WO2019188376A1 - 光硬化性熱硬化性樹脂組成物及びドライフィルム及び硬化物ならびにプリント配線板 - Google Patents

光硬化性熱硬化性樹脂組成物及びドライフィルム及び硬化物ならびにプリント配線板 Download PDF

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WO2019188376A1
WO2019188376A1 PCT/JP2019/010702 JP2019010702W WO2019188376A1 WO 2019188376 A1 WO2019188376 A1 WO 2019188376A1 JP 2019010702 W JP2019010702 W JP 2019010702W WO 2019188376 A1 WO2019188376 A1 WO 2019188376A1
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mass
monomer
polymer
carboxyl group
radical polymerizable
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PCT/JP2019/010702
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English (en)
French (fr)
Japanese (ja)
Inventor
知哉 工藤
岡田　和也
千穂 植田
沙和子 嶋田
信人 伊藤
雅年 吉田
前田　順啓
大槻　信章
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太陽インキ製造株式会社
株式会社日本触媒
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Application filed by 太陽インキ製造株式会社, 株式会社日本触媒 filed Critical 太陽インキ製造株式会社
Priority to KR1020207030286A priority Critical patent/KR20200138286A/ko
Priority to CN201980020641.4A priority patent/CN111886545B/zh
Publication of WO2019188376A1 publication Critical patent/WO2019188376A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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 containing a radical polymerizable polymer soluble in an alkaline aqueous solution, a dry film and a cured product thereof, and an electronic component.
  • a curable resin composition is generally employed for forming a permanent film such as a solder resist in the production of printed wiring boards.
  • a curable resin composition a dry film type composition and a liquid composition have been developed.
  • the curable resin composition can be finely processed by applying the principle of a photographic method (photolithography).
  • photolithography an alkali developing type that can be developed with a dilute weak alkaline aqueous solution has become the mainstream from the viewpoint of environmental measures.
  • the curable resin composition generally contains a prepolymer having an unsaturated double bond, a polymerizable monomer, and a photopolymerization initiator as essential components.
  • the prepolymer mainly used as a photocurable component include acrylate resins such as polyester acrylate, urethane acrylate, and epoxy acrylate. These acrylate resins are widely used because they are easy to manufacture and have excellent photocurability. For example, (meth) acrylate compounds having two carboxyl groups in the molecule and 2 in the molecule.
  • the resin composition containing an unsaturated group-containing polycarboxylic acid resin obtained by reacting an epoxy resin having a single epoxy group has good characteristics such as alkali developability, heat resistance and flexibility. It is known (see Patent Document 1).
  • an object of the present invention is to provide a curable resin composition excellent in insulation reliability such as B-HAST resistance, its dry film and cured product, and an electron while maintaining characteristics such as alkali developability, curability and heat resistance. To provide parts.
  • a resin composition containing a specific carboxyl group-containing photosensitive resin and a thermosetting compound is flexible while maintaining excellent alkali developability, heat resistance, and the like. It has been found that a cured product having an insulation reliability such as imparting and excellent B-HAST resistance can be obtained, and the present invention has been completed.
  • the curable resin composition of the present invention is a curable resin composition comprising (A) a carboxyl group-containing photosensitive resin, (B) a photopolymerization initiator, and (C) a thermosetting compound,
  • the (A) carboxyl group-containing photosensitive resin contains a radical polymerizable polymer, and the radical polymerizable polymer is composed of 10 to 10 constituent units derived from a maleimide monomer in 100% by mass of the base polymer.
  • Formula (2): Solid content concentration Y (mass%) ⁇ mass (g) of solid content obtained by heating and drying 0.3 g of radical polymerizable polymer (mass before heat drying) at 160 ° C. for 1 hour 30 minutes under vacuum ⁇ / ⁇ Mass before heating and drying of radical polymerizable polymer 0.3 (g) ⁇
  • the dry film of this invention has the resin layer obtained by apply
  • the cured product of the present invention is characterized in that the curable resin composition or the dry film is cured.
  • the electronic component of the present invention is characterized by having the above cured product.
  • the curable resin composition of the present invention is excellent in alkali developability, curability, heat resistance, and insulation reliability. Furthermore, the curable resin composition of this invention can have as said hardened
  • the curable resin composition of the present invention is a curable resin composition comprising (A) a carboxyl group-containing photosensitive resin, (B) a photopolymerization initiator, and (C) a thermosetting compound,
  • the (A) carboxyl group-containing photosensitive resin contains a radical polymerizable polymer, and the radical polymerizable polymer is composed of 10 to 60 structural units derived from maleimide monomers in 100% by mass of the polymer as the base polymer.
  • Containing 10 to 40% by mass of a structural unit derived from an unsaturated carboxylic acid monomer having no ester bond, and 10 to 40% by mass of a structural unit derived from a monomer having a hydroxyl group as essential units It has a structure obtained by reacting a monomer having a functional group capable of reacting with the carboxyl group of a polymer which is a polymer, and The relative value represented by the ratio X / Y between the post-heat treatment residual ratio X (mass%) obtained by the following formula (1) and the solid content concentration Y (mass%) obtained by the following formula (2) is 0.95. It is the above.
  • Formula (2): Solid content concentration Y (mass%) ⁇ mass (g) of solid content obtained by heating and drying 0.3 g of radical polymerizable polymer (mass before heat drying) at 160 ° C. for 1 hour 30 minutes under vacuum ⁇ / ⁇ Mass before heating and drying of radical polymerizable polymer 0.3 (g) ⁇
  • the curable resin composition of the present invention contains a carboxyl group-containing photosensitive resin.
