds
• the catalyst is not limited to these, and may be a heat curing catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of at least one of an epoxy group and an oxetanyl group with a carboxyl group, and may be used alone or in combination of two or more.
• S-triazine derivatives such as 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-isocyanuric acid adduct, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct may also be used, and preferably, these compounds that also function as adhesion-imparting agents may be used in combination with the heat curing catalyst.
• the above compounds can be used alone or in combination of two or more.
• Commercially available products include CUA-4 (primary amine) manufactured by Kumiai Chemical Industry Co., Ltd., DMP-30 (tertiary amine) manufactured by ThreeBond Co., Ltd., and melamine (primary amine) manufactured by Nissan Chemical Industries, Ltd.
• the amount of the catalyst containing a nucleophilic functional group that is added is sufficient in the usual quantitative ratio, and is preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the carboxyl group-containing resin, calculated as solid content.
• the amount of at least one of the primary amine, secondary amine and tertiary amine compounds is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 12 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin, calculated as solid content. If the amount of at least one of the primary amine, secondary amine and tertiary amine compounds is 0.1 parts by mass or more, this is preferred because it improves the photocurability on copper and also improves the coating properties such as chemical resistance. On the other hand, if it is less than 20 parts by mass, this is preferred because it provides adequate light absorption on the surface of the solder resist coating film and tends to improve deep curing.
• Epoxy compound having a weight average molecular weight of 700 or more examples include bisphenol A type epoxy compounds, phenol novolac type epoxy compounds, and hydrogenated bisphenol A type epoxy compounds.
• the lower limit of the weight average molecular weight of these epoxy compounds is 700 or more, preferably 800 or more, more preferably 850 or more.
• the upper limit of the weight average molecular weight of this epoxy compound is preferably 5,000 or less, more preferably 3,000 or less. These lower limit values and upper limit values can be combined arbitrarily.
• the weight average molecular weight of this epoxy compound can be measured, for example, by gel permeation chromatography (GPC).
• an epoxy compound having a weight average molecular weight in the above range can be obtained by the technical common knowledge of a person skilled in the art.
• the epoxy compound having a weight average molecular weight of 700 or more can be used alone or in combination of two or more kinds.
• Examples of commercially available products include N-870 manufactured by DIC Corporation, P201 manufactured by Nippon Kayaku Co., Ltd., and ST-5100 manufactured by Nippon Steel Chemical & Material Co., Ltd.
• the content of the epoxy compound having a weight average molecular weight of 700 or more is preferably 1 to 100 mass %, more preferably 5 to 60 mass %, of the total composition, calculated as solid content.
• the multi-component curable resin composition of the present invention may further include an epoxy compound having a weight average molecular weight of less than 700.
• the epoxy compound in the epoxy compound having a weight average molecular weight of less than 700 include hydrogenated resin type epoxy compounds, biphenyl type epoxy compounds, and bisphenol A type epoxy compounds.
• the lower limit of the weight average molecular weight of these epoxy compounds is preferably 5 or more, preferably 10 or more.
• the upper limit of the weight average molecular weight of this epoxy compound is less than 700.
• the weight average molecular weight of this epoxy compound can be obtained, for example, by the same measurement method as that described in the description of the epoxy compound having a weight average molecular weight of 700 or more.
• the epoxy compound having a weight average molecular weight in the above range can be obtained by the technical common sense of a person skilled in the art.
• the epoxy compounds having a weight average molecular weight of less than 700 may be used alone or in combination of two or more kinds.
• Commercially available products include YX-8034 and jER834 manufactured by Mitsubishi Chemical Corporation.
• the content of the epoxy compound having a weight average molecular weight of less than 700 is preferably 1 to 100 mass%, more preferably 5 to 60 mass%, of the total composition, calculated as solid content.
• the epoxy compound having a weight average molecular weight of less than 700 may accelerate the reaction with at least one of the primary amine, secondary amine, and tertiary amine, so it is preferable that the epoxy compound is blended in a composition liquid different from the composition liquid containing at least one of the primary amine, secondary amine, and tertiary amine.
