Curable resin composition, dry film, cured product, and electronic component

Abstract

[Problem] To provide a curable resin composition capable of imparting high thermal discoloration resistance and a cured product thereof. [Solution] At least, the following components (A) to (C): (A) A compound having an isocyanurate structure and two or more (meth)acryloyl groups, (B) Epoxy resin having an isocyanurate structure, and (C) Photopolymerization initiator Curable resin composition containing

Description

Technology Field

[0001] The present invention relates to a curable resin composition, a dry film having the curable resin composition as a resin layer, a cured product of the resin layer of the dry film, and an electronic component having the cured product. Background Technology

[0002] In the manufacture of printed circuit boards, solder resist is typically used to protect conductor circuits on a substrate from solder adhesion, and to form such solder resist, curable resin compositions containing various components having various structures have been proposed in the past.

[0003] For example, Patent Document 1 discloses a photosensitive resin composition containing a (meth)acrylic copolymer of a specific structure having (meth)acryloyl groups, a monomer having ethylenically unsaturated bonds, and a photoinitiator. Prior art literature

[0004] Japanese Patent Publication No. 2004-191680 The problem to be solved

[0005] However, solder resists require various characteristics depending on the application of the printed circuit board, and heat resistance is one of them. This is because if the heat resistance of the solder resist is insufficient, there is a risk that the solder resist itself will discolor. For example, solder resists used on circuit boards on which light-emitting devices such as light-emitting diodes (LEDs) are mounted contain a white coloring agent to increase the reflection efficiency of light from the LEDs and thereby improve their utilization efficiency; therefore, when the solder resist discolors from white to yellow (yellowing), the reflection efficiency of the LED light drops significantly.

[0006] Since solder resist is susceptible to solder heat, particularly during mounting of electronic components onto a substrate, heat generation from electronic components after mounting, and other thermal stresses after its formation, resistance to discoloration due to such thermal stress is an important characteristic.

[0007] However, regarding this point, it could not be said that conventional curable resin compositions, such as the photosensitive resin composition described in Patent Document 1, sufficiently considered the heat resistance of the solder resist, particularly its resistance to thermal discoloration. means of solving the problem

[0008] In order to solve the above problem, the inventors of the present invention, after repeated careful examination, discovered that by combining a compound having an isocyanurate structure and two or more (meth)acryloyl groups with an epoxy resin having an isocyanurate structure in a curable resin composition, a cured film (e.g., solder resist) with increased resistance to thermal discoloration can be formed, and thus completed the present invention.

[0009] That is, the problem in the present invention is,

[0010] At least, the following components (A) to (C):

[0011] (A) A compound having an isocyanurate structure and two or more (meth)acryloyl groups,

[0012] (B) Epoxy resin having an isocyanurate structure, and

[0013] (C) It was found that this can be solved by a curable resin composition containing a photopolymerization initiator.

[0014] Among these, a preferred embodiment of the present invention relates to the curable resin composition further comprising (D) an antioxidant having an isocyanurate structure.

[0015] A more preferred embodiment relates to the above-mentioned curable resin composition further comprising (E) a white coloring agent.

[0016] Another preferred embodiment relates to the above-mentioned curable resin composition containing at least one of a carboxyl group-containing fluoropolymer resin and a carboxyl group-containing copolymer resin that does not contain fluorine atoms.

[0017] Another desirable form is one with a specific surface area of ​​10 m² 2 / g or more than 100m 2 Silica with less than 1 / g, and a specific surface area of ​​100m² 2 / g or more than 300m 2 The present invention relates to a curable resin composition containing at least one type of silica with a value of less than 1 g.

[0018] In addition, another aspect of the present invention relates to a dry film having the curable resin composition as a resin layer, a cured product of the curable resin composition or the resin layer of the dry film, and an electronic component having the cured product. Effects of the invention

[0019] According to the present invention, a cured product (cured film) having higher heat resistance and a curable resin composition capable of forming said cured product are provided. Accordingly, said cured product can be more suitably used as a solder resist layer, particularly as a white solder resist layer for a wiring board on which an LED is mounted, in that it has high resistance to discoloration caused by heat. Specific details for implementing the invention

[0020] High thermal discoloration resistance of the cured product obtained from the curable resin composition of the present invention can basically be achieved by using (A) a compound having an isocyanurate structure and two or more (meth)acryloyl groups and (B) an epoxy resin having an isocyanurate structure.

[0021] In the present invention, thermal discoloration resistance may also be expressed as the degree of color change (color difference: ΔE) of a cured film formed from a curable resin composition before and after applying thermal stress. It can be said that the smaller the ΔE, the higher the thermal discoloration resistance, and the larger the ΔE, the lower the thermal discoloration resistance.

[0022] For example, ΔE can be calculated as the amount of color change from the initial value by applying, drying, exposure, development, and curing treatment of a curable resin composition, and performing a heat treatment for 10 seconds with a peak top temperature of 285°C.

[0023] In addition, the curable resin composition of the present invention itself possesses good long-term storage stability. Therefore, it has the advantage that the quality at the time of use can be maintained even after the curable resin composition has been transported over a long period, such as by ship to overseas destinations.

[0024] Hereinafter, each component constituting the curable resin composition of the present invention will be described.

[0025] [(A) Compounds having an isocyanurate structure and two or more (meth)acryloyl groups]

[0026] (A) A compound having an isocyanurate structure and two or more (meth)acryloyl groups has, in its unit structure, an isocyanurate ring and two or more (meth)acryloyl groups.

[0027] (A) Examples of compounds include difunctional or trifunctional (meth)acrylates.

[0028] Among these, as having a difunctional (meth)acrylate, ethoxylated isocyanuric acid di(meth)acrylate or propoxylated isocyanuric acid di(meth)acrylate is preferred.

[0029] In addition, as having trifunctional (meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate or propoxylated isocyanuric acid tri(meth)acrylate is preferred.

[0030] Furthermore, their caprolactone modified forms can also be preferably cited.

