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

Abstract

The present invention relates to a curable resin composition, a dry film, a cured product, and an electronic component. [Problem] To provide: a curable resin composition capable of imparting high heat resistance to color change, and a cured product thereof. [Solution] A curable resin composition containing 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, and (C) a photopolymerization initiator.

Description

Technical 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 Art

[0002] In the production of printed circuit boards, a solder resist layer is usually used to protect the conductor circuits on the substrate from the attachment of solder, and heretofore, curable resin compositions containing various components having various structures have been proposed for forming such a solder resist layer.

[0003] For example, Patent Document 1 discloses a photosensitive resin composition containing: a (meth)acrylic copolymer having a specific structure having a (meth)acryloyl group, a monomer having an ethylenically unsaturated bond, and a photoinitiator.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2004-191680 Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] However, depending on the use of the printed circuit board, the solder resist layer requires various properties, and one of them is heat resistance. This is because if the heat resistance of the solder resist layer is insufficient, there is a concern that the solder resist layer itself may change color. For example, in order to improve the reflection efficiency of light from an LED and achieve the efficiency of its utilization, a white colorant is contained in the solder resist layer used in a circuit board on which a light-emitting element such as a light-emitting diode (LED) is mounted. Therefore, when the solder resist layer changes color from white to yellow (yellowing), the reflection efficiency of LED light will decrease sharply.

[0009] The solder resist layer is particularly susceptible to the heat of solder during the mounting of electronic components on the substrate, the heat dissipation from the electronic components after mounting, and other thermal stresses after its formation. Therefore, the resistance to color change due to such thermal stresses can be said to be an important property.

[0010] However, in this regard, it can be said that the conventional curable resin compositions such as the photosensitive resin composition described in Patent Document 1 do not sufficiently consider the heat resistance, particularly the heat discoloration resistance, of the solder resist layer.

[0011] Solutions for Solving the Problems

[0012] In order to solve the above problems, the present inventors conducted repeated and in-depth studies, and as a result, found that: by using in combination a compound having an isocyanurate structure and two or more (meth)acryloyl groups and an epoxy resin having an isocyanurate structure in a curable resin composition, a cured coating film (for example, a solder resist layer) with improved heat discoloration resistance can be formed, and thus the present invention was completed.

[0013] That is, it was found that the problems in the present invention can be solved by a curable resin composition,

[0014] The curable resin composition contains at least the following components (A) to (C):

[0015] (A) A compound having an isocyanurate structure and two or more (meth)acryloyl groups,

[0016] (B) An epoxy resin having an isocyanurate structure, and

[0017] (C) A photopolymerization initiator.

[0018] Among them, a preferred embodiment of the present invention relates to the above curable resin composition, which further contains (D) an antioxidant having an isocyanurate structure.

[0019] A further preferred embodiment relates to the above curable resin composition, which further contains (E) a white colorant.

[0020] A further preferred embodiment relates to the above curable resin composition, which further contains at least one of a carboxyl group-containing fluororesin and a carboxyl group-containing copolymer resin without fluorine atoms.

[0021] A further preferred embodiment relates to the above curable resin composition, which further contains silica having a specific surface area of 10 m 2 / g or more and less than 100 m 2 / g, and at least one of silica having a specific surface area of 100 m 2 / g or more and less than 300 m 2 / g.

[0022] Moreover, another embodiment of the present invention also relates to a dry film having the above curable resin composition as a resin layer, the above curable resin composition, or a cured product of the foregoing dry film resin layer, and an electronic component having the foregoing cured product.

[0023] Effects of the Invention

[0024] According to the present invention, there are provided: a cured product (cured coating film) having higher heat resistance, and a curable resin composition capable of forming the cured product. Therefore, the cured product has high resistance to discoloration caused by heat, and thus can be more suitably used as a solder mask, particularly as a white solder mask for a circuit board on which LEDs are mounted. Detailed Description

[0025] The high heat discoloration resistance of the cured product obtained from the curable resin composition of the present invention can be basically achieved by using in combination (A) a compound having an isocyanurate structure and two or more (meth)acryloyl groups and (B) an epoxy resin having an isocyanurate structure.

[0026] In the present invention, the heat discoloration resistance can also be represented by the degree of change (color difference: ΔE) in the hue of the cured coating film before and after applying a heat stress to the cured coating film formed from the curable resin composition. It can be said that the smaller the ΔE, the higher the heat discoloration resistance, and the larger the ΔE, the lower the heat discoloration resistance.

[0027] For example, ΔE can be calculated as follows: For a cured product that has been subjected to the coating, drying, exposure, development, and curing processes of the curable resin composition, heat treatment is performed at a peak temperature of 285 °C for 10 seconds, and it is calculated based on the amount of change in color from the initial value.

[0028] In addition, the curable resin composition of the present invention itself also has good long-term storage stability. Therefore, for example, there is also an advantage that the quality during use can be maintained even after a long time of transportation of the curable resin composition, such as transportation overseas by ship.

[0029] Hereinafter, each component constituting the curable resin composition of the present invention will be described.

[0030] [(A) Compound having an isocyanurate structure and two or more (meth)acryloyl groups]

[0031] (A) The compound having an isocyanurate structure and two or more (meth)acryloyl groups has an isocyanurate ring and two or more (meth)acryloyl groups in its unit structure.

[0032] As the (A) compound, for example, bifunctional or trifunctional (meth)acrylate can be cited.

[0033] Among them, as the substance having bifunctional (meth)acrylate, ethoxylated isocyanuric acid di(meth)acrylate or propoxylated isocyanuric acid di(meth)acrylate is preferred.

[0034] In addition, as the substance having trifunctional (meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate or propoxylated isocyanuric acid tri(meth)acrylate is preferred.