• the photopolymerizable monomer ((meth)acrylate component) is photocured by irradiation with active energy rays, and makes the multi-component curable resin composition of the present invention insoluble or helps to make it insoluble in an alkaline aqueous solution.
• Examples of such compounds include diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxyethyl isocyanurate, and polyhydric acrylates such as ethylene oxide adducts, propylene oxide adducts, and ⁇ -caprolactone adducts of these alcohols; polyhydric acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl
• epoxy acrylate resins in which acrylic acid is reacted with multifunctional epoxy resins such as cresol novolac epoxy resins, and epoxy urethane acrylate compounds in which the hydroxyl groups of the epoxy acrylate resins are reacted with half-urethane compounds of hydroxyacrylates such as pentaerythritol triacrylate and diisocyanates such as isophorone diisocyanate.
• epoxy acrylate resins can improve photocuring properties without reducing tactile dryness.
• the above compounds can be used alone or in combination of two or more.
• Commercially available products include DPCA-60 manufactured by Nippon Kayaku Co., Ltd. and DPHA manufactured by Kyoeisha Chemical Co., Ltd.
• the amount of such (meth)acrylate components is, in terms of solid content, 5 to 80 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the carboxyl group-containing resin.
• the amount is 5 parts by mass or more, this is preferable because it improves photocurability and facilitates pattern formation by alkaline development after irradiation with active energy rays.
• the amount is less than 80 parts by mass, this is preferable because it provides a coating film with a suitable surface hardness.
• the multi-component curable resin composition of the present invention may further contain a photopolymerization initiator that does not contain a nucleophilic group (nucleophilic functional group).
• a photopolymerization initiator that does not contain a nucleophilic functional group it is preferable to use one or more photopolymerization initiators selected from the group consisting of acylphosphine oxide-based photopolymerization initiators having a group represented by the following formula (VI).
• Examples of the acylphosphine oxide photopolymerization initiator having a group represented by the above general formula (VI) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide.
• the above compounds may be used alone or in combination of two or more.
• Commercially available products include Omnirad 819 and Omnirad 1173 manufactured by IGM Resins.
• Acylphosphine oxide initiators having a group represented by the above general formula (VI) have the best light transmittance due to their photobleaching performance, and are effective in terms of flame retardancy.
• the amount of the photopolymerization initiator not containing a nucleophilic functional group as described above is suitably in the range of 0.1 to 80 parts by mass, preferably 2 to 50 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin, calculated as solid content.
• the photopolymerization initiator not containing a nucleophilic functional group When the amount of the photopolymerization initiator not containing a nucleophilic functional group is 0.1 parts by mass or more, the photocurability on copper is sufficient, and the coating film properties such as chemical resistance are improved, which is preferable, whereas when the amount is less than 80 parts by mass, the photopolymerization initiator not containing a nucleophilic functional group has a moderate light absorption on the solder resist coating film surface, and the deep curing property tends to be improved, which is preferable.
• the multi-component curable resin composition of the present invention may further contain a flame retardant.
• the flame retardant may be blended for the purpose of imparting flame retardancy to the cured product obtained after curing of the curable composition. It is preferable that the flame retardant is one that can increase the flame retardancy of the cured product without impairing the coatability, resolution, or warpage of the cured product.
• the flame retardant used in the present invention has the advantage of being able to improve the warpage, tackiness, transparency, and storage stability after exposure in a well-balanced manner.
• the flame retardant does not include compounds which are at least one of the above primary amines, secondary amines, and tertiary amines.
• [Other ingredients] in the multi-component curable resin composition of the present invention it is of course possible to compound further additives as other components, if necessary, within the scope of the object of the present invention.
• Such components include colorants, solvents, thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, antioxidants, antibacterial and antifungal agents, leveling agents, thickeners, adhesion imparting agents, thixotropy imparting agents, photoinitiator assistants, sensitizers, photobase generators, thermoplastic resins, elastomers, organic fillers such as urethane beads, inorganic fillers, release agents, surface treatment agents, dispersants, dispersion assistants, surface modifiers, stabilizers, fluorescent materials, cellulose resins, and the like.