  • This carboxyl group-containing photosensitive resin contains a radical polymerizable polymer.
  • the radical polymerizable polymer is composed of a maleimide monomer-derived structural unit, a structural unit derived from an unsaturated carboxylic acid monomer having no ester bond, and a structural unit derived from a monomer having a hydroxyl group as essential units. It has a structure obtained by reacting a monomer having a functional group capable of reacting with a carboxyl group with respect to a carboxyl group that the polymer (base polymer) has.
  • the said carboxyl group is contained in the structural unit derived from the unsaturated carboxylic acid monomer which does not have the said ester bond in the said polymer (base polymer).
  • the carboxyl group of the constituent unit derived from the unsaturated carboxylic acid monomer having no ester bond preferably a part of which has a functional group capable of reacting with the carboxyl group. It has a structure to which a monomer is added.
  • the structural unit derived from the polymer (base polymer) constitutes a main chain.
  • the structural unit derived from the monomer having a functional group capable of reacting with the carboxyl group constitutes a side chain of the radical polymerizable polymer.
  • the monomer having a functional group capable of reacting with the carboxyl group preferably has a radical polymerizable carbon-carbon double bond (hereinafter sometimes simply referred to as a radical polymerizable double bond).
  • the radical polymerizable polymer is preferably a constituent unit derived from an unsaturated carboxylic acid monomer having no ester bond, and a constituent unit derived from a maleimide monomer in a main chain of 100% by mass. It contains 10 to 40% by mass and 10 to 40% by mass of a structural unit derived from a monomer having a hydroxyl group, and has a radically polymerizable carbon-carbon double bond in the side chain.
  • a maleimide monomer unit refers to a structural unit derived from a monomer, and a polymerizable carbon-carbon double bond (C ⁇ C) in the monomer is a single bond (C— C) is a structural unit.
  • a maleimide monomer unit means a structural unit derived from a maleimide monomer when a maleimide monomer is copolymerized or graft polymerized.
  • a maleimide monomer unit, an unsaturated carboxylic acid (monomer) unit having no ester bond, a polymer having a monomer unit having a hydroxyl group as an essential unit (base polymer) is a maleimide monomer, It is preferably obtained by radical polymerization using an unsaturated carboxylic acid having no ester bond and a monomer having a hydroxyl group as essential components. The monomer will be described below.
  • maleimide monomers include N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2- Chlorophenyl) maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmethylmaleimide, N- (2,4,6-tri Bromophenyl) maleimide, N- [3- (triethoxysilyl) propyl] maleimide, N-octadecenylmaleimide, N-dodecenylmaleimide, N- (2-methoxyphenyl) maleimide, N- (2, 4,6-trichlorophenyl) maleimide, N- (4-hydroxyphenyl)
  • N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (2,6-diethylphenyl) are advantageous in that they have a large effect of improving heat resistance, good copolymerization, and are easily available.
  • Maleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and the like are preferable, N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide are more preferable, and N-phenylmaleimide and N-benzylmaleimide are most preferable.
  • N-phenylmaleimide and N-benzylmaleimide are also preferable to use.
  • a preferred ratio of N-phenylmaleimide and N-benzylmaleimide when used in combination is 99: 1 to 1:99 by mass ratio.
  • an unsaturated carboxylic acid (monomer) having no ester bond is used as an essential component in order to introduce a carboxyl group that is essential for alkali development and to further improve the properties of the cured product.
  • Specific examples include (meth) acrylic acid, crotonic acid, cinnamic acid, sorbic acid, fumaric acid, maleic acid and the like. Among them, (meth) acrylic acid is preferable because of excellent properties of the cured product.
  • another acid group may be introduced together with the carboxyl group or instead of the carboxyl group.
  • Examples of other acid groups include functional groups that neutralize with alkaline water, such as phenolic hydroxyl groups, carboxylic acid anhydride groups, phosphoric acid groups, and sulfonic acid groups, and have only one of these. Or you may have 2 or more types. In the following description, the description for the carboxyl group also applies to the other acid groups.
  • a monomer having a hydroxyl group (hydroxyl group) is used as an essential component.
  • a polymer having (meth) acrylic acid copolymerized as a polymer having a carboxyl group is known, but there is room for improvement in terms of alkali developability.
  • a method for improving alkali developability a method in which a monomer unit having a hydroxyl group is copolymerized and a polybasic acid anhydride is reacted with a hydroxyl group in a hydroxyl group-containing skeleton is described in Patent Document 2.
  • the glycidyl group in the glycidyl group-containing skeleton is reacted with an unsaturated monobasic acid such as (meth) acrylic acid, and the glycidyl group is opened to produce a polybasic acid.
  • an unsaturated monobasic acid such as (meth) acrylic acid
  • a product obtained by reacting an anhydride is known, but both have room for improvement in terms of both alkali developability and heat resistance.
  • the present invention it is possible to develop good alkali developability by copolymerizing unsaturated carboxylic acid having no ester bond, monomer having a hydroxyl group, and both as essential components.
  • the properties of the cured product can also be excellent.
  • Monomers having a hydroxyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy (meth) acrylate.
  • hydroxyalkyl (meth) acrylates such as butyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, and 2-hydroxymethyl (Meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (meth) acrylamide, hydroxypivalyl (meth) acrylamide, 5 -Hydroxy pliers (Meth) acrylamide, 6-hydroxyhexyl (meth) include hydroxyalkyl (meth) acrylamides such as acrylamide, one or more of these can be used. Of these, hydroxyalkyl (meth) acrylate is preferable from the viewpoint of copolymerizability, and 2-hydroxyethyl (meth) acrylate is particularly preferable.