[0031] A compound having the above (A) isocyanurate structure and two or more (meth)acryloyl groups is more preferred as ethoxylated isocyanuric acid tri(meth)acrylate. Commercial products of compounds having the (A) isocyanurate structure and two or more (meth)acryloyl groups include M-215, M-313, and M-315 manufactured by Doa Kose Co., Ltd., A-9300, A-9300-1CL, and A-9300YN manufactured by Shin-Nakamura Kagaku Co., Ltd., Photomer4356 manufactured by IGM Resins Co., Ltd., and FA-731A manufactured by Hitachi Kasei Co., Ltd.

[0032] In the present invention, the content of (A) a compound having an isocyanurate structure and two or more (meth)acryloyl groups is preferably 3 to 25 mass% with respect to the total amount of solids of the entire composition. In particular, when the curable resin composition of the present invention contains a white coloring agent, the content of (A) a compound having an isocyanurate structure and two or more (meth)acryloyl groups is preferably 3 to 10 mass%, and more preferably 5 to 7 mass%. In the case of 3 to 25 mass%, the resulting cured product has good resistance to thermal discoloration, good cured film strength, and the viscosity of the composition is appropriate, which can improve applicability.

[0033] [(B) Epoxy resin having an isocyanurate structure]

[0034] The curable resin composition of the present invention contains an epoxy resin having an isocyanurate structure, wherein the nitrogen atom in the isocyanurate structure and the epoxy group are bonded by an alkylene chain. In particular, it is preferred to have an epoxy resin having a structure in which the number of carbon atoms in the alkylene chain is two or more. If the number of carbon atoms in the alkylene chain is within the range of 2 to 5, good resistance to thermal discoloration is obtained in the resulting cured product.

[0035] As for the epoxy resin having an isocyanurate structure (B) used in the present invention, it is preferable to have a structure represented by the following formula (I).

[0036]

[0037] (during the meal,

[0038] R1, R2, and R3 each independently represent an alkylene group having 2 to 5 carbon atoms, and

[0039] n is 0 or 1, provided that not all n represent 0 simultaneously.

[0040] Among these, particularly desirable is a structure in which R1, R2 and R3 simultaneously represent an alkylene group having 3 carbon atoms, and n simultaneously represents 1.

[0041] Specific products of the (B) isocyanurate structure epoxy resin preferably used in the present invention include, for example, TEPIC (registered trademark)-VL and TEPIC (registered trademark)-FL (both manufactured by Nissan Kagaku Co., Ltd.).

[0042] The content of the epoxy resin having such (B) isocyanurate structure is preferably 30 to 70 mass% with respect to 100 mass parts of the compound having (A) isocyanurate structure and two or more (meth)acryloyl groups. In particular, when the curable resin composition of the present invention contains (E) a white coloring agent, the content of the compound having (A) isocyanurate structure and two or more (meth)acryloyl groups is preferably 48 to 68 mass parts. If within the range of 30 to 70 mass%, the thermal discoloration resistance of the resulting cured product is improved, and the storage stability of the curable resin composition is also improved.

[0043] [(C) Photopolymerization Initiator]

[0044] (C) As a photopolymerization initiator, any photopolymerization initiator known as a photopolymerization initiator or a photoradical generator may be used, for example, bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. Bis-acylphosphine oxides; monoacylphosphine oxides such as 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphine isopropyl ester, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Hydroxyacetophenones such as 1-hydroxy-cyclohexylphenylketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, etc.; benzoin alkyl ethers; Benzophenones such as benzophenone, p-methylbenzophenone, mihler ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone;Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone; Thioxantones such as thioxantone, 2-ethylthioxantone, 2-isopropylthioxantone, 2,4-dimethylthioxantone, 2,4-diethylthioxantone, 2-chlorothioxantone, 2,4-diisopropylthioxantone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone; ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, and p-dimethylbenzoate ethyl ester; Examples include oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanoone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, and 1-(O-acetyloxime); titanocenes such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, and bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-phil-1-yl)ethyl)phenyl]titanium; and phenyldisulfide 2-nitrofluorene, butyloin, anisoine ethyl ether, azobis-isobutyronitrile, tetramethylthiuram-disulfide, etc. A photopolymerization initiator may be used as a single type or in combination of two or more types.

[0045] (C) The content of the photopolymerization initiator is preferably 5 to 20 parts by weight per 100 parts by weight of (A) a compound having an isocyanurate structure and two or more (meth)acryloyl groups, and more preferably 10 to 20 parts by weight. If the content is within the range of 5 to 20 parts by weight, the surface curability is improved, and good resolution is obtained as it is difficult for halation to occur.

[0046] [(D) Antioxidant having an isocyanurate structure]

[0047] The curable resin composition of the present invention may further contain an antioxidant having an isocyanurate structure (D). By doing so, the effect of increasing the thermal discoloration resistance of the cured film can be achieved.

[0048] Antioxidants having such (D) isocyanurate structures are preferably represented by the following formula (II).

[0049]

[0050] (during the meal,

[0051] Groups R4, R5, and R6 each independently represent a hydrogen atom, or represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group that may be substituted by at least one substituent selected from the group consisting of a hydroxyl group and a hydrocarbon group having 1 to 10 carbon atoms, and also

[0052] The nitrogen atom in the formula and group R4, R5, or R6 may be directly bonded, or may be bonded through an alkylene group having 1 to 10 carbon atoms.

[0053] A more preferred antioxidant having an isocyanurate structure (D) is a structure in which the groups R4, R5 and R6 of formula (II) each represent a phenyl group substituted with one hydroxyl group and a hydrocarbon group having 1 to 3 carbon atoms and 1 to 4 carbon atoms, and each nitrogen atom is bonded to an alkylene group having 1 to 3 carbon atoms through each of the groups R4, R5 or R6.

[0054] An antioxidant having a particularly desirable (D) isocyanurate structure is 1,3,5-tris(3,5-di-tert-butyl)-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione represented by the following formula (II') (product name: Irganox 3114; manufactured by BASF Japan). In addition, commercially available antioxidants having a (D) isocyanurate structure include Cyanox 1790 manufactured by Nippon Cytec Industries and AdekaStab AO-20 manufactured by Adeka.