• the multi-component curable resin composition of the present invention can be prepared by mixing and dispersing predetermined amounts of each component liquid at a high temperature (e.g., about 60°C) using, for example, a bead mill, and then mixing these component liquids when in use.
• a high temperature e.g., about 60°C
• the curable resin composition of the present invention can be used in liquid form or in the form of a dry film.
• the dry film of the present invention can be produced by applying the curable resin composition of the present invention onto a first film, drying the composition, and forming a resin layer as a dry coating film. If necessary, a second film can be laminated onto the resin layer.
• the first film has a role of supporting the resin layer of the dry film, and is a film onto which a curable resin composition is applied when the resin layer is formed.
• the first film include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyamideimide films, polyethylene films, polytetrafluoroethylene films, polypropylene films, polystyrene films, and other thermoplastic resin films, as well as surface-treated paper.
• polyester films are preferably used from the viewpoints of heat resistance, mechanical strength, and ease of handling.
• the thickness of the first film is not particularly limited, but is appropriately selected from the range of approximately 10 to 150 ⁇ m depending on the application.
• the surface of the first film on which the resin layer is provided may be subjected to a release treatment.
• sputtering or copper foil may be formed on the surface of the first film on which the resin layer is provided.
• the second film is provided on the side of the resin layer opposite the first film in order to prevent dust and other particles from adhering to the surface of the resin layer of the dry film and to improve handling.
• the second film may be, for example, a film made of a thermoplastic resin as exemplified for the first film, or surface-treated paper, among which polyester film, polyethylene film, and polypropylene film are preferred.
• the thickness of the second film is not particularly limited, but is appropriately selected from the range of approximately 10 to 150 ⁇ m depending on the application.
• the surface of the second film on which the resin layer is provided may be subjected to a release treatment.
• the cured product of the present invention can be obtained by curing the curable resin composition of the present invention or the resin layer of the dry film of the present invention.
• the individual composition liquids are mixed. There are no particular restrictions on the number of composition liquids as long as there are two or more liquids, but two liquids are preferred. As a mixing method, it is preferred to mix using a stirring blade such as a dissolver. Next, the mixed composition is applied to a substrate, and the resin layer obtained after evaporating and drying the solvent is exposed (irradiated with light) to cure the exposed parts (parts irradiated with light).
• a resist pattern is formed by selectively exposing the resin to active energy rays through a photomask with a pattern formed thereon using a contact or non-contact method, or directly exposing the pattern using a laser direct exposure machine, and developing the unexposed parts with an alkaline aqueous solution (for example, a 0.3 to 3 mass% aqueous solution of sodium carbonate). Furthermore, by heating to a temperature of about 100 to 220°C for thermal curing (post-curing), a cured coating (cured product) with excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties can be formed.
• either the first film or the second film is peeled off from the dry film, and the film is heat-laminated to a circuit board on which a circuit pattern is formed, and then heat-cured.
• Heat curing may be performed in an oven or by hot plate pressing.
• laminating or hot plate pressing the dry film of the present invention to the circuit board copper foil or a circuit board can be laminated at the same time.
• a printed wiring board can be manufactured by forming a pattern or a via hole by laser irradiation or drilling at a position corresponding to a predetermined position on the circuit board, and exposing the circuit wiring.
• a desmear treatment is performed.
• the remaining first or second film may be peeled off either after lamination, heat curing, laser processing, or desmear treatment.
• each composition liquid is mixed.
• the composition liquid is not particularly limited as long as it is two or more liquids, but two liquids are preferable.
• a mixing method it is preferable to stir using a stirring blade such as a dissolver.
• the multi-liquid curable resin composition is applied to a substrate, and the resin layer obtained after volatilizing and drying the solvent is exposed (irradiated with light), thereby curing the exposed part (light-irradiated part).