  • the maleimide monomer (maleimide monomer unit) is 100% by mass of the base polymer, in other words, all monomer components constituting the base polymer (all monomer units constituting the base polymer). 100 mass%) to 10 mass% to 60 mass%.
  • the preferable lower limit of the maleimide monomer is 15% by mass, and the more preferable lower limit is 20% by mass.
  • a preferable upper limit is 55 mass%, and a more preferable upper limit is 50 mass%.
  • Unsaturated carboxylic acid having no ester bond is composed of all monomer components constituting the base polymer (100% by mass of all monomer units constituting the base polymer).
  • the content is 10 to 40% by mass.
  • the content of the unsaturated carboxylic acid is 10% by mass or more, good alkali developability can be expressed.
  • by setting the content to 40% by mass or less it is possible to sufficiently impart cured product characteristics such as heat resistance caused by the maleimide monomer.
  • a preferable lower limit of the unsaturated carboxylic acid is 15% by mass, and a more preferable lower limit is 20% by mass.
  • a preferable upper limit is 35 mass%, and a more preferable upper limit is 30 mass%.
  • the monomer having a hydroxyl group (monomer unit having a hydroxyl group) is 10 to 40% by mass in all monomer components constituting the base polymer (100% by mass of all monomer units constituting the base polymer). .
  • the content of the monomer having a hydroxyl group is 10% by mass or more, good alkali developability can be expressed.
  • by setting the content to 40% by mass or less it is possible to sufficiently impart cured product characteristics such as heat resistance caused by the maleimide monomer.
  • the minimum with a preferable monomer which has a hydroxyl group is 12 mass%, and a more preferable minimum is 15 mass%.
  • a preferable upper limit is 35 mass%, and a more preferable upper limit is 30 mass%.
  • copolymerizable monomer components may be used when obtaining a polymer (base polymer) as long as the properties are not adversely affected.
  • monomer components include aromatic monomers having no ester bond; vinyl ester monomers such as vinyl acetate and vinyl adipate; methyl (meth) acrylate, ethyl (meth) acrylate, (Meth) acrylic monomers such as butyl (meth) acrylate; alkyl vinyl ethers such as n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, n-hexyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether and the like Alkyl vinyl (thio) ethers; monomers containing acid anhydride groups such as maleic anhydride, or monomers obtained by ring-opening modification of acid anhydride groups with alcohols, etc.
  • an aromatic monomer having no ester bond is preferable because it has good copolymerizability with a maleimide monomer and is excellent in properties of a cured product.
  • Specific examples include styrene, ⁇ -methylstyrene, ⁇ -chlorostyrene, vinyltoluene and the like. Styrene is most preferable because of its excellent electrical characteristics and low cost.
  • the total content of the other copolymerizable monomer components is preferably 0 to a total of all monomer components constituting the base polymer (100% by mass of all monomer units constituting the base polymer). It is 70% by mass, more preferably 0 to 55% by mass, still more preferably 0 to 20% by mass.
  • an aromatic monomer having no ester bond (aromatic monomer unit having no ester bond) is composed of all monomer components constituting the base polymer (total single monomer constituting the base polymer).
  • the body unit is preferably 1 to 35% by mass in 100% by mass).
  • the content is 35% by mass or less, the heat resistance and alkali developability due to the maleimide monomer, the unsaturated carboxylic acid, and the monomer having a hydroxyl group can be more sufficiently imparted.
  • the more preferable lower limit of the aromatic monomer having no ester bond is 5% by mass, the more preferable lower limit is 7% by mass, and the particularly preferable lower limit is 8% by mass.
  • a more preferable upper limit is 33 mass%, and a more preferable upper limit is 30 mass%.
  • the relative value X / Y between the post-heat treatment residual ratio X (mass%) and the solid content concentration Y (mass%) obtained by the method is a method for producing a radical polymerizable polymer, which is 0.95 or more, In 100% by mass of the monomer component, 10 to 60% by mass of maleimide monomer, 10 to 40% by mass of unsaturated carboxylic acid monomer having no ester bond, and 10 to 40% by mass of monomer having a hydroxyl group A step of obtaining a polymer (base polymer) by reacting the monomer component containing, as an essential component,%, A step of reacting a monomer having a functional group capable of reacting with the carboxyl group with respect to the carboxyl group of the polymer to obtain a radical polymerizable polymer; Is included.
  • the method for obtaining the polymer is not particularly limited, and a conventionally known polymerization method such as a solution polymerization method or a bulk polymerization method can be employed. is there. Among these, a solution polymerization method is preferable because temperature control during the polymerization reaction is easy.
  • the solvent for the solution polymerization is not particularly limited as long as it does not inhibit the polymerization or alter each component of the raw material monomer.
  • usable solvents include hydrocarbons such as toluene and xylene; cellosolve acetate, carbitol acetate, (di) propylene glycol monomethyl ether acetate, glutaric acid (di) methyl, succinic acid (di) methyl, and adipine Acid (di) methyl, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc .; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, Examples include ethers such as methyl-t-butyl ether and (di) ethylene glycol dimethyl ether; amides such as N, N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide, and the like.
  • Others can be used in combination of two or more.
  • the monomer or polymer In order to improve the solubility, a mixed solvent of esters such as propylene glycol monomethyl ether acetate and carbitol acetate and alcohols such as propylene glycol monomethyl ether and isopropanol is preferable.