[0035] Furthermore, caprolactone-modified products thereof are preferably cited.

[0036] As the compound (A) having an isocyanurate structure and two or more (meth)acryloyl groups, ethoxylated tris(meth)acrylate isocyanurate is further preferred. Commercially available products of the compound (A) having an isocyanurate structure and two or more (meth)acryloyl groups include: M-215, M-313, M-315 manufactured by Toagosei Co., Ltd.; A-9300, A-9300-1CL, A-9300YN manufactured by Shin-Nakamura Chemical Co., Ltd.; Photomer 4356 manufactured by IGM Resins; FA-731A manufactured by Hitachi Chemical Co., Ltd.

[0037] In the present invention, the content of the compound (A) having an isocyanurate structure and two or more (meth)acryloyl groups is preferably 3 to 25% by mass relative to the total solid content of the entire composition. In particular, when the curable resin composition of the present invention contains a white colorant, the content of the compound (A) having an isocyanurate structure and two or more (meth)acryloyl groups is preferably 3 to 10% by mass, more preferably 5 to 7% by mass. When it is 3 to 25% by mass, not only the heat-resistant discoloration property of the obtained cured product is good, but also the strength of the cured coating film is good, and the viscosity of the composition is appropriate, and the coatability and the like can be improved.

[0038] [(B) Epoxy resin having an isocyanurate structure]

[0039] In the curable resin composition of the present invention, an epoxy resin having an isocyanurate structure and having a structure in which a nitrogen atom in the isocyanurate structure is bonded to an epoxy group by an alkylene chain is included. In particular, an epoxy resin having a structure in which the carbon number of the alkylene chain is two or more is preferred. When the carbon number of the alkylene chain is in the range of 2 to 5, the obtained cured product can have good heat-resistant discoloration property.

[0040] As such an epoxy resin (B) having an isocyanurate structure used in the present invention, a structure represented by the following formula (I) is preferred.

[0041]

[0042] (In the formula,

[0043] R1, R2 and R3 each independently represent an alkylene group having 2 to 5 carbon atoms,

[0044] n is 0 or 1, provided that not all n represent 0)

[0045] Among them, particularly preferably, in the formula, R1, R2 and R3 simultaneously represent an alkylene group having 3 carbon atoms, and n simultaneously represents a structure of 1.

[0046] As specific products of the epoxy resin having an isocyanurate structure which is preferably used in the present invention (B), for example, TEPIC (registered trademark)-VL and TEPIC (registered trademark)-FL (both manufactured by Nissan Chemical Industries, Ltd.) can be cited.

[0047] The content of such an epoxy resin having an isocyanurate structure (B) is preferably 30 to 70% by mass with respect to 100 parts by mass of the compound (A) having an isocyanurate structure and two or more (meth)acryloyl groups. In particular, when the curable resin composition of the present invention contains (E) a white colorant, the content of the compound (A) having an isocyanurate structure and two or more (meth)acryloyl groups is preferably 48 to 68 parts by mass. If it is in the range of 30 to 70% by mass, the heat discoloration resistance of the obtained cured product becomes good, and the storage stability of the curable resin composition is also improved.

[0048] [(C) Photoinitiator]

[0049] As the (C) photoinitiator, any known photoinitiator that functions as a photoinitiator or a photo radical generator can be used. For example, the following can be cited: 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 and other bisacylphosphine oxides; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, methyl 2,4,6-trimethylbenzoylphenylphosphonate, 2-methylbenzoyldiphenylphosphine oxide, isopropyl neopentanoyl phenylphosphonate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and other monoacylphosphine oxides; 1-hydroxycyclohexyl phenyl ketone, 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 and other hydroxyacetophenones; benzoin, benzil, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether and other benzoins; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone and other benzophenones; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone and other acetophenones; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and other thioxanthones; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-pentylanthraquinone, 2-aminoanthraquinone and other anthraquinones; acetophenone dimethyl ketal, benzil dimethyl ketal and other ketals; ethyl 4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, ethyl p-dimethylbenzoate and other benzoates;{1-[4-(phenylthio)-2-(O-benzoyl oxime)]}1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime)ethanone and other oxime esters; bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyrrol-1-yl)ethyl)phenyl]titanium and other titanocene compounds; phenyl disulfide 2-nitrofluorene, benzoin, benzoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. The photoinitiator can be used alone as one kind, or two or more kinds can be used in combination.;

[0050] (C) The content of the photoinitiator is preferably 5 to 20 parts by mass, more preferably 10 to 20 parts by mass, based on 100 parts by mass of the compound having an isocyanurate structure and two or more (meth)acryloyl groups (A). If it is in the range of 5 to 20 parts by mass, the surface curability becomes good, and halation is not likely to occur, and good resolution can be obtained.

[0051] [(D) Antioxidant having an isocyanurate structure]

[0052] In the curable resin composition of the present invention, (D) an antioxidant having an isocyanurate structure may also be contained. Thereby, the effect of further improving the heat discoloration resistance of the cured coating film can be exhibited.

[0053] Such an antioxidant (D) having an isocyanurate structure preferably includes the substance represented by the following formula (II).

[0054]

[0055] (In the formula,

[0056] The groups R4, R5 and R6 each independently represent a hydrogen atom, or an aliphatic hydrocarbon group or an aromatic hydrocarbon group optionally substituted with at least one substituent selected from the group consisting of a hydroxyl group and a hydrocarbon group having 1 to 10 carbon atoms, and

[0057] The nitrogen atom in the formula is optionally directly bonded to the group R4, R5 or R6, or is optionally bonded via an alkylene group having 1 to 10 carbon atoms)

[0058] A more preferable antioxidant (D) having an isocyanurate structure is a structure in which the groups R4, R5 and R6 in the formula (II) each represent a phenyl group substituted with one hydroxyl group and 1 to 3 hydrocarbon groups having 1 to 4 carbon atoms, and each nitrogen atom is bonded to the group R4, R5 or R6 via an alkylene group having 1 to 3 carbon atoms.