• a contact or non-contact method selective exposure to active energy rays through a photomask on which a pattern is formed, or direct pattern exposure by a laser direct exposure machine is performed. Thereafter, a resist pattern is formed by developing the unexposed part with an alkaline aqueous solution (for example, a 0.3 to 3 mass% aqueous solution of sodium carbonate). Furthermore, by heating to a temperature of about 100 to 220 ° C. and thermally curing (post-curing), a cured product such as a cured coating excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties can be formed.
• an alkaline aqueous solution for example, a 0.3 to 3 mass% aqueous solution of sodium carbonate.
• a cured product such as a cured coating excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties can be formed.
• the multi-component curable resin composition of the present invention can be adjusted to a viscosity suitable for the application method using an organic solvent, and applied to a substrate by a method such as dip coating, flow coating, roll coating, bar coating, screen printing, or curtain coating, and then the organic solvent contained in the composition can be evaporated and dried (pre-dried) at a temperature of about 60 to 100°C to form a tack-free resin layer.
• the substrates include printed wiring boards and flexible printed wiring boards with circuits already formed using copper, etc., as well as materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, copper-clad laminates for high-frequency circuits using fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc., including copper-clad laminates of all grades (FR-4, etc.), as well as metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, etc.
• materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, copper-clad laminates for high-frequency circuits using fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc., including copper-clad laminates of
• Volatilization drying or thermal curing can be carried out using, for example, a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, etc. (a method in which hot air in the dryer is brought into countercurrent contact using a heat source that uses steam for air heating, or a method in which hot air is blown onto the support from a nozzle).
• the exposure machine used for the active energy ray irradiation may be a machine equipped with a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like, and capable of irradiating ultraviolet rays in the range of 350 to 450 nm, and further, a direct imaging machine (for example, a laser direct imaging machine that draws an image directly with a laser based on CAD data from a computer) may also be used.
• the lamp light source or laser light source of the direct imaging machine may have a maximum wavelength in the range of 350 to 410 nm.
• the exposure dose for forming an image varies depending on the film thickness, etc., but can generally be within the range of 20 to 2,000 mJ/cm 2 , preferably 20 to 1,500 mJ/cm 2 .
• the development method can be a dipping method, a shower method, a spray method, a brush method, etc.
• the developer can be an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc.
• the multi-component curable resin composition of the present invention is preferably used to form a cured film on a printed wiring board, more preferably used to form a permanent coating, and even more preferably used to form a solder resist, an interlayer insulating layer, or a coverlay. It is particularly suitable for use in flexible printed wiring boards that require properties such as bending resistance.
• the photopolymerization initiator component in the cured product can be identified and quantified, for example, by the following method.
• the identification can be carried out, for example, by using a known Fourier transform infrared spectrometer (FT-IR) and a visible ultraviolet spectrophotometer.
• FT-IR Fourier transform infrared spectrometer
• a preferred method is to measure the infrared absorption spectrum of the cured product with a Fourier transform infrared spectrometer (FT-IR) and identify the photopolymerization initiator component in the cured product.
• the identification and quantification can be carried out, for example, using a known ultraviolet-visible spectrophotometer and a Fourier transform infrared spectrophotometer (FT-IR).
• a preferred method is to obtain a UV spectrum using a ultraviolet-visible spectrophotometer and identify and quantify the photopolymerization initiator component in the cured product. For example, since oxime ester-based photopolymerization initiators have strong absorption in the range of 320 nm to 350 nm, they can be quantified in that range.
• the present invention also provides an electronic component having the above-mentioned cured product.
• an electronic component having high quality, durability, and reliability is provided.
• the electronic component means a component used in an electronic circuit, and includes active components such as printed wiring boards, transistors, light-emitting diodes, and laser diodes, as well as passive components such as resistors, capacitors, inductors, and connectors.