  • polymerization initiator examples include ordinary radical polymerization initiators. Specifically, 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvalero) Nitrile), 2,2′-azobis (2-methylisobutyronitrile) and the like; lauroyl peroxide, benzoyl peroxide, t-butylperoxyneodecanate, t-butylperoxypivalate, t -Organic peroxides such as amyl peroxy octoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy benzoate, methyl ethyl ketone peroxide, dicumyl peroxide, etc. are desirable. What is necessary is just to select it suitably according to reaction conditions and the required characteristic with
  • the amount of the polymerization initiator used is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass with respect to 100% by mass of the monomer component used in the polymerization reaction. is there.
  • the specific method for obtaining the polymer (base polymer) is not particularly limited, but a method of polymerizing all components in a solvent at once, the remaining components in a reaction vessel in which a solvent and a part of the components have been charged in advance. It is possible to employ a method of polymerizing by continuously adding or sequentially adding.
  • a monomer having 10 to 40% by mass of a monomer having a hydroxyl group as an essential component is preferably radically polymerized using the polymerization initiator.
  • the total monomer component preferably further contains 1 to 35% by mass of an aromatic monomer having no ester bond.
  • the reaction may be performed under normal pressure or pressurized conditions.
  • the temperature during the polymerization reaction although it depends on the type and composition ratio of the raw material monomer to be used and the type of solvent used, it is usually preferably 20 to 150 ° C., more preferably 30 to 120 ° C. .
  • the amount of the solvent and each monomer component so that the final solid content of the polymer solution is 10 to 70% by mass. If this final solid content concentration is less than 10% by mass, productivity is lowered, which is not preferable. On the other hand, when the final solid content concentration exceeds 70% by mass, the viscosity of the polymerization solution may increase even in the case of solution polymerization, and the polymerization conversion rate may not increase.
  • a more preferable final solid content concentration is 20 to 65% by mass, and further preferably 25 to 60% by mass.
  • the weight average molecular weight Mw of the polymer is determined by gel permeation chromatography (hereinafter referred to as gel permeation chromatography). , Also referred to as “GPC”), a polystyrene conversion value of 1,000 to 100,000 is preferable.
  • GPC gel permeation chromatography
  • Mw polystyrene conversion value of 1,000 to 100,000 is preferable.
  • a more preferred upper limit is 50,000, and a more preferred upper limit is 30,000.
  • a chain transfer agent may be used during the polymerization reaction, but if it is not used, a resin composition having no mercaptan odor can be obtained.
  • any chain transfer agent that does not adversely affect each monomer component used for polymerization may be used, and a thiol compound is usually used.
  • alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan; aryl mercaptans such as thiophenol; mercapto group-containing aliphatic carboxylic acids such as mercaptopropionic acid and methyl mercaptopropionate, and the like Ester etc. are mentioned as a preferable thing.
  • the amount of the chain transfer agent used is not particularly limited, and may be adjusted as appropriate so as to obtain a polymer having a desired molecular weight.
  • the amount of chain transfer agent is 0 with respect to the total amount of monomers used for polymerization.
  • the content is preferably 1 to 15% by mass, more preferably 0.5 to 10% by mass.
  • a monomer having a functional group capable of reacting with a carboxyl group is reacted with the carboxyl group of the polymer (base polymer) to impart radical polymerizability.
  • a radical polymerizable carbon-carbon double bond introduction reaction is preferably performed.
  • the radical polymerizable group (preferably carbon-carbon double bond) introduction reaction is carried out by introducing a carboxyl group of the polymer, a functional group capable of reacting with the carboxyl group, and a radical polymerizable group (preferably a carbon-carbon double bond).
  • a polymerization inhibitor such as methylhydroquinone and oxygen, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, 2-ethyl-4-methyl, and the like.
  • the reaction can be performed at about 80 to 130 ° C. in the presence of a reaction catalyst such as imidazoles such as imidazole, phosphorus compounds such as triphenylphosphine, metal organic acid salts and inorganic acid salts, and chelate compounds.
  • a reaction catalyst such as imidazoles such as imidazole, phosphorus compounds such as triphenylphosphine, metal organic acid salts and inorganic acid salts, and chelate compounds.
  • the functional group capable of reacting with an acid group such as a carboxyl group is preferably selected from the group consisting of a glycidyl group, an oxazolinyl group, an isocyanate group and an oxetanyl group.
  • the radical polymerizable carbon-carbon double bond is preferably a (meth) acryloyl group.
  • the monomer having a glycidyl group examples include glycidyl (meth) acrylate, allyl glycidyl ether, ⁇ -ethylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl acrylate (for example, “Cyclocycling” manufactured by Daicel Corporation).
  • Mer A400 ") 3,4-epoxycyclohexylmethyl methacrylate (for example,” Cyclomer M100 "manufactured by Daicel Corporation) and the like.
  • the monomer having an oxazolinyl group include N-vinyloxazoline and 2-isopropenyl-2-oxazoline.
  • the monomer having an isocyanate group examples include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxyethoxyethyl isocyanate, bis (acryloxymethyl) ethyl isocyanate, and modified products thereof.
  • Karenz MOI methacryloyloxyethyl isocyanate
  • Karenz AOI acryloyloxyethoxyethyl isocyanate
  • Karenz MOI-EG methacryloyloxyethoxyethyl isocyanate
  • Karenz MOI-BM Karenz MOI isocyanate block
  • Karenz MOIBP Karenz MOI isocyanate block
  • Karenz BEI bis (acryloxymethyl) ethyl isocyanate
  • the monomer having an oxetanyl group examples include 3- (meth) acryloyloxymethyl oxetane and 3-ethyl-3- (meth) acryloyloxymethyl oxetane.
  • glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl methacrylate are preferable from the viewpoint of reactivity and industrial availability. Particularly preferred are glycidyl methacrylate and 3,4-epoxycyclohexylmethyl methacrylate.