[0059] Particularly preferred antioxidants (D) having an isocyanurate structure are 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (trade name: Irganox 3114; manufactured by BASF Japan Ltd.) represented by the following formula (II’). In addition, as commercially available products of antioxidants (D) having an isocyanurate structure, there are CYANOX 1790 manufactured by Japan Cytec Industries, Inc. and ADECASTAB AO-20 manufactured by Adeka Corporation.

[0060]

[0061] The content of the antioxidant (D) having an isocyanurate structure is preferably 1 to 8% by mass relative to 100 parts by mass of the compound (A) having an isocyanurate structure and two or more (meth)acryloyl groups. If it is in the range of 1 to 8% by mass, the heat-resistant discoloration of the cured coating film can be further improved.

[0062] [(E) White colorant]

[0063] When the curable resin composition of the present invention is used for, for example, a solder resist layer of a printed circuit board for an LED, a white colorant can be contained. Thereby, the reflectance of the cured coating film can be improved, and the efficiency of utilization of the light of the LED can be achieved.

[0064] Examples of the white colorant (E) include titanium oxide, zinc oxide, potassium titanate, zirconium oxide, antimony oxide, lead white, zinc sulfide, lead titanate, etc. From the viewpoint of high inhibition effect of discoloration caused by heat, titanium oxide is preferably used.

[0065] As the titanium oxide, it can be titanium oxide having any structure of rutile type, anatase type, or orthorhombic type (ramsdellite type), and one kind can be used alone, or two or more kinds can be used in combination. Among them, orthorhombic titanium oxide can be obtained by performing a lithium desorption treatment based on chemical oxidation on orthorhombic Li 0.5 TiO2.

[0066] In the above, if rutile type titanium oxide is used, the heat resistance of the cured coating film can be further improved, so it is preferred. In particular, by using rutile type titanium oxide surface-treated with aluminum oxide such as alumina and silica, the reflectance and heat resistance of the cured coating film can be further improved.

[0067] In addition, on the basis of the surface treatment, other surface treatments can also be further carried out. In particular, on the basis of the surface treatment with alumina, zirconia is further used for surface treatment, so that the reflectivity can be further improved.

[0068] Examples of the rutile titanium oxide surface-treated with the above-mentioned aluminum oxide include: CR-58 manufactured by Ishihara Sangyo Co., Ltd. belonging to rutile chloride process titanium oxide, and R-630 manufactured by the same company belonging to rutile sulfuric acid process titanium oxide. In addition, rutile titanium oxide surface-treated with silicon oxide is also preferably used. In this case, the heat resistance can be further improved. Further, rutile titanium oxide surface-treated with both aluminum oxide and silicon oxide is also preferably used. Examples include: CR-90 manufactured by Ishihara Sangyo Co., Ltd. belonging to rutile chloride process titanium oxide.

[0069] The compounding amount of such (E) white colorant is preferably in the range of 750 to 950 parts by mass, more preferably in the range of 800 to 900 parts by mass, based on 100 parts by mass of the compound (A) having an isocyanurate structure and two or more (meth)acryloyl groups.

[0070] [Resin containing carboxyl group]

[0071] In the curable resin composition of the present invention, it is preferably further contained at least one of a fluororesin containing a carboxyl group or a resin containing a carboxyl group without fluorine atoms.

[0072] As the fluororesin containing a carboxyl group, a known fluororesin containing a carboxyl group can be used. A fluororesin refers to a polymer or oligomer having at least one fluorine atom. Due to the presence of the carboxyl group, the curable resin composition can be made alkali-developable, and due to the presence of the fluorine atom, the heat-resistant discoloration property can be improved.

[0073] In addition, from the viewpoints of making the curable resin composition of the present invention photocurable and developability-resistant, in addition to the carboxyl group and the fluorine atom, an ethylenically unsaturated bond can also be present in the molecule. As the ethylenically unsaturated double bond, it can be derived from acrylic acid or methacrylic acid or their derivatives.

[0074] Specific examples of the fluororesin containing a carboxyl group that can be used in the curable resin composition of the present invention include the compounds (either oligomers or polymers) listed below. It should be noted that the "fluorinated product" described below refers to a compound in which one or more hydrogen atoms other than the hydrogen atoms of the functional groups constituting the specified compound are replaced by fluorine.

[0075] (1) A carboxyl group-containing fluororesin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with a fluorinated derivative of a compound containing an unsaturated group such as styrene, α-methylstyrene, an alkyl (meth)acrylate (where the alkyl is, for example, an alkyl having 2 to 15 carbon atoms, preferably 2 to 8 carbon atoms), or isobutylene.

[0076] (2) A carboxyl group-containing polyurethane resin containing a carboxyl group and a urethane bond, obtained by the addition polymerization of a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate, a carboxyl group-containing diol compound such as dimethylolpropionic acid or dimethylolbutyric acid, and a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, and at least one of the recited raw materials is a fluorinated derivative.

[0077] (3) A carboxyl group-containing urethane resin is obtained by the addition polymerization of a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate, and a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, and the resulting urethane resin is reacted at its terminal with an acid anhydride to form a carboxyl group-containing terminal urethane resin, and at least one of the recited raw materials is a fluorinated derivative, a fluororesin containing a carboxyl group and a urethane bond.