• the epoxy resin (a) obtained was calculated from the epoxy equivalent, and about 5 of the 6.2 alcoholic hydroxyl groups in the starting material bisphenol F type epoxy resin were epoxidized. 310 parts of this epoxy resin (a) and 282 parts of carbitol acetate were charged in a flask, heated to 90°C, stirred, and dissolved. The resulting solution was once cooled to 60°C, and 72 parts (1 mole) of acrylic acid, 0.5 parts of methylhydroquinone, and 2 parts of triphenylphosphine were added, heated to 100°C, and reacted for about 60 hours to obtain a reaction product with an acid value of 0.2 mgKOH/g.
• Carboxyl group-containing resin A Carboxyl group-containing resin A obtained in the above "Synthesis of carboxyl group-containing resin A"
• N-870 N-870 (bisphenol A type epoxy compound) manufactured by DIC Corporation [equivalent weight 200; weight average molecular weight 1,000 to 2,000]
• P201 P201 (phenol novolac type epoxy compound) manufactured by Nippon Kayaku Co., Ltd. [equivalent weight 200; weight average molecular weight 1,000 to 2,000] ST-5100: Nippon Steel Chemical & Material Co., Ltd.
• DPCA-60 KAYARAD DPCA-60 (caprolactone modified acrylate) manufactured by Nippon Kayaku Co., Ltd.
• OXE02 Irgacure OXE02 (oxime ester photopolymerization initiator) manufactured by BASF Japan Ltd.; Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime)
• OXE04 Irgacure OXE04 (oxime ester photopolymerization initiator) manufactured by BASF Japan Ltd.
• Omnirad 369 Omnirad 369 ( ⁇ -aminoalkylphenone, photopolymerization initiator) manufactured by IGM Resins; 2-benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone 379: Omnirad 379EG ( ⁇ -aminoalkylphenone, photopolymerization initiator) manufactured by IGM Resins; 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one CUA-4 (primary amine): CUA-4 (trimethylene-bis(4-aminobenzoate)) manufactured by Kumiai Chemical Industry Co., Ltd.
• 2E4MZ (secondary amine): 2E4MZ (2-ethyl-4-methylimidazole) manufactured by Shikoku Chemical Industry Co., Ltd.
• DMP-30 (tertiary amine): DMP-30 (2,4,6-tris(dimethylaminomethyl)phenol) manufactured by ThreeBond Co., Ltd.
• Melamine Melamine (primary amine) manufactured by Nissan Chemical Co., Ltd.
• TPO 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide 819: Omnirad 819 (bisacylphosphine oxide initiator) manufactured by IGM Resins; Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide 1173: Omnirad 1173 (photopolymerization initiator, ⁇ -hydroxyacetophenone) manufactured by IGM Resins; 2-hydroxy-2-methyl-1-phenylpropanone YX-8034: Mitsubishi Chemical Corporation (biphenyl type epoxy compound) [equivalent weight 270; weight average molecular weight 540] DPHA: Dipentaerythritol hexaacrylate 2MZ-A (primary amine): 2MZ-A (2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine) manufactured by Shikoku Chemical Industry Co., Ltd.
• the first composition liquid and the second composition liquid prepared by mixing and dispersing in a bead mill were thoroughly mixed in a ratio of 1:1 using a dissolver (rotation speed 800 rpm, room temperature for 15 minutes), and then coated entirely on an etched-out substrate so that the film thickness after drying would be 30 ⁇ m, and dried at 80° C. for 30 minutes.
• a step tablet (Kodak No. 2) was attached to each coating film, and exposed to an exposure amount of 500 mJ/cm 2 using a metal halide lamp exposure machine (HMW-680-GW20 manufactured by Oak Manufacturing Co., Ltd.).
• sensitivity was obtained from the remaining step number and gloss step number obtained from the step tablet (Kodak No. 2) (hereinafter referred to as sensitivity 1).
• various components shown in Table 1 were mixed in the ratios shown in Table 1 (unit: parts by mass) and kneaded with a three-roll mill to prepare a first composition liquid and a second composition liquid constituting a two-liquid curable resin composition.