  • the radical polymerizable carbon-carbon double bond introduction reaction is preferably performed so that the double bond equivalent is 600 to 4000 g / equivalent.
  • the double bond equivalent is related to the photocurability and the physical properties of the cured product.
  • a cured product having excellent physical properties such as heat resistance, strength, and flexibility can be provided.
  • a well-balanced photosensitive resin in which photocurability and alkali developability are compatible can be obtained.
  • a more preferable range of the double bond equivalent is 700 to 3000 g / equivalent, and further preferably 800 to 2500 g / equivalent.
  • the acid value of the radical polymerizable polymer obtained as described above is preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 50 mgKOH / g or more, and preferably 160 mgKOH / g or less, and 155 mgKOH / g. g or less is more preferable, and 150 mgKOH / g or less is more preferable.
  • the acid value of the radical polymerizable polymer is 30 mgKOH / g or more, good alkali developability is easily developed.
  • the acid value of the radical polymerizable polymer is 160 mgKOH / g or less, the exposed portion is hardly eroded by the alkali developer, and the water resistance and moisture resistance of the cured product are improved.
  • the amount of the monomer having a functional group capable of reacting with a carboxyl group is 0.01 to 0.99 relative to 1 equivalent of the carboxyl group of the polymer before the radical polymerizable carbon-carbon double bond introduction reaction. It is preferable that the double bond equivalent and the acid value of the obtained radical polymerizable polymer are determined so as to fall within the above-mentioned preferable range.
  • the preferred range of Mw of the radical polymerizable polymer is the same as the preferred range of Mw of the polymer before the radical polymerizable carbon-carbon double bond introduction reaction.
  • the relative value X / Y between the post-heat treatment residual ratio X (mass%) and the solid content concentration Y (mass%) obtained by the following formula is 0.95 or more.
  • Residual ratio after heat treatment X (mass%) ⁇ mass of dry mixture obtained by heating and drying a mixture of 0.3 g of radical polymerizable polymer (mass before heat drying) and 2 ml of acetone at 200 ° C. for 30 minutes.
  • the radical polymerizable polymer may contain the above solvent.
  • the heat-drying of the radically polymerizable polymer is preferably performed in a container having high thermal conductivity such as an aluminum cup.
  • a container having high thermal conductivity such as an aluminum cup.
  • the mass 0.3 g of the radical polymerizable polymer before heat drying it is sufficient that the mass weighed accurately is known, and may be around 0.3 g (for example, 0.28 to 0.32 g).
  • radical polymerizable polymer 10 to 60% by mass of a structural unit derived from a maleimide monomer in 100% by mass of a structural unit derived from all monomers of the polymer before the radical polymerizable group introduction reaction, and an ester bond. Since it has 10 to 40% by mass of a structural unit derived from an unsaturated carboxylic acid monomer not contained and 10 to 40% by mass of a structural unit derived from a monomer having a hydroxyl group as essential units, the ester bond content is kept low. Excellent thermal decomposition resistance can be obtained.
  • the relative value X / Y is 1 when no thermal decomposition occurs, and the closer the relative value X / Y is to 1, the better the thermal decomposition resistance.
  • the relative value X / Y is preferably 0.96 or more, more preferably 0.97 or more, and further preferably 0.98 or more.
  • the (A) carboxyl group-containing photosensitive resin is a copolymer resin having a maleimide skeleton that does not use an epoxy resin as a starting material and has a balance between alkali developability and heat resistance. Therefore, the curable resin composition of the present invention can provide a resin composition having good heat resistance and alkali developability by including the above-mentioned (A) carboxyl group-containing photosensitive resin. Also excellent in properties. In the curable resin composition of this invention, you may contain carboxyl group-containing resin other than (A) further. As the carboxyl group-containing resin other than (A), various conventionally known carboxyl group-containing resins having a carboxyl group in the molecule can be used.
  • a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferable from the viewpoint of photocurability and development resistance.
  • the ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof.
  • Specific examples of the carboxyl group-containing resin other than (A) include the following compounds (any of oligomers and polymers).
  • a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
  • Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers
  • carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
  • Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
  • bisphenol A type epoxy resin hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
  • one isocyanate group and one or more (meth) acryloyl groups are added in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate.
  • a carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal (meth) acrylate.
  • a carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or higher polyfunctional (solid) epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group present in the side chain.
  • Two bases such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are reacted with a dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid by reacting the bifunctional oxetane resin.
  • An epoxy compound having a plurality of epoxy groups in one molecule a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and (meth) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as an acid.
  • Reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with an unsaturated group-containing monocarboxylic acid.
  • a carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.
  • a carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule to the resins (1) to (11).
  • (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
  • the acid value of the carboxyl group-containing resin is suitably in the range of 30 to 150 mgKOH / g, more preferably in the range of 50 to 120 mgKOH / g. If the acid value of the carboxyl group-containing resin is less than 30 mgKOH / g, alkali development becomes difficult. On the other hand, if it exceeds 150 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so there is no distinction between the exposed and unexposed portions It is not preferable because the resist is dissolved and peeled off by a developer, and it becomes difficult to draw a normal 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, more preferably 5,000 to 100,000. When the weight average molecular weight is less than 2,000, the moisture resistance of the coated film after exposure is poor, film loss occurs during development, and resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated and storage stability may be inferior.
  • the weight average molecular weight can be measured by GPC.
  • carboxyl group-containing resins synthesized using a phenol compound such as the carboxyl group-containing resins (10) and (11) as starting materials are excellent in HAST resistance and PCT resistance, and can be suitably used.