[0078] (4) A photosensitive carboxyl group-containing polyurethane resin containing a carboxyl group and a urethane bond, obtained by the addition polymerization of a diisocyanate, a (meth)acrylate or a partially acid anhydride-modified product thereof of a 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, dimethylxylenol-type epoxy resin, or biphenol-type epoxy resin, a carboxyl group-containing diol compound, and a diol compound, and at least one of the recited raw materials is a fluorinated derivative.

[0079] (5) A fluororesin containing a carboxyl group and a urethane bond, obtained by subjecting the resin of (2) or (4) above to terminal (meth)acrylation by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as a (meth)acrylic acid hydroxyalkyl ester, during the synthesis of the resin.

[0080] (6) A fluororesin containing a carboxyl group and a urethane bond, which is obtained by subjecting the resin of (2) or (4) above to terminal (meth)acrylation by adding an equimolar reactant such as isophorone diisocyanate and pentaerythritol triacrylate, or a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule.

[0081] (7) A photosensitive resin containing a carboxyl group, which is obtained by reacting a fluorinated derivative of a polyfunctional epoxy resin described below with (meth)acrylic acid and adding a dibasic anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the hydroxyl group present in the side chain.

[0082] (8) A photosensitive fluororesin containing a carboxyl group, which is obtained by reacting a fluorinated derivative of a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin with (meth)acrylic acid and adding a dibasic anhydride to the resulting hydroxyl group.

[0083] (9) A fluororesin containing a carboxyl group and an ester bond, which is obtained by reacting a fluorinated derivative of a polyfunctional oxetane resin described below with a dicarboxylic acid and adding a dibasic anhydride to the resulting primary hydroxyl group.

[0084] (10) A photosensitive fluororesin containing a carboxyl group, which is obtained by reacting a fluorinated derivative of a compound having a plurality of 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 anhydride.

[0085] (11) A photosensitive fluororesin containing a carboxyl group, which is obtained by reacting a fluorinated derivative of a compound having a plurality of 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 anhydride.

[0086] (12) A photosensitive fluororesin containing a carboxyl group, which is obtained by reacting a fluorinated derivative of an epoxy compound having a plurality of epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol and 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 anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic anhydride.

[0087] (13) A photosensitive fluororesin containing a carboxyl group, which is obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in the molecule such as glycidyl (meth)acrylate or α-methylglycidyl (meth)acrylate to any of the resins in (1) to (12) above.

[0088] The above-mentioned fluorinated compounds can be obtained by fluorinating a specified compound. As the fluorination method, known methods can be used, such as low-temperature fluorination, contact fluorination, aqueous solution fluorination, liquid-phase fluorination, solid-phase fluorination, gas-phase fluorination, etc.

[0089] As the fluororesin containing a carboxyl group, specifically, a fluororesin containing a carboxyl group manufactured by Shin-Nakamura Chemical Co., Ltd. (product names: TIF-1, TIF-2, TIF-3) can be used.

[0090] The compounding amount of the above-mentioned fluororesin containing a carboxyl group is preferably 135 to 360 parts by mass, more preferably 150 to 300 parts by mass, relative to 100 parts by mass of the compound having an isocyanurate structure and two or more (meth)acryloyl groups in (A). In the case of 135 to 300 parts by mass, the film strength is good, and the viscosity of the composition is appropriate, which can improve the coatability, etc.

[0091] In the curable resin composition of the present invention, it is preferably further contained a resin containing a carboxyl group other than the above-mentioned fluororesin containing a carboxyl group, that is, a resin containing a carboxyl group without fluorine atoms. By containing a resin containing a carboxyl group without fluorine atoms, the developability is further improved.

[0092] As the resin containing a carboxyl group without fluorine atoms, a known resin containing a carboxyl group can be used. From the viewpoints of making the curable resin composition of the present invention photocurable and developability-resistant, in addition to the carboxyl group, it is preferably further having an ethylenically unsaturated bond in the molecule, but a resin containing a carboxyl group without an ethylenically unsaturated double bond can also be used alone. As the ethylenically unsaturated double bond, it is preferably derived from acrylic acid or methacrylic acid or their derivatives.

[0093] As specific examples of the resin containing a carboxyl group that can be used in the curable resin composition of the present invention, the following listed compounds (either oligomers or polymers) can be cited.

[0094] (1) A carboxyl-containing copolymer resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with a compound containing an unsaturated group such as styrene, α-methylstyrene, a lower alkyl (meth)acrylate, isobutylene, etc.

[0095] (2) A carboxyl-containing polyurethane resin obtained by the addition polymerization reaction of a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, etc., a carboxyl-containing diol compound such as dimethylolpropionic acid, dimethylolbutyric acid, and a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, an adduct diol of bisphenol A-based alkylene oxide, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, etc.

[0096] (3) A polyurethane resin is obtained by the addition polymerization reaction of diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, cycloaliphatic diisocyanates, and aromatic diisocyanates, and diol compounds such as polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups. The polyurethane resin with a terminal carboxyl group is obtained by reacting the terminal of the polyurethane resin with an acid anhydride.

[0097] (4) A photosensitive carboxyl-containing polyurethane resin is obtained by the addition polymerization reaction of a diisocyanate and (meth)acrylate or a partial acid anhydride-modified product thereof of a 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, dimethylbiphenol-type epoxy resin, and biphenol-type epoxy resin, a carboxyl-containing diol compound, and a diol compound.

[0098] (5) A carboxyl-containing polyurethane resin having terminal (meth)acrylation is obtained by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as (meth)acrylic hydroxyalkyl ester, to the synthesis of the resin in (2) or (4) above.