[0055]

[0056] (D) The content of the antioxidant having an isocyanurate structure is preferably 1 to 8 mass% with respect to 100 mass parts of a compound having an isocyanurate structure and two or more (meth)acryloyl groups. If the range is 1 to 8 mass%, the thermal discoloration resistance of the cured film can be further increased.

[0057] [(E) White coloring agent]

[0058] When the curable resin composition of the present invention is used, for example, in a solder resist for a printed circuit board for an LED, it may contain a white coloring agent. By doing so, the reflectivity of the cured film can be increased, thereby improving the utilization efficiency of the LED's light.

[0059] (E) Examples of white coloring agents include titanium oxide, zinc oxide, potassium titaniumate, zirconium oxide, antimony oxide, lead white, zinc sulfide, lead titaniumate, etc., but titanium oxide is preferred because it has a high effect in inhibiting discoloration caused by heat.

[0060] As for titanium oxide, any titanium oxide of the rutile, anatase, or ramsdelite type structure may be used, and one type may be used alone or two or more types may be used in combination. Among these, ramsdelite type titanium oxide can be obtained by performing lithium desorption treatment by chemical oxidation on ramsdelite type Li0.5TiO2.

[0061] Using rutile-type titanium oxide among the above is preferable because it can further improve the heat resistance of the cured film. In particular, by using rutile-type titanium oxide surface-treated with aluminum oxide such as alumina or silica, the reflectivity and heat resistance of the cured film can be further improved.

[0062] In addition, other surface treatments may be performed after the initial surface treatment. In particular, reflectivity can be further enhanced by additionally surface-treating with zirconia after surface-treating with alumina.

[0063] Examples of rutile-type titanium oxide surface-treated with the above aluminum oxide include CR-58 manufactured by Ishihara Sangyo Co., Ltd., which is rutile-type chlorinated titanium oxide, and R-630 manufactured by the same company, which is rutile-type sulfuric acid titanium oxide. In addition, it is also preferable to use rutile-type titanium oxide surface-treated with silicon oxide, and in this case, heat resistance can be further improved. In addition, it is also preferable to use rutile-type titanium oxide surface-treated with both aluminum oxide and silicon oxide, and examples include CR-90 manufactured by Ishihara Sangyo Co., Ltd., which is rutile-type chlorinated titanium oxide.

[0064] The amount of this (E) white coloring agent is preferably in the range of 750 to 950 parts by mass, more preferably in the range of 800 to 900 parts by mass, with respect to 100 parts by mass of a compound having an isocyanurate structure and two or more (meth)acryloyl groups.

[0065] [Carboxyl group-containing resin]

[0066] It is preferable that the curable resin composition of the present invention further contains at least one of a carboxyl group-containing fluoropolymer resin or a carboxyl group-containing resin that does not contain fluorine atoms.

[0067] As a carboxyl group-containing fluoropolymer, a known fluoropolymer containing carboxyl groups may be used. A fluoropolymer refers to a polymer or oligomer having at least one fluorine atom. The presence of carboxyl groups can make the curable resin composition alkali-developable, and the presence of fluorine atoms can improve heat discoloration resistance.

[0068] In addition, for the sake of making the curable resin composition of the present invention photocurable or for the sake of development resistance, in addition to carboxyl groups and fluorine atoms, the molecule may have ethylenically unsaturated bonds. As for the ethylenically unsaturated double bonds, they may be derived from acrylic acid, methacrylic acid, or derivatives thereof.

[0069] Specific examples of carboxyl group-containing fluoropolymers that can be used in the curable resin composition of the present invention include compounds listed below (which may be either oligomers or polymers). Furthermore, the term "fluorine substituent" described below refers to a compound in which one or more hydrogen atoms other than the hydrogen atoms constituting the functional group of a predetermined compound are substituted with fluorine.

[0070] (1) A carboxyl group-containing fluoropolymer obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with a fluorine substituent of an unsaturated group-containing compound such as styrene, α-methylstyrene, alkyl (meth)acrylate (alkyl is, for example, an alkyl having 2 to 15 carbon atoms, preferably 2 to 8), isobutylene.

[0071] (2) A carboxyl group-containing urethane resin formed by the addition reaction of a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid, dimethylolbutanoic acid, and a diol compound such as a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic-based polyol, a bisphenol A-based alkylene oxide adduct diol, and a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, wherein at least one of the described raw materials is a fluorine substitute.

[0072] (3) A fluorine resin containing a terminal carboxyl group, wherein at least one of the described raw materials is a fluorine substitute, and the fluorine resin containing a carboxyl group and a urethane bond, wherein the urethane resin is formed by reacting an acid anhydride with the terminal end of a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, etc., and a diol compound such as a polycarbonate-based polyol, polyether-based polyol, polyester-based polyol, polyolefin-based polyol, acrylic-based polyol, bisphenol A-based alkylene oxide adduct diol, etc., and a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

[0073] (4) A photosensitive carboxyl group-containing urethane resin formed by the addition reaction of a diisocyanate, a (meth)acrylate or a partial acid anhydride modified product thereof of a difunctional epoxy resin such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bixylenol type epoxy resin, a biphenol type epoxy resin, etc., a carboxyl group-containing dialol compound, and a diol compound, wherein at least one of the described raw materials is a fluorine substitute.

[0074] (5) During the synthesis of the resin of (2) or (4) above, a compound having one hydroxyl group and one or more (meth)acryloyl groups in a molecule such as hydroxyalkyl (meth)acrylate is added to produce a fluoropolymer containing terminal (meth)acrylated carboxyl groups and urethane bonds.

[0075] (6) During the synthesis of the resin of (2) or (4) above, a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule is added, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, to produce a fluorine resin containing terminal (meth)acrylated carboxyl groups and urethane bonds.

[0076] (7) A photosensitive carboxyl group-containing fluorine resin in which (meth)acrylic acid is reacted with a fluorine substitute of a polyfunctional epoxy resin as described below, and a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is added to the hydroxyl group present in the side chain.