  • the carboxyl group-containing resin other than (A) is used in an amount of 700 parts by mass or less with respect to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin of the present invention. It is preferable.
  • a more preferable upper limit value is 600 parts by mass, and a more preferable upper limit value is 500 parts by mass.
  • the curable resin composition of the present invention may further contain a known radical polymerizable compound.
  • radically polymerizable compounds include radically polymerizable resins and radically polymerizable monomers.
  • radical polymerizable resin unsaturated polyester, epoxy acrylate, urethane acrylate, polyester acrylate, or the like can be used.
  • the radically polymerizable resin it is preferable to use the radically polymerizable resin at 80 parts by mass or less with respect to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin of the present invention.
  • a more preferred upper limit is 70 parts by mass, and a more preferred upper limit is 60 parts by mass.
  • the radical polymerizable monomer either a monofunctional monomer (one radical polymerizable double bond) or a polyfunctional monomer (two or more radical polymerizable double bonds) can be used. Since the radical polymerizable monomer is involved in the polymerization, the viscosity of the resin composition can be adjusted while improving the properties of the resulting cured product.
  • the preferable usage-amount is 300 mass parts or less with respect to 100 mass parts of (A) carboxyl group-containing photosensitive resin of this invention, More preferably, it is 100 mass parts or less.
  • the usage-amount of a radically polymerizable monomer is other than (A) carboxyl group-containing photosensitive resin and (A). It is set as said range with respect to 100 mass parts of total amounts of carboxyl group-containing resin.
  • radical polymerizable monomer examples include N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- ( 2-chlorophenyl) maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmethylmaleimide, N- (2,4,6-tribromophenyl) Maleimide, N- [3- (triethoxysilyl) propyl] maleimide, N-octadecenylmaleimide, N-dodecenylmaleimide, N- (2-methoxyphenyl) maleimide, N- (2,4,6 -Trichlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimi N- (4
  • the resin composition comprising (A) a carboxyl group-containing photosensitive resin of the present invention, a carboxyl group-containing resin other than (A), and a radical polymerizable compound is a known heat such as benzoyl peroxide or cumene hydroperoxide.
  • Thermal polymerization is possible by using a polymerization initiator, but radical polymerization by light becomes possible by using a curable resin composition containing a photopolymerization initiator. In particular, it can be a negative curable resin composition.
  • the curable resin composition of the present invention contains (B) a photopolymerization initiator.
  • a photopolymerization initiator such as benzoin such as benzoin, benzoin methyl ether, and benzoin ethyl ether, and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone.
  • Acetophenones such as 4- (1-t-butyldioxy-1-methylethyl) acetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4 -Thioxanthones such as dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; Benzophenone, 4- (1- -Benzophenones such as butyldioxy-1-methylethyl) benzophenone and 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone; 2-methyl-1- [4- (methylthio) phenyl]- Examples include 2-
  • an oxime ester photopolymerization initiator having an oxime ester group, an ⁇ -aminoacetophenone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, a titanocene photopolymerization initiator, or the like is used. You can also.
  • oxime ester photopolymerization initiator examples include commercially available products such as CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, NCI-831 manufactured by ADEKA, and the like.
  • ⁇ -aminoacetophenone photopolymerization initiator examples include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone N, N-dimethylaminoacetophenone and the like, and as commercially available products, Omnirad 907, Omnirad 369, Omnirad 379, etc. manufactured by IGM Resins can be used.
  • acylphosphine oxide photopolymerization initiator examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6 -Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like, and commercially available products include Omnirad TPO manufactured by IGM Resins, Omnirad 819 manufactured by IGM Resins, etc. be able to.
  • titanocene photopolymerization initiator examples include bis (cyclopentadienyl) -di-phenyl-titanium, bis (cyclopentadienyl) -di-chloro-titanium, and bis (cyclopentadienyl).
  • Examples of commercially available products include Omnirad 784 manufactured by IGM Resins.
  • photopolymerization initiators are used as one type or a mixture of two or more types, and may be contained in an amount of 0.005 to 40 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin of the present invention. preferable.
  • the amount of the photopolymerization initiator is less than 0.005 parts by mass, it is necessary to increase the light irradiation time or it is difficult for polymerization to occur even if light irradiation is performed, so that an appropriate surface hardness can be obtained. Disappear.
  • even if it mixes a photoinitiator exceeding 30 mass parts there are few merits to use in large quantities.
  • the amount of (B) photopolymerization initiator used is (A) a carboxyl group-containing photosensitive resin and (A ),
  • the curable resin composition of the present invention contains (C) a thermosetting compound.
  • the curable resin composition of the present invention further contains a thermosetting compound, it can react with the polar group imparted with alkali developability to disappear the polar group. As a result, the water absorption rate that adversely affects the insulation reliability is lowered, so that the insulation reliability can be improved.
  • heat resistance can further be improved by including a thermosetting compound.
  • thermosetting compound As a thermosetting compound, well-known and usual thermosetting resins, such as a block isocyanate compound, an amino resin, a maleimide compound, a carbodiimide resin, a polyfunctional epoxy compound, a polyfunctional oxetane compound, can be used. Among these, a preferable thermosetting component has at least one of two or more cyclic ether groups and cyclic thioether groups (hereinafter abbreviated as a cyclic (thio) ether group) in one molecule. It is. There are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on the structure.
  • thermosetting resins such as a block isocyanate compound, an amino resin, a maleimide compound, a carbodiimide resin, a polyfunctional epoxy compound, a polyfunctional oxetane compound.
  • a preferable thermosetting component has at least one of two or more cyclic ether
  • thermosetting component having two or more cyclic (thio) ether groups in the molecule contains either one of the three, four or five-membered cyclic ether groups, or the cyclic thioether group or two kinds of groups in the molecule.