[0099] (6) A carboxyl-containing polyurethane resin having terminal (meth)acrylation is obtained by adding an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, etc., a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule, to the synthesis of the resin in (2) or (4) above.

[0100] (7) A photosensitive carboxyl-containing resin is obtained by reacting a polyfunctional epoxy resin described later with (meth)acrylic acid and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride to the hydroxyl group present in the side chain.

[0101] (8) A photosensitive carboxyl-containing resin is obtained by reacting a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin with (meth)acrylic acid and adding a dibasic acid anhydride to the generated hydroxyl group.

[0102] (9) A carboxyl-containing polyester resin is obtained by reacting a polyfunctional oxetane resin described later with a dicarboxylic acid and adding a dibasic acid anhydride to the generated primary hydroxyl group.

[0103] (10) A carboxyl-containing photosensitive resin is obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide and propylene oxide to obtain a reaction product, reacting the reaction product with a monocarboxylic acid having an unsaturated group, and reacting the resulting reaction product with a polybasic acid anhydride.

[0104] (11) A compound having multiple phenolic hydroxyl groups in one molecule is reacted with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate to obtain a reaction product. The reaction product is reacted with a monocarboxylic acid containing an unsaturated group, and the resulting reaction product is reacted with a polyanhydride to obtain a photosensitive carboxyl-containing resin.

[0105] (12) An epoxy compound having multiple epoxy groups in one molecule is reacted with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and a monocarboxylic acid containing an unsaturated group such as (meth)acrylic acid. The alcoholic hydroxyl group of the obtained reaction product is reacted with a polyanhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, or adipic anhydride to obtain a photosensitive carboxyl-containing resin.

[0106] (13) A photosensitive carboxyl-containing resin obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in the molecule such as glycidyl (meth)acrylate or α-methylglycidyl (meth)acrylate to any of the resins in the above (1) to (12).

[0107] The above carboxyl-containing fluororesin and the carboxyl-containing resin without fluorine atoms each have a large number of carboxyl groups on the side chain of the main chain polymer, and thus can be developed using a dilute aqueous alkali solution.

[0108] In addition, the acid values of the above carboxyl-containing fluororesin and the carboxyl-containing resin without fluorine atoms are preferably in the range of 20 to 200 mgKOH / g, more preferably in the range of 40 to 150 mgKOH / g. When the acid value of the carboxyl-containing resin is 20 mgKOH / g or more, the adhesion of the coating film becomes good and the alkali development becomes good. On the other hand, when the acid value is 200 mgKOH / g or less, the dissolution of the exposed part generated by the developer can be suppressed. Therefore, the line width can be suppressed from becoming narrower than required, or in some cases, the exposed part and the unexposed part can be prevented from being dissolved and peeled off in the developer without distinction, and the pattern of the cured film can be well drawn.

[0109] In addition, the weight average molecular weights of the above carboxyl-containing fluororesin and the carboxyl-containing resin without fluorine atoms vary depending on the resin skeleton, and are preferably in the range of 2000 to 150000, more preferably in the range of 5000 to 100000. When the weight average molecular weight is 2000 or more, the non-sticky property is good, the moisture resistance of the coated film after exposure is good, and the film loss can be suppressed and the resolution can be suppressed from decreasing during development. On the other hand, when the weight average molecular weight is 150000 or less, the developability is good and the storage stability is also excellent.

[0110] It should be noted that in this specification, "(meth)acrylate" refers to a term collectively referring to acrylate, methacrylate, and their mixtures, and the same applies to other similar expressions.

[0111] In the case of containing a carboxyl group-containing resin without fluorine atoms, its compounding amount is preferably equal to or less than that of the carboxyl group-containing fluororesin. Specifically, relative to 100 parts by mass of the compound (A) having an isocyanurate structure and two or more (meth)acryloyl groups, it 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, the viscosity of the composition is appropriate, and coatability and the like can be improved.

[0112] In addition, the mass ratio of the carboxyl group-containing fluororesin to the carboxyl group-containing resin without fluorine atoms is, for example, 95:5 to 50:50, preferably 90:10 to 60:40.

[0113] [Silica]

[0114] In the curable resin composition of the present invention, in order to impart the effect of suppressing the separation of the compounding components in the curable resin composition and further improving its long-term storage stability, it is preferably further contains silica. In this case, at least one of silica having a relatively large specific surface area and silica having a specific surface area smaller than it can be used. Or, when these two kinds of silica are used in combination, the above-mentioned effect is improved, so it is preferred.

[0115] In the present invention, the silica having a relatively large specific surface area preferably has a specific surface area of 100 m 2 / g or more and less than 300 m 2 / g. The compounding amount of the silica having a relatively large specific surface area is preferably 1 to 20 parts by mass relative to 100 parts by mass of the compound (A) having an isocyanurate structure and two or more (meth)acryloyl groups. On the other hand, the silica having a relatively small specific surface area preferably has a specific surface area of 10 m 2 / g or more and less than 100 m 2 / g. The compounding amount of the silica having a relatively small specific surface area is preferably 5 to 20 parts by mass relative to 100 parts by mass of the compound (A) having an isocyanurate structure and two or more (meth)acryloyl groups.

[0116] In addition, the compounding ratio of the silica having a relatively large specific surface area to the silica having a relatively small specific surface area is preferably 1:3 to 1:6 based on mass parts. If it is within this range, the storage stability of the composition is improved.

[0117] It should be noted that the specific surface area can be measured by the "BET method". More specifically, for example, the following method can be adopted: using the fully automatic BET specific surface area measuring device Massorb HM-1201 manufactured by Mountech Co., Ltd., and measuring the actual value by the BET one-point method.