[0077] (8) A photosensitive carboxyl group-containing fluorine resin in which (meth)acrylic acid is reacted with a fluorine substitute of a polyfunctional epoxy resin in which the hydroxyl group of a difunctional epoxy resin is further epoxidized with epichlorohydrin, and a dibasic acid anhydride is added to the resulting hydroxyl group.

[0078] (9) A fluorine resin containing carboxyl groups and ester bonds, wherein a dicarboxylic acid is reacted with a fluorine substituent of a polyfunctional oxetane resin as described below, and a dibasic acid anhydride is added to the primary hydroxyl group generated.

[0079] (10) A carboxyl group-containing photosensitive fluoropolymer obtained by reacting a reaction product obtained by reacting a fluorine substituent of a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide with a monocarboxylic acid containing an unsaturated group, and then reacting the resulting reaction product with a polybasic acid anhydride.

[0080] (11) A carboxyl group-containing photosensitive fluoropolymer obtained by reacting a reaction product obtained by reacting a cyclic carbonate compound, such as ethylene carbonate or propylene carbonate, with a fluorine substituent of a compound having multiple phenolic hydroxyl groups in one molecule, with a monocarboxylic acid containing an unsaturated group, and then reacting the resulting reaction product with a polybasic acid anhydride.

[0081] (12) A carboxyl group-containing photosensitive fluoropolymer obtained by reacting a fluorine substituent of 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, with a monocarboxylic acid containing an unsaturated group, such as (meth)acrylic acid, and reacting a polybasic acid anhydride, such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic acid, with the alcoholic hydroxyl group of the resulting reaction product.

[0082] (13) A photosensitive carboxyl group-containing fluoropolymer resin formed by adding a compound having one epoxy group and one or more (meth)acryloyl groups among molecules such as glycidyl (meth)acrylate and α-methylglycidyl (meth)acrylate to any of the resins (1) to (12) above.

[0083] The above-described fluoride substituent can be obtained by fluorinating a predetermined compound. Any known method may be used as the fluorination method, and examples include low-temperature fluorination, contact fluorination, aqueous solution fluorination, liquid phase fluorination, solid phase fluorination, gas phase fluorination, etc.

[0084] As a carboxyl group-containing fluoropolymer, specifically, a carboxyl group-containing fluoropolymer manufactured by Shinnakamura Chemical (product names: TIF-1, TIF-2, TIF-3) can be used.

[0085] The amount of the carboxyl group-containing fluoropolymer resin described above is preferably 135 to 360 parts by weight, more preferably 150 to 300 parts by weight, with respect to 100 parts by weight of (A) a compound having an isocyanurate structure and two or more (meth)acryloyl groups. In the case of 135 to 300 parts by weight, the coating film strength is good, and the viscosity of the composition is appropriate, which can improve coating properties, etc.

[0086] It is preferable that the curable resin composition of the present invention further contains a carboxyl group-containing resin other than the carboxyl group-containing fluoropolymer resin, namely, a carboxyl group-containing resin that does not contain fluorine atoms. By including a carboxyl group-containing resin that does not contain fluorine atoms, the developability is further improved.

[0087] As a carboxyl group-containing resin that does not contain fluorine atoms, a known resin containing carboxyl groups may be used. In terms of making the curable resin composition of the present invention photocurable or developing resistance, it is preferable to have ethylenically unsaturated bonds within the molecule in addition to carboxyl groups, but only a carboxyl group-containing resin that does not have ethylenically unsaturated double bonds may be used. As for the ethylenically unsaturated double bonds, those derived from acrylic acid, methacrylic acid, or derivatives thereof are preferred.

[0088] Specific examples of carboxyl group-containing resins that can be used in the curable resin composition of the present invention include compounds listed below (which may be either oligomers or polymers).

[0089] (1) A carboxyl group-containing copolymer resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene.

[0090] (2) A carboxyl group-containing urethane resin produced by the addition reaction of a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid, dimethylolbutanoic acid, and a diol compound such as a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic-based polyol, a bisphenol A-based alkylene oxide adduct diol, and a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

[0091] (3) A terminal carboxyl group-containing urethane resin formed by reacting an acid anhydride with the terminal end of a urethane resin by a diisocyanate compound such as an aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, etc., and a diol compound such as a polycarbonate-based polyol, polyether-based polyol, polyester-based polyol, polyolefin-based polyol, acrylic-based polyol, bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

[0092] (4) A photosensitive carboxyl group-containing urethane resin formed by the addition reaction of a diisocyanate, a (meth)acrylate or a partial acid anhydride modified product thereof of a difunctional epoxy resin such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bixylenol type epoxy resin, a biphenol type epoxy resin, etc., a carboxyl group-containing dialal compound, and a diol compound.

[0093] (5) A carboxyl group-containing urethane resin that has one hydroxyl group and one or more (meth)acryloyl groups in the molecule of a hydroxyalkyl (meth)acrylate, etc., is synthesized during the synthesis of the resin of (2) or (4) above.

[0094] (6) A carboxyl group-containing urethane resin that has one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, is synthesized during the synthesis of the resin of (2) or (4) above, and is added to the resin to produce a carboxyl group-containing resin that has been terminally (meth)acrylated.

[0095] (7) A photosensitive carboxyl group-containing resin in which (meth)acrylic acid is reacted with a polyfunctional epoxy resin as described below, and a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is added to the hydroxyl group present in the side chain.

[0096] (8) A photosensitive carboxyl group-containing resin formed by reacting (meth)acrylic acid with a polyfunctional epoxy resin in which the hydroxyl groups of a difunctional epoxy resin have been further epoxidized with epichlorohydrin, and adding a dibasic acid anhydride to the resulting hydroxyl groups.

[0097] (9) A carboxyl group-containing polyester resin produced by reacting a dicarboxylic acid with a polyfunctional oxetane resin as described below and adding a dibasic acid anhydride to the generated primary hydroxyl group.