  • a compound having at least two epoxy groups in the molecule that is, a polyfunctional epoxy compound (C-1), a compound having at least two oxetanyl groups in the molecule, Examples thereof include a polyfunctional oxetane compound (C-2), a compound having two or more thioether groups in the molecule, that is, an episulfide resin (C-3).
  • polyfunctional epoxy compound (C-1) for example, jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. YD-011, YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. E. R. 664, Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Co., Ltd. E. R. 330, A.I. E. R.
  • A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Mitsubishi Chemical Co., Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Dow Chemical D. E. R. 542, Sumitomo Epoxy ESB-400 and ESB-700 manufactured by Sumitomo Chemical Co., Ltd. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152, jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N.
  • ELM-120 (all trade names), glycidylamine type epoxy resin; Product name) alicyclic epoxy resin; YL- from Mitsubishi Chemical Corporation 33, Dow Chemical Co., Ltd. of T. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names), etc.
  • Type or biphenol type epoxy resin or a mixture thereof bisphenol S type epoxy resin such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by DIC Co., Ltd .; Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; tetraphenylolethane type epoxy resin such as jERYL-931 (trade name) manufactured by Mitsubishi Chemical Corporation; TEPIC manufactured by Nissan Chemical Industries Co., Ltd.
  • bisphenol S type epoxy resin such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by DIC Co., Ltd .
  • Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation
  • heterocyclic epoxy resin such as NOF's Bremer DDT Residyl phthalate resin; Tetraglycidylxylenoylethane resin such as Nippon Steel & Sumikin Chemical Co., Ltd. ZX-1063; Nippon Steel & Sumikin Chemical Co., Ltd.
  • epoxy resins can be used alone or in combination of two or more.
  • novolak-type epoxy resins modified novolak-type epoxy resins, heterocyclic epoxy resins, bixylenol-type epoxy resins or mixtures thereof are particularly preferable.
  • Examples of the polyfunctional oxetane compound (C-2) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [ (3-Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl -3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and polyfunctional oxetanes such as oligomers and copolymers thereof, as well as oxetane alcohol And novolac resin, poly (
  • Examples of the episulfide resin (C-3) having two or more cyclic thioether groups in the molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Mitsubishi Chemical Corporation and YSLV-120TE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. It is done. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.
  • the compounding amount of the thermosetting compound is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin based on the solid content excluding the organic solvent of the curable resin composition.
  • the blending amount of the thermosetting compound having two or more cyclic (thio) ether groups in the molecule is based on the solid content basis excluding the organic solvent of the curable resin composition (A) carboxyl group of the carboxyl group-containing resin.
  • the cyclic (thio) ether group is preferably in the range of 0.5 to 4.0 equivalents, more preferably 0.8 to 3.5 equivalents with respect to 1 equivalent.
  • thermosetting compound When the blending amount of the thermosetting compound is within the above range, the heat resistance, alkali resistance, electrical insulation, strength of the cured film, and the like are good.
  • the usage-amount of (C) thermosetting compound is (A) carboxyl group-containing photosensitive resin and (A ), The above-mentioned range with respect to 100 parts by mass of the total amount of the carboxyl group-containing resin.
  • thermosetting compound (C) used in the present invention is an epoxy resin, urethane resin, polyester resin, hydroxyl group, amino group or carboxyl group-containing polyurethane, polyester, polycarbonate, polyol, phenoxy resin, acrylic copolymer resin, vinyl.
  • thermosetting resins such as resin, polyimide, polyamideimide, oxazine resin, and cyanate resin can be used.
  • (block) isocyanates, amines, phenols and the like can be used as curing agents corresponding to them.
  • 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
  • a filler can be blended as necessary in order to increase the physical strength of the coating film.
  • known inorganic or organic fillers can be used.
  • barium sulfate, spherical silica, hydrotalcite and talc are preferably used.
  • metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers.
  • the blending amount of the filler is preferably 70% by mass or less of the total amount of the composition.
  • the viscosity of an insulating composition will become high, application
  • the resin composition of the present invention further includes a coloring pigment, an antifoaming agent, a coupling agent, a leveling agent, a sensitizer, a release agent, a lubricant, a plasticizer, an antioxidant, and an ultraviolet absorber.
  • a coloring pigment such as flame retardants, polymerization inhibitors, thickeners, adhesion assistants, and crosslinking agents may be added.
  • various reinforcing fibers can be used as reinforcing fibers to form a fiber-reinforced composite material.
  • the curable resin composition of this invention can also be made into the form of the dry film provided with the support (carrier) film and the resin layer which consists of the said curable resin composition formed on this support film.
  • the curable resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and is applied to a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater.
  • a film can be obtained by applying a uniform thickness on a carrier film with a gravure coater, spray coater or the like, and drying usually at a temperature of 50 to 130 ° C. for 1 to 30 minutes.
  • the coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 1 to 150 ⁇ m, preferably 10 to 60 ⁇ m.
  • a plastic film is used, and it is preferable to use a polyester film such as polyethylene terephthalate (PET), a plastic film such as a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film.
  • PET polyethylene terephthalate
  • the thickness of the support film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 ⁇ m.
  • the protective layer (cover) that can be peeled off from the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer.
  • a peelable protective film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used. As long as the adhesive strength between the resin layer and the protective film is smaller.
  • a resin layer may be formed by applying and drying the curable resin composition of the present invention on the protective film, and a support film may be laminated on the surface. That is, as a film to which the curable resin composition of the present invention is applied when producing a dry film in the present invention, either a support film or a protective film may be used.