[0118] As the silica used in the present invention, a pulverized product of synthetic or natural crystalline silica, a pulverized product of fused silica, a spherical processed product of fused silica, synthetic spherical silica, synthetic fine powder silica, etc. can be used.

[0119] Synthetic silica, that is, hydrous amorphous silica (SiO2·nH2O) is manufactured by reacting a sodium silicate solution (water glass) with sulfuric acid in a reaction tank, and the shape and particle size can be controlled according to the reaction conditions to form synthetic spherical silica or synthetic fine powder silica.

[0120] As the silica preferably used in the present invention, for example, the following can be cited: 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, 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 TOSOH SILICA) and other synthetic fine silica powders, FUSELEX RD-8, FUSELEX RD-8AL, FUSELEX RD-120, FUSELEX MCF-200C, FUSELEX GP-200TC, FUSELEX TZ-20, FUSELEX ZA-30C, FUSELEX E-1, FUSELEX E-2, FUSELEX AS-1, FUSELEX X (manufactured by Ryushin Co., Ltd.), FS-3DC, FS-5DC (manufactured by Denka Co., Ltd.Fused and ground silica, 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 (manufactured by Denka Co., Ltd.), MSR-2212, MSR-25, MSR-3512, MSR-2212M4, MSV-2212N, MSV-2212NH, MSV-2507NH, 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 Ryusen Co., Ltd.), etc., fused spherical silica, SO-E1, SO-E2, SO-E3, SO-E5, SO-E6, SO-C1, SO-C2, SO-C3, SO-C5, SO-C6 (Admatex Co., Ltd.), etc., synthetic spherical silica, 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, CRYSTALITE A-1, CRYSTALITE A-A, CRYSTALITE VX-S2 (manufactured by Ryusen Co., Ltd.), etc., crystalline crushed silica.

[0121] [Bifunctional (meth)acrylate monomer]

[0122] In the curable resin composition of the present invention, in order to further improve the heat resistance discoloration of the cured coating film, it is preferably further contained a bifunctional (meth)acrylate monomer.

[0123] As such a bifunctional (meth)acrylate monomer, for example, 1,3-butanediol 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. can be cited.

[0124] As commercially available products, for example, HDDA (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), A-NOD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.), B1065 (manufactured by Tokyo Chemical Industry Co., Ltd.), VISCOAT #195 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), A-DOD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. can be cited.

[0125] The blending amount of the above bifunctional (meth)acrylate monomer is preferably 5 to 65 parts by mass with respect to 100 parts by mass of the compound (A) having an isocyanurate structure and two or more (meth)acryloyl groups. In the curable resin composition of the present invention, a monofunctional (meth)acrylate monomer or a trifunctional or higher functional (meth)acrylate monomer can be contained as needed.

[0126] [Other antioxidants]

[0127] In the curable resin composition of the present invention, in order to further improve the heat discoloration resistance of the cured product, in addition to the antioxidant (D) having an isocyanurate structure, an antioxidant other than this can also be contained.

[0128] As such an antioxidant, for example, phenolic compounds such as hydroquinone, 4-tert-butylcatechol, 2-tert-butylhydroquinone, methyl hydroquinone, 2,6-di-tert-butyl-p-cresol, 2,2-methylenebis(4-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, etc., quinone compounds such as p-methoxyphenol, benzoquinone, etc., amine compounds such as bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, phenothiazine, etc., phosphorus compounds such as triphenyl phosphite, sulfur compounds such as pentaerythritol tetralauryl thiodipropionate, dilauryl thiodipropionate, distearyl 3,3'-thiodipropionate, etc. can be cited.

[0129] As commercially available products, for example, ADECASTAB AO-30, ADECASTAB AO-330, ADECASTAB AO-20, ADECASTAB LA-77, ADECASTAB LA-57, ADECASTAB LA-67, ADECASTAB LA-68, ADECASTAB LA-87 (above, manufactured by ADEKA CORPORATION, trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, manufactured by BASF Japan Ltd., trade name), ADECASTAB TPP (manufactured by ADEKA CORPORATION, trade name), Mark AO-412S (manufactured by ADEKA CORPORATION, trade name), Smilizer TPS (manufactured by Sumitomo Chemical Co., Ltd., trade name), etc. can be cited.

[0130] When such an antioxidant is used in combination with the antioxidant (D) having an isocyanurate structure, it is preferably compounded in a mass ratio of 0.5 to 3, more preferably 0.5 to 2, per 1 part by mass of the antioxidant (D) having an isocyanurate structure.

[0131] [Organic solvent]

[0132] In addition, in the curable resin composition of the present invention, for the purpose of adjusting the viscosity when preparing the composition, coating it on a substrate or a carrier film, etc., an organic solvent may be contained. As the organic solvent, 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; esters such as 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 such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha, etc., which are well-known and commonly used organic solvents can be used. These organic solvents can be used alone or in combination of two or more.

[0133] [Other components]

[0134] In the curable resin composition of the present invention, other additives commonly known and used in the field of electronic materials may be further contained as needed. Examples of such additives include thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial agents / mildew-proof agents, defoaming agents, leveling agents, thickeners, adhesion-imparting agents, photoinitiator aids, sensitizers, thermoplastic resins, organic fillers, mold release agents, surface treatment agents, dispersants, dispersion aids, surface modifiers, stabilizers, phosphors, etc.

[0135] [Dry film]

[0136] The curable resin composition of the present invention can be used in the form of a dry film or in a liquid state. When used in a liquid state, it can be one-component or two-component or more.