[0098] (10) 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 to obtain a reaction product, reacting the reaction product with a monocarboxylic acid containing an unsaturated group, and reacting the resulting reaction product with a polybasic acid anhydride.

[0099] (11) A photosensitive carboxyl group-containing 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 to obtain a reaction product, reacting the reaction product with a monocarboxylic acid containing an unsaturated group, and reacting the resulting reaction product with a polybasic acid anhydride.

[0100] (12) A photosensitive carboxyl group-containing 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-hydroxyphenylalcohol, and a monocarboxylic acid containing an unsaturated group, such as (meth)acrylic acid, and 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, and adipic acid.

[0101] (13) A photosensitive carboxyl group-containing resin formed by adding a compound having one epoxy group and one or more (meth)acryloyl groups among molecules such as glycidyl (meth)acrylate and α-methylglycidyl (meth)acrylate to any of the resins (1) to (12) above.

[0102] The above-mentioned carboxyl group-containing fluoropolymer and carboxyl group-containing resin that does not contain fluorine atoms each have multiple carboxyl groups in the side chains of the backbone polymer, so they can be developed by a dilute alkaline aqueous solution.

[0103] In addition, the acid value of the above-mentioned carboxyl group-containing fluoropolymer resin and the carboxyl group-containing resin that does not contain fluorine atoms is preferably in the range of 20 to 200 mgKOH / g, and more preferably in the range of 40 to 150 mgKOH / g. When the acid value of the carboxyl group-containing resin is 20 mgKOH / g or higher, the adhesion of the coating film is improved and the alkali development is improved. On the other hand, when the acid value is 200 mgKOH / g or lower, the dissolution of the exposed area by the developer can be suppressed, thereby preventing the line from becoming thinner than necessary or, in some cases, dissolving and peeling off by the developer without distinguishing between the exposed and unexposed areas, thereby allowing the pattern of the cured film to be drawn well.

[0104] In addition, the mass average molecular weight of the above-mentioned carboxyl group-containing fluoropolymer and the carboxyl group-containing resin that does not contain fluorine atoms varies depending on the resin backbone, but is preferably in the range of 2,000 to 150,000 and further in the range of 5,000 to 100,000, respectively. When the mass average molecular weight is 2,000 or higher, the tack-free drying performance is good, the moisture resistance of the coating film after exposure is good, and film reduction during development is suppressed, thereby suppressing the deterioration of resolution. On the other hand, when the mass average molecular weight is 150,000 or lower, the developability is good and storage stability is also excellent.

[0105] Additionally, in this specification, the term (meth)acrylate is a collective term for acrylates, methacrylates, and mixtures thereof, and the same applies to other similar expressions.

[0106] When a carboxyl group-containing resin that does not contain fluorine atoms is included, the amount of the resin is preferably equal to or less than that of the carboxyl group-containing fluorine resin. Specifically, with respect to 100 parts by mass of (A) a compound having an isocyanurate structure and two or more (meth)acryloyl groups, the amount is preferably 100 to 250 parts by mass, more preferably 100 to 200 parts by mass. In the case of 100 to 250 parts by mass, the film strength is good, and the viscosity of the composition is appropriate, which can improve coating properties, etc.

[0107] In addition, the mass ratio of the carboxyl group-containing fluoropolymer resin and the carboxyl group-containing resin that does not contain fluorine atoms is, for example, 95:5 to 50:50, preferably 90:10 to 60:40.

[0108] [Silica]

[0109] In the curable resin composition of the present invention, it is preferable to further include silica to suppress the separation of the blended components within the curable resin composition and to provide the effect of further improving its long-term storage stability. In this case, at least one of silica having a relatively large specific surface area and silica having a smaller specific surface area may be used. Alternatively, it is preferable to use both types of silica in combination to enhance the above effect.

[0110] In the present invention, silica with a relatively large specific surface area is 100m 2 / g or more than 300m 2 It is desirable to have a specific surface area of ​​less than / g. The amount of silica with a relatively large specific surface area is preferably 1 to 20 parts by weight per 100 parts by weight of (A) a compound having an isocyanurate structure and two or more (meth)acryloyl groups. Meanwhile, silica with a relatively small specific surface area is 10 m 2 / g or more than 100m 2It is desirable to have a specific surface area of ​​less than / g. The amount of silica with a relatively small specific surface area is preferably 5 to 20 parts by mass with respect to 100 parts by mass of (A) a compound having an isocyanurate structure and two or more (meth)acryloyl groups.

[0111] In addition, the mixing ratio of silica with a relatively large specific surface area and silica with a relatively small specific surface area is preferably 1:3 to 1:6 based on parts by mass. Within this range, the storage stability of the composition is improved.

[0112] In addition, the specific surface area can be measured by the "BET method." More specifically, for example, a method of measuring by the BET 1-point method using the fully automatic BET specific surface area measuring device MassorbHM-1201 manufactured by Mounttech Co., Ltd. may be adopted.

[0113] As the silica used in the present invention, crushed synthetic or natural crystalline silica, crushed molten silica or spherical molten silica, synthetic spherical silica, synthetic fine silica, etc. may be used.

[0114] Synthetic silica, i.e., hydrated amorphous silicon dioxide (SiO2·nH2O), is produced by reacting a sodium silicate solution (water glass) with sulfuric acid in a reaction vessel, and by controlling the shape or particle size according to the reaction conditions, it can be made into synthetic spherical silica or synthetic fine silica.