  • the cured product of the present invention is obtained by curing the curable resin composition of the present invention or the resin layer of the dry film of the present invention, and has high insulation reliability.
  • 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 resin layer is formed on the substrate, it is selectively exposed with active energy rays through a photomask having a predetermined pattern, and the unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3 to 3 mass% sodium carbonate aqueous solution).
  • a dilute alkaline aqueous solution for example, 0.3 to 3 mass% sodium carbonate aqueous solution.
  • 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 subjected to final finish curing (main curing) only by heat-curing.
  • a cured film having excellent properties such as properties and hardness is formed.
  • 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.
  • potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines
  • the curable resin composition of the present invention is preferably used for forming a cured film on an electronic component, particularly for forming a cured film on a printed wiring board, and more preferably for forming a permanent film. More preferably, it is used to form a solder resist, an interlayer insulating layer, and a coverlay. Further, it is suitable for forming a printed wiring board requiring high reliability, for example, a package substrate, particularly a permanent film (particularly a solder resist) for FC-BGA.
  • Synthesis Examples 1 to 7 The radical polymerizable polymers of Synthesis Examples 1 to 7 shown below were synthesized.
  • Synthesis Examples 6 and 7 are radical polymerizable polymers that do not correspond to the radical polymerizable polymer contained in the (A) carboxyl group-containing photosensitive resin in the curable resin composition of the present invention, that is, a comparative example. It is a radically polymerizable polymer for
  • a mixture of 10 parts of a hydrocarbon solution and 21.2 parts of carbitol acetate was charged. While maintaining the reaction temperature at 80 ° C., dropping was performed over 3 hours from dropping tanks 1, 2, 4 and 2.5 hours from dropping tank 3. The reaction was further continued at 80 ° C. for 30 minutes after the completion of the dropwise addition. Thereafter, the reaction temperature was raised to 95 ° C., and the reaction was continued for 1.5 hours to obtain a polymer solution before the radical polymerizable double bond introduction reaction.
  • a mixture of 27 parts of methacrylic acid and 22.2 parts of isopropanol, perbutyl O as a polymerization initiator in the dropping tank 3 (trade name; t-butyl peroxy-2-ethylhexanoate, manufactured by NOF Corporation) Ten copies were charged each. While maintaining the reaction temperature at 100 ° C., the dropwise addition was carried out from the dropping tanks 1 to 3 over 3 hours. The reaction was further continued at 100 ° C. for 30 minutes after the completion of the dropwise addition. Thereafter, the reaction temperature was raised to 115 ° C., and the reaction was continued for 1.5 hours to obtain a polymer solution before the radical polymerizable double bond introduction reaction.
  • B-1 in Table 1 Irgacure OXE02 (manufactured by BASF Japan; oxime ester photopolymerization initiator).
  • C-1 in Table 1 Epicron N-730A, (manufactured by DIC: cresol novolac type thermosetting component).
  • Filler D in Table 1 was prepared by the following production method. Dispersion treatment was performed using 700 g of spherical silica (Admafine SO-E2) manufactured by Admatech, 300 g of PEGMEA (propylene glycol monomethyl ether acetate) as a solvent, and 0.5 ⁇ m zirconia beads in a bead mill. This was repeated three times and filtered through a 3 ⁇ m filter to prepare a silica slurry having an average particle size of 500 nm. The inorganic filler had a particle diameter D10 of 250 nm and a maximum particle diameter D100 of 3 ⁇ m. Solvent E-1 in Table 1 is PGMEA (propylene glycol monomethyl ether acetate).
  • solder heat resistance The evaluation criteria of solder heat resistance in Table 1 are as follows. ⁇ : The cured coating film does not swell and peel. ⁇ : The cured coating film slightly swells or peels. X: The cured coating film clearly has swelling and peeling.
  • the evaluation criteria for insulation reliability in Table 1 are as follows. ⁇ : No abnormality after 350 hours ⁇ : Short circuit between 250 and 350h ⁇ : Short circuit within 250h
  • the curable resin composition was applied onto the copper foil so as to have a film thickness of about 40 ⁇ m, and the entire surface was exposed, followed by development and curing under the same conditions as the solder heat resistance test substrate. Thereafter, the cured coating film is peeled off from the copper foil, cut into test pieces having a width of about 5 mm and a length of about 80 mm, and elongation at break using a tensile tester (manufactured by Shimadzu Corporation, Autograph AGS-100N). Was measured.
  • the measurement conditions were a sample width of about 10 mm, a fulcrum distance of about 40 mm, a pulling speed of 1.0 mm / min, and the elongation rate until breakage was the elongation at breakage point.
  • the evaluation criteria for flexibility in Table 1 are as follows. ⁇ : Elongation at break is 3% or more ⁇ : Elongation at break is 1.5% or more and less than 3% ⁇ : Elongation at break is less than 1.5%
  • Examples 1 to 7 containing a specific radical polymerizable polymer and a thermosetting compound are alkali developability, photocurability, solder heat resistance, insulation reliability, and flexibility. It had a good balance.
  • Comparative Example 1 uses the radical polymerizable polymer of Synthesis Example 6 and does not contain the specific radical polymerizable polymer of the present invention. Photocurability, insulation reliability, and solder heat resistance were not evaluated.
  • Comparative Example 2 uses the radically polymerizable polymer of Synthesis Example 7 and does not contain a specific carboxyl group-containing photosensitive resin, so that the solder heat resistance and B-HAST resistance are not sufficient. Further, since Comparative Example 3 did not contain a thermosetting compound, B-HAST resistance was not sufficient.

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