[0137] The dry film of the present invention has a resin layer, which is obtained by coating the curable resin composition of the present invention on a carrier film and drying. When forming the dry film, first, the curable resin composition of the present invention is diluted with the above-mentioned organic solvent to adjust the viscosity to an appropriate value, and then it is coated on the carrier film to a uniform thickness by using a comma coater, a doctor blade coater, a lip coater, a rod coater, a roll coater, an inverse coater, a transfer roll coater, an intaglio coater, a spray coater, etc. After that, the coated composition is usually dried at a temperature of 50 to 130°C for 1 to 30 minutes, thereby forming a resin layer. There is no particular limitation on the coating film thickness, and it is usually preferably selected in the range of 10 to 150 μm, more preferably 20 to 60 μm, in terms of the dried film thickness.

[0138] As the carrier film, a plastic film is used. For example, polyester films such as polyethylene terephthalate (PET), polyimide films, polyamideimide films, polypropylene films, polystyrene films, etc. can be used. There is no particular limitation on the thickness of the carrier film, and it is usually preferably selected in the range of 10 to 150 μm.

[0139] After forming a resin layer formed from the curable resin composition of the present invention on the carrier film, for the purpose of preventing dust from adhering to the surface of the film, etc., it is preferable to further laminate a peelable protective film on the surface of the film. As the peelable protective film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used. As the protective film, as long as the adhesion force when peeling the protective film is less than the adhesion force between the resin layer and the carrier film.

[0140] It should be noted that in the present invention, the curable resin composition of the present invention is coated on the above-mentioned protective film and dried to form a resin layer, and a carrier film can be laminated on this surface. That is, when manufacturing the dry film in the present invention, either the carrier film or the protective film can be used as the film for coating the curable resin composition of the present invention.

[0141] [Cured product]

[0142] When forming a cured product using the curable resin composition of the present invention, the composition is coated on a substrate, and after the solvent is volatilized and dried, a resin layer is obtained. The obtained resin layer is exposed (irradiated with light), so that the exposed portion (the portion irradiated with light) is cured. Specifically, by a contact or non-contact method, through a patterned photomask, the active energy ray is selectively used for exposure, or direct pattern exposure is directly performed using a laser direct exposure machine. The unexposed portion is developed using an alkaline aqueous solution (for example, 0.3 to 3% by mass sodium carbonate aqueous solution), thereby forming a resist pattern. Further heating to a temperature of about 100 to 180 °C for thermal curing (post-curing) can form a cured coating film (cured product) with excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties.

[0143] The curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method using the above-mentioned organic solvent, and after being coated on a substrate by methods such as dip coating, flow coating, roll coating, bar coating, screen printing, and curtain coating, the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of about 60 to 100 °C, thereby forming a non-sticky resin layer. In addition, in the case of a dry film obtained by coating the above-mentioned curable resin composition on a carrier film or a protective film and drying it, and winding it up in the form of a film, after laminating it in such a way that the resin layer is in contact with the substrate using a laminator or the like, the carrier film is peeled off, and thus the resin layer can be transferred to the substrate.

[0144] As the substrate, in addition to printed circuit boards and flexible printed circuit boards having circuits formed of copper or the like in advance, the following can be cited: copper-clad laminates of all grades (such as FR-4), metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer boards, etc. The copper-clad laminates use materials such as paper-phenolic resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven fabric-epoxy resin, glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin; copper-clad laminates for high-frequency circuits such as fluororesin, polyethylene, polyphenylene oxide (polyphenylene oxide), and cyanate ester.

[0145] The above-mentioned volatilization drying or thermal curing can be carried out using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, etc. (a method of making the hot air in the dryer convectively contact using a heat source equipped with an air heating method using steam and a method of blowing it onto the support using a nozzle).

[0146] As the exposure machine used in the above-mentioned active energy ray irradiation, any device that is equipped with a high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, mercury short-arc lamp, etc. and irradiates active energy rays in the range of 350 to 450 nm can be used. Furthermore, a direct drawing device (for example, a laser direct imaging device that directly draws an image with a laser using CAD data from a computer) can also be used. As the light source or laser source of the direct drawing machine, the maximum wavelength only needs to be in the range of 350 to 410 nm. The exposure amount for image formation varies depending on the film thickness, etc. Generally, it can be set to 20 to 1000 mJ / cm 2 , preferably set to be in the range of 20 to 800 mJ / cm 2 .

[0147] As the above-mentioned developing method, it can be based on the dipping method, spraying method, atomizing method, brushing method, etc. As the developer, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. can be used.

[0148] The curable resin composition of the present invention is suitable for forming a surface protective film such as a solder resist layer on a printed circuit board. It should be noted that the curable resin composition of the present invention can be used as an interlayer insulating layer of a multilayer printed circuit board.

[0149] [Electronic component]

[0150] In addition, the present invention also provides an electronic component having a cured product obtained 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 can be provided.

[0151] It should be noted that the electronic component of the present invention refers to a component used in an electronic circuit. In addition to active components such as printed circuit boards, transistors, light-emitting diodes, and laser diodes, it also includes passive components such as resistors, capacitors, inductors, and connectors. The cured product of the present invention exerts the effects of the present invention as these insulating cured coating films.

[0152] [Manufacture of the curable resin composition of the present invention]

[0153] 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, (C) a photoinitiator, and other components as desired in a specified amount, for example, using a three-roll mill.

[0154] Hereinafter, according to the examples, a specific embodiment of the present invention is shown, but of course, the scope of the invention claimed in the present application is not limited thereto.

[0155] Examples

[0156] Hereinafter, examples and comparative examples will be shown to specifically illustrate the present invention, but the present invention is of course not limited to the following examples.

[0157] It should be noted that unless otherwise stated, "parts" and "%" are based on mass.