[0115] As silica preferably used in the present invention, for example, Aerosil 90, Aerosil 130, Aerosil 150, Aerosil 200, Aerosil 225, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R104, Aerosil R106, Aerosil R202, Aerosil R711, Aerosil R805, Aerosil R812, Aerosil R816, Aerosil R972, Aerosil R974, Aerosil R7200, Aerosil R8200, Aerosil R9200 (manufactured by Nippon Aerosil Co., Ltd.), ACEMATT 82, ACEMATT HK125, ACEMATT HK400, ACEMATT HK460, ACEMATT TS100, ACEMATT 82 (manufactured by EVONIK DEGUSSA) E-200A, Synthetic fine silica such as E-220A, K-500, E-1009, E-1011, E-1030, E-150J, E-170, E-200, E-220, E-743, E-974, E-75, HD, HD-2, L-250, L-300, G-300, SS-10, SS-50, SS-30P, SS-30V, SS-30X, SS-50, SS-70 (manufactured by Toso Silica Co., Ltd.), FUSELEX RD-8, FUSELEX RD-8AL, FUSELEX RD-120, FUSELEX MCF-200C, FUSELEXGP-200TC, FUSELEX TZ-20, FUSELEX ZA-30C, FUSELEX E-1, FUSELEX Fused pulverized silica such as E-2, FUSELEX AS-1, FUSELEX X (manufactured by Tatsumori Co., Ltd.), FS-3DC, FS-5DC (manufactured by Denka Co., Ltd.), FB-5D, FB-12D, FB-20D, FB-105, FB-940, FB-9454, FB-950, FB-105FC, FB-870FC, FB-875FC, FB-9454FC, FB-950FC, FB-300FC, FB-105FD,FB-970FD, FB-975FD, FB-950FD, FB-300FD, FB-400FD, FB-7SDC, FB-5SDC, FB-3SDC, FB-74X, FB-25SX, FB-35X, FB-302X, FB-105X, FB-940X, FB-950X, FB-105XFC, FB-950XFC, FB-100XFD, FB-950XFD, FB-7SDX, FB-5SDX, FB-3SDX (made by Denka Corporation), MSR-2212, MSR-25, MSR-3512, MSR-2212M4, MSV-2212N, MSV-2212NH, MSV-2507NH, Molten spherical silica such as MSV-3512N, MSV-3512NH, MSS-7, MSS-6, EXR-4, EXR-3, AC-5VLD, B-21, A-21, MP-15EF, AC-5V, MP-8FS (manufactured by Tatsumori Co., Ltd.), synthetic spherical silica such as SO-E1, SO-E2, SO-E3, SO-E5, SO-E6, SO-C1, SO-C2, SO-C3, SO-C5, SO-C6 (manufactured by Admatex Co., Ltd.), CRYSTALITE 3K, CRYSTALITE 3K-S, CRYSTALITE C, CRYSTALITE TNC-1, CRYSTALITE NX-7, CRYSTALITE SMT-10, CRYSTALITE CMC-12S, CRYSTALITE XJ-7, CRYSTALITE C-BASE-1, Examples of crystalline crushed silica include CRYSTALITE A-1, CRYSTALITE AA, and CRYSTALITE VX-S2 (manufactured by Tatsumori Co., Ltd.).

[0116] [2-functional (meth)acrylate monomer]

[0117] In order to further increase the thermal discoloration resistance of the curable resin composition of the present invention, it is preferable to further include a difunctional (meth)acrylate monomer in the curable resin composition of the present invention.

[0118] Examples of such difunctional (meth)acrylate monomers include 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol acrylate, 1,10-decanediol diacrylate, 1,16-hexadecanediol diacrylate, etc.

[0119] Examples of commercially available products include HDDA (manufactured by Daiichi High School Seiyaku Co., Ltd.), A-NOD-N (manufactured by Shin-Nakamura Kagaku High School), B1065 (manufactured by Tokyo Kasei High School Co., Ltd.), Biscot #195 (manufactured by Osaka Yuki Kagaku High School Co., Ltd.), and A-DOD-N (manufactured by Shin-Nakamura Kagaku High School).

[0120] The amount of the above-mentioned difunctional (meth)acrylate monomer is preferably 5 to 65 parts by weight per 100 parts by weight of a compound having an isocyanurate structure and two or more (meth)acryloyl groups. The curable resin composition of the present invention may, if necessary, contain a monofunctional (meth)acrylate monomer or a trifunctional (meth)acrylate monomer.

[0121] [Other Antioxidants]

[0122] In order to further increase the thermal discoloration resistance of the cured product, the curable resin composition of the present invention may, of course, contain additional antioxidants in addition to the antioxidant having (D) an isocyanurate structure.

[0123] As such antioxidants, for example, phenolic compounds such as hydroquinone, 4-tert-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methylene-bis-(4-methyl-6-t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, quinone compounds such as metaquinone, benzoquinone, amine compounds such as bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, phenothiazine, phosphorus compounds such as triphenylphosphite, pentaerythritol tetralaurylthiopropionate, Examples include sulfur compounds such as dilauryl thiodipropionate and distearyl 3,3'-thiodipropionate.

[0124] As commercially available products, for example, AdekaStab AO-30, AdekaStab AO-330, AdekaStab AO-20, AdekaStab LA-77, AdekaStab LA-57, AdekaStab LA-67, AdekaStab LA-68, AdekaStab LA-87 (all manufactured by ADEKA, product names), IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (all manufactured by BASF Japan, product names), AdekaStab TPP (manufactured by ADEKA, product name), Mark AO-412S (manufactured by ADEKA, product name), Smilizer TPS (Sumitomo Examples include Gagakusa-made, product name, etc.

[0125] When such an antioxidant is used in combination with an antioxidant having (D) an isocyanurate structure, it is preferable to mix it in a mass ratio of 0.5 to 3 with respect to 1 mass part of the antioxidant having (D) an isocyanurate structure, and more preferably in a mass ratio of 0.5 to 2.

[0126] [Organic Solvents]

[0127] In addition, the curable resin composition of the present invention may contain an organic solvent for purposes such as preparing the composition or adjusting the viscosity when applied to a substrate or carrier film. As organic solvents, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, and tripropylene glycol monomethyl ether; Known and commonly used organic solvents may be used, such as esters including ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons including octane and decane; and petroleum-based solvents including petroleum ether, petroleum naphtha, and solvent naphtha. These organic solvents may be used alone or in combination of two or more types.