• the prepared first composition liquid and second composition liquid were thoroughly mixed in a ratio of 1:1 using a dissolver (rotation speed 800 rpm, room temperature for 15 minutes), and then coated on the entire surface of an etched-out substrate so that the film thickness after drying was 30 ⁇ m, dried at 80 ° C. for 30 minutes, and a step tablet (Kodak No. 2) was adhered to each coating film, exposed to an exposure amount of 500 mJ / cm 2 using a metal halide lamp exposure machine (Oak Manufacturing Co., Ltd. HMW-680-GW20), developed with a 1.0 mass % sodium carbonate aqueous solution at a spray pressure of 0.2 MPa at 30 ° C.
• Sensitivity 1 and Sensitivity 2 were compared and evaluated according to the following criteria. ⁇ : No change in sensitivity (variation between sensitivity 1 and sensitivity 2 is within ⁇ 1 step for both residual sensitivity and gloss sensitivity) ⁇ : Sensitivity is decreased (the variation between Sensitivity 1 and Sensitivity 2 is ⁇ 2 steps or more for both residual sensitivity and gloss sensitivity)
• the first and second composition liquids were thoroughly mixed (rotation speed 800 rpm, 15 minutes) using a dissolver to obtain a two-liquid curable resin composition.
• the optimum exposure dose was determined as the exposure dose at which the surface of the dried coating film was exposed through a step tablet (Kodak No. 2) using an exposure machine equipped with a metal halide lamp as a light source, and the remaining step tablet pattern was determined to have 6 to 7 steps when developed with a 1.0 mass % aqueous sodium carbonate solution at a spray pressure of 0.2 MPa at 30°C for 1 minute.
• ⁇ A 70 ⁇ m line remains, and the shape is good.
• A A 100 ⁇ m line remains, and the shape is good.
• ⁇ No 100 um line remains.
• the optimal exposure amount was an exposure amount at which the above-mentioned dried coating surface was exposed through a step tablet (Kodak No.
• step tablet was 6 to 7 steps when developed with a 1.0 mass% sodium carbonate aqueous solution at a spray pressure of 0.2 MPa at 30 ° C. for 1 minute. Then, the substrate was heat-treated at 150°C for 60 minutes in a hot air circulation drying oven to obtain an evaluation substrate having a cured coating.
• the evaluation substrate was plated using a commercially available electroless nickel plating bath and electroless gold plating bath under the conditions of nickel 3 ⁇ m and gold 0.03 ⁇ m, and the presence or absence of peeling of the resist layer and the presence or absence of plating penetration were evaluated by tape peeling, and then the presence or absence of peeling of the resist layer was evaluated by tape peeling.
• the evaluation criteria are as follows. ⁇ : No peeling is observed. ⁇ : Peeling occurs after plating.
• the optimal exposure amount was an exposure amount at which the dried coating surface was exposed through a step tablet (Kodak No. 2) using an exposure machine (Oak Manufacturing Co., Ltd.
• the remaining step tablet pattern was 6 to 7 steps when developed with a 1.0 mass% sodium carbonate aqueous solution at a spray pressure of 0.2 MPa at 30° C. for 1 minute.
• the substrate was heat-treated at 150°C for 60 minutes in a hot air circulating drying oven to obtain an evaluation substrate having a cured coating.
• the evaluation substrate coated with rosin-based flux was immersed in a solder bath previously set at 260°C, and the flux was washed off with denatured alcohol.
• the resist layer was visually evaluated for swelling and peeling. The evaluation criteria were as follows: A: No peeling was observed after immersion for 10 seconds once. x: After immersion for 10 seconds once, the resist layer swells and peels off.
• the two-part curable resin compositions of Examples 1 to 7 were good in all of the sensitivity, resolution, electroless gold plating resistance, and solder heat resistance of the curable resin compositions after mixing.
• the two-part curable resin compositions of Comparative Examples 1 and 2 were poor in all of the sensitivity, resolution, and electroless gold plating resistance of the curable resin compositions after mixing.
• productivity when a photopolymerization initiator was also blended in the same composition liquid as the carboxyl group-containing resin, the mixing and dispersion time was shortened and the productivity was also improved.

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