[0158] [Examples 1 to 7 and Comparative Examples 1 to 3]

[0159] After premixing each of the components shown in Table 1 below in each compounding amount using a blender, they were kneaded with a three-roll mill to prepare curable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3, respectively. The stirring conditions of the blender were as follows: pre-stirring was carried out at a rotation speed of 500 rpm and a stirring time of 10 minutes, and formal stirring was carried out at a rotation speed of 800 rpm and a stirring time of 15 minutes. The blender blades used in any stirring were 12 cm. It should be noted that the values in the table are the values of the solid components except for the organic solvents.

[0160] [Synthesis Example 1]

[0161] Into a 2-liter detachable flask equipped with a blender, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, 900 g of diethylene glycol dimethyl ether as a solvent and 21.4 g of tert-butyl peroxy-2-ethylhexanoate (PERBUTYL O manufactured by NOF Corporation) as a polymerization initiator were added and heated to 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 (Praxel FM1 manufactured by Daicel Chemical Industry Co., Ltd.) and 21.4 g of bis(4-tert-butylcyclohexyl) peroxydicarbonate (Peroyl TCP manufactured by NOF Corporation) as a polymerization initiator were added dropwise thereto over 3 hours, and further aged for 6 hours to obtain a carboxyl-containing copolymer resin. It should be noted that the reaction was carried out under a nitrogen atmosphere.

[0162] Next, 363.9 g of 3,4-epoxycyclohexylmethyl methacrylate (Cyclomer A200 manufactured by Daicel Chemical 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-containing copolymer resin, and heated to 100°C and stirred to carry out a ring-opening addition reaction of epoxy. After 16 hours, a solution of a carboxyl-containing resin having an acid value of 108.9 mgKOH / g and a weight average molecular weight of 25,000 and not having an aromatic ring was obtained.

[0163] [Table 1]

[0164] Table 1. Ingredients and Their Blending Quantities of the Curable Resin Compositions of Examples 1 to 7 and Comparative Examples 1 to 3

[0165]

[0166] * 1 A-9300YN; Tris(2-hydroxyethyl)isocyanurate triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0167] * 2 A-DOD-N; 1,10-Decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0168] * 3 A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.

[0169] * 4 Laromer LR8863; manufactured by BASF SE

[0170] * 5 TEPIC (registered trademark)-VL; manufactured by Nissan Chemical Industries, Ltd.

[0171] * 6 jER828; manufactured by Mitsubishi Chemical Corporation

[0172] * 7 Synthesis Example 1

[0173] * 8 TIF-3 (acid value 130 mgKOH / g); manufactured by Shin-Nakamura Chemical Co., Ltd.

[0174] * 9 Omnirad TPO; 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide; manufactured by IGM Resins

[0175] * 10 Omnirad 819; Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; manufactured by IGM Resins

[0176] * 11 Irganox3114; manufactured by BASF Japan Ltd.

[0177] * 12 Irganox1010; manufactured by BASF Japan Ltd.

[0178] * 13 Irganox1330; manufactured by BASF Japan Ltd.

[0179] * 14 PX-3788; manufactured by Sakai Chemical Industry Co., Ltd.

[0180] * 15 Nipsil E-743 (average particle size 1.5 - 2.2 μm; specific surface area: 45 m 2 / g); manufactured by Tosoh Silica Corporation.

[0181] * 16 AEROSIL R974 (primary particle size 12 nm; specific surface area: 150 - 190 m 2 / g); manufactured by Nippon Aerosil Co., Ltd.

[0182] For the obtained curable resin compositions of Examples 1 - 7 and Comparative Examples 1 - 3, tests on color difference ΔE and storage stability were conducted as described below.

[0183] [Test on color difference ΔE (heat resistance discoloration)]

[0184] Using an applicator, the curable resin compositions of Examples 1 - 7 and Comparative Example 3 prepared above were respectively coated on a glass substrate, and subjected to a drying treatment at 80°C for 30 minutes to obtain a dried coating film with a film thickness of 20 μm. Then, through a patterned negative film, it was irradiated with a metal halide lamp light source with an exposure amount of 600 mJ / cm 2 After that, it was immersed in a 1% by mass aqueous sodium carbonate solution and developed, and then cured by heating at 150°C for 60 minutes.

[0185] For the obtained substrate, the peak temperature was set to 285°C, and a heat treatment was performed once for 10 seconds. The change amount ΔE (color difference) of the color from the initial value was calculated.

[0186] The case where ΔE is 2.0 or less is denoted as The case where ΔE is 2.1 or more and less than 4.0 is denoted as ○, and the case where ΔE is 4.0 or more is denoted as ×.

[0187] [Test on storage stability]

[0188] The curable resin compositions of Examples 1 - 7 and Comparative Examples 1 - 3 were allowed to stand at 20°C, and the number of days until separation occurred on the surface of these curable resin compositions was recorded starting from the time of standing.

[0189] [Table 2]

[0190] Table 2. Test results

[0191]

Claims

1. A curable resin composition containing 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, Among them, The curable resin composition further contains a carboxyl group-containing fluororesin and a carboxyl group-containing resin without fluorine atoms, The specific surface area is 10 m 2 / g or more and less than 100 m 2 / g of silica, and the specific surface area is 100 m 2 / g or more and less than 300 m 2 / g of silica.

2. The curable resin composition according to claim 1, wherein, It further contains (D) an antioxidant having an isocyanurate structure.

3. The curable resin composition according to claim 1 or 2, wherein It further contains (E) a white colorant.

4. A dry film having the curable resin composition according to any one of claims 1 to 3 as a resin layer.

5. A cured product which is a cured product of the curable resin composition according to any one of claims 1 to 3, or a cured product of the resin layer of the dry film according to claim 4.

6. An electronic component having the cured product according to claim 5.

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