[0128] [Other ingredients]

[0129] The curable resin composition of the present invention may additionally contain other additives known and commonly used in the field of electronic materials, if necessary. Examples of such additives include thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial and antifungal agents, defoaming agents, leveling agents, thickeners, adhesion improvers, photoinitiation aids, sensitizers, thermoplastic resins, organic fillers, release agents, surface treatment agents, dispersants, dispersion aids, surface modifiers, stabilizers, phosphors, etc.

[0130] [Dry Film]

[0131] The curable resin composition of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-component or two-component or more-component.

[0132] The dry film of the present invention has a resin layer obtained by applying and drying a curable resin composition of the present invention onto a carrier film. When forming the dry film, first, the curable resin composition of the present invention is diluted with the organic solvent to adjust the viscosity to an appropriate level, and then applied to the carrier film with a uniform thickness using a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc. After that, the resin layer can be formed by drying the applied composition at a temperature of typically 50 to 130°C for 1 to 30 minutes. Although there are no particular limitations on the thickness of the applied film, the film thickness after drying is generally appropriately selected in the range of 10 to 150 μm, preferably 20 to 60 μm.

[0133] Plastic films are used as carrier films, and for example, polyester films such as polyethylene terephthalate (PET), polyimide films, polyamideimide films, polypropylene films, polystyrene films, etc., can be used. There are no particular restrictions on the thickness of the carrier film, but it is generally appropriately selected in the range of 10 to 150 μm.

[0134] After forming a resin layer containing the curable resin composition of the present invention on a carrier film, it is preferable to further laminate a peelable cover film on the surface of the film for purposes such as preventing dust from adhering to the surface of the film. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, or surface-treated paper may be used. As for the cover film, it is sufficient that the adhesive force between the resin layer and the carrier film is smaller than the adhesive force when the cover film is peeled off.

[0135] In addition, in the present invention, a resin layer may be formed by applying and drying the curable resin composition of the present invention onto the cover film, and a carrier film may be laminated on the surface thereof. That is, when manufacturing a dry film in the present invention, either a carrier film or a cover film may be used as the film to which the curable resin composition of the present invention is applied.

[0136] [Hardened material]

[0137] In order to form a cured product using the curable resin composition of the present invention, the composition is applied onto a substrate, and after drying the solvent, exposure (light irradiation) is performed on the resulting resin layer, thereby curing the exposed portion (the portion irradiated with light). Specifically, through a photomask formed by a contact or non-contact method, exposure is selectively performed by an active energy line, or the pattern is directly exposed by a laser direct exposure machine, and an unexposed portion is developed with an alkaline aqueous solution (e.g., an aqueous solution of sodium carbonate at 0.3 to 3 mass%) to form a resist pattern. Additionally, by heating at a temperature of about 100 to 180°C to perform heat curing (post-curing), a cured film (cured product) with excellent properties such as heat resistance, chemical resistance, moisture resistance, adhesion, and electrical properties can be formed.

[0138] The curable resin composition of the present invention can form a tack-free resin layer by adjusting the viscosity to suit a coating method using, for example, the above organic solvent, applying it onto a substrate by a method such as a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, or a curtain coating method, and then evaporating and drying (pre-drying) the organic solvent contained in the composition at a temperature of about 60 to 100°C. In addition, in the case of a dry film in which the above curable resin composition is applied onto a carrier film or a cover film and dried to be wound as a film, the resin layer can be transferred onto a substrate by bonding it to contact the substrate using a laminator or the like, and then peeling off the carrier film.

[0139] As for the substrate, in addition to printed circuit boards or flexible printed circuit boards in which circuits are formed in advance using copper, etc., materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, copper-clad laminates for high-frequency circuits using fluoropolymer, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc. are used, and copper-clad laminates of all grades (FR-4, etc.) are used, as well as metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer boards, etc. can be used.

[0140] The above volatile drying or heat curing can be performed using a hot air circulation type dryer, an IR oven, a hot plate, a convection oven, etc. (a method of making counter-flow contact of hot air inside the dryer using a heat source equipped with a steam-based air heating method and a method of spraying onto a support from a nozzle).

[0141] As the exposure device used for the above active energy irradiation, it is sufficient to be a device equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and irradiating active energy rays in the range of 350 to 450 nm; additionally, a direct imaging device (for example, a laser direct imaging device that draws an image directly with a laser based on CAD data from a computer) may also be used. As for the lamp light source or laser light source of the direct imaging device, it is sufficient to have a maximum wavelength in the range of 350 to 410 nm. The exposure amount for image formation varies depending on the film thickness, etc., but is generally 20 to 1000 mJ / cm² 2 , preferably 20 to 800 mJ / cm² 2 It can be done within the range of.

[0142] The above development method may be the dipping method, shower method, spray method, brush method, etc., and as the developer, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. may be used.

[0143] The curable resin composition of the present invention is suitably used to form a surface protective film, such as a solder resist, on a printed circuit board. In addition, the curable resin composition of the present invention may be used as an interlayer insulating layer of a multilayer printed circuit board.

[0144] [Electronic Components]

[0145] In addition, the present invention provides an electronic component having a cured product formed by curing the curable resin composition of the present invention. By using the curable resin composition of the present invention, an electronic component with high quality and reliability is provided.

[0146] In addition, in the present invention, the term "electronic component" refers to a component used in an electronic circuit, and includes active components such as printed circuit boards, transistors, light-emitting diodes, and laser diodes, as well as passive components such as resistors, capacitors, inductors, and connectors, and the cured product of the present invention exhibits the effects of the present invention as an insulating cured film thereof.

[0147] [Preparation of the curable resin composition of the present invention]

[0148] The curable resin composition of the present invention can be prepared by mixing and dispersing (A) a compound having an isocyanurate structure and two or more (meth)acryloyl groups, (B) an epoxy resin having an isocyanurate structure, and (C) a photopolymerization initiator, and if desired, other components in predetermined amounts, for example, using a three-roll mill or the like.

[0149] Hereinafter, an embodiment of the present invention is specifically described by way of examples, but of course, it is not intended to limit the scope of the invention according to the claims herein.

[0150] [Example]

[0151] The present invention will be described in detail below by presenting examples and comparative examples, but it should be understood that the present invention is not limited to the following examples.

[0152] In addition, unless otherwise noted, the "parts" and "%" that appear are based on mass.

[0153] [Examples 1 to 7 and Comparative Examples 1 to 3]

[0154] Each component as shown in Table 1 below was pre-mixed in a stirrer in the respective mixing amounts, and then kneaded in a three-roll mill to prepare the curable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3, respectively. The stirring conditions of the stirrer were such that pre-stirring was performed at a rotation speed of 500 rpm and a stirring time of 10 min, and main stirring was performed at a rotation speed of 800 rpm and a stirring time of 15 min. The stirring blades used for each stirring were 12 cm in length. In addition, the values ​​in the table represent the solid content excluding organic solvents.

[0155] (Synthesized Example 1)

[0156] 900 g of diethylene glycol dimethyl ether as a solvent and 21.4 g of t-butylperoxy2-ethylhexanoate (perbutyl O manufactured by Nihon Yushi Corporation) as a polymerization initiator were added to a 2-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, and heated at 90°C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (Flaxel FM1, manufactured by Daicel Kagaku Kogyo Co., Ltd.) were added dropwise over 3 hours along with 21.4 g of bis(4-t-butylcyclohexyl) peroxydicarbonate (Perloyl TCP, manufactured by Nippon Yushi Corp.), a polymerization initiator, and aged for an additional 6 hours to obtain a carboxyl group-containing copolymer resin. In addition, the reaction was carried out under a nitrogen atmosphere.

[0157] Subsequently, 363.9 g of 3,4-epoxycyclohexylmethylacrylate (Cyclomer A200 manufactured by Daicel Kagaku Co., Ltd.), 3.6 g of dimethylbenzylamine as a ring-opening catalyst, and 1.80 g of hydroquinone monomethyl ether as a polymerization inhibitor were added to the obtained carboxyl group-containing copolymer resin, and the ring-opening addition reaction of the epoxy was carried out by heating at 100°C and stirring. After 16 hours, a solution containing a carboxyl group-containing resin without an aromatic ring was obtained, having an acid value of 108.9 mgKOH / g of solids and a weight average molecular weight of 25,000.

[0158]

[0159] *1 A-9300YN; Ethoxylated isocyanuric acid triacrylate, manufactured by Shinnakamura Co., Ltd.

[0160] *2 A-DOD-N; 1,10-Decanediold Acrylate, manufactured by Shinnakamura Co., Ltd.

[0161] *3 A-DPH; Shin-Nakamura Kagakusa

[0162] *4 Laromer LR8863; BASF priest

[0163] *5 TEPIC (Registered Trademark)-VL; Manufactured by Nissan Kagaku

[0164] *6 jER828; Mitsubishi Chemical

[0165] *7 Synthesis Example 1

[0166] *8 TIF-3 (acid value 130 mgKOH / g); manufactured by Shinnakamura Co., Ltd.

[0167] *9 Omnirad TPO; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; manufactured by IGM Resins

[0168] *10 Omnirad 819; Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; IGM Resins

[0169] *11 Irganox3114; manufactured by BASF Japan

[0170] *12 Irganox 1010; Manufactured by BASF Japan

[0171] *13 Irganox1330; manufactured by BASF Japan

[0172] *14 PX-3788; Sakai Kagaku High School Co., Ltd.

[0173] *15 Nipsil E-743 (average particle size 1.5 to 2.2 µm; specific surface area: 45 m²) 2 / g); Doso·Silica Saje

[0174] *16 AEROSIL R974 (Primary particle size 12 nm; Specific surface area: 150 to 190 m²) 2 / g); Nippon Aerosil thread

[0175] For the curable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 obtained, tests regarding color difference ΔE and storage stability were performed as follows.

[0176] [Test regarding Color Difference ΔE (Thermal Discoloration Resistance)]

[0177] The curable resin compositions of Examples 1 to 7 and Comparative Example 3 prepared above were each applied to a glass substrate using an applicator, and a drying treatment was performed at 80°C for 30 minutes to obtain a dried film with a thickness of 20 μm. Subsequently, a metal halide lamp light source was used through a patterned negative at an exposure dose of 600 mJ / cm² 2 After investigating, the sample was immersed in a 1 mass% aqueous sodium carbonate solution to develop it, and then heated at 150°C for 60 minutes to perform a curing treatment.

[0178] For the obtained substrate, heat treatment was performed once for 10 seconds at a peak top temperature of 285°C. The amount of color change ΔE (color difference) from the initial value was calculated.

[0179] ΔE that was 2.0 or less was marked as ◎, ΔE that was 2.1 or more or less than 4.0 was marked as ○, and ΔE that was 4.0 or more was marked as ×.

[0180] [Test regarding preservation stability]

[0181] Each of the curable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was left standing at 20°C, and the number of days from the time of standing until separation occurred on the surface of the curable resin compositions was recorded.

[0182]

Claims

Claim 1 A curable resin composition comprising at least the following components (A) to (C): (A) a compound having an isocyanurate structure and two or more (meth)acryloyl groups, (B) an epoxy resin having an isocyanurate structure, (C) a photopolymerization initiator, and a carboxyl group-containing fluoropolymer. Claim 2 In claim 1, (D) a curable resin composition further comprising an antioxidant having an isocyanurate structure. Claim 3 A curable resin composition according to claim 1 or 2, further comprising (E) a white coloring agent. Claim 4 A curable resin composition according to claim 1 or 2, further comprising a carboxyl group-containing resin that does not contain fluorine atoms. Claim 5 In paragraph 1 or 2, the specific surface area is 10m 2 / g or more than 100m 2 Silica with less than 1 / g, and a specific surface area of ​​100m² 2 / g or more than 300m 2 A curable resin composition containing at least one type of silica less than / g. Claim 6 A dry film having a curable resin composition described in claim 1 or 2 as a resin layer. Claim 7 A curable resin composition described in claim 1 or 2, or a cured product of a resin layer of a dry film having said curable resin composition as a resin layer. Claim 8 An electronic component having the hardened material described in paragraph 7.

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