TW202146501A - Curable composition, and dry film and cured object obtained therefrom - Google Patents

Abstract

To provide a curable composition capable of forming solder resists which combine flux resistance and folding endurance. The curable composition comprises (A) an alkali-soluble resin having at least any one structure selected from among a bisphenol A structure, a bisphenol F structure, and a urethane structure, (B) a photopolymerization initiator, and (C) an epoxy resin having an isocyanurate structure, wherein the epoxy resin (C) having an isocyanurate structure has a structure in which a nitrogen atom contained in the isocyanurate structure has been bonded to an epoxy group by an alkylene chain having two or more carbon atoms.

Description

Curable composition, its dry film and cured product

The present invention relates to a curable composition, in particular, a curable composition capable of forming a cured product that can achieve both flux resistance and bendability.

Conventionally, on a printed circuit board, a solder resist (SR) was formed to protect a circuit, and a semiconductor wafer or the like was soldered (mounted) on the printed circuit board on which the solder resist was formed. As a composition for forming such a solder resist, for example, the solder resist ink for circuit boards described in Patent Document 1, which is based on a photosensitive resin composition containing a carboxyl group-containing photosensitive polymer, can be mentioned.

On the other hand, during soldering, the surface of the circuit connection is usually coated with flux, however, during the coating step, the entire printed circuit board where the solder resist is formed is exposed to the flux. This flux is used to remove oxides or dirt on the circuit connection surface, prevent oxidation during heating, and even reduce the surface tension of the molten solder to improve the wettability of the solder to the joint. On the other hand, the use of the so-called flexible printed circuit board is increasing in the use of the printed circuit board for bending. In view of this, the solder resist forming the circuit board also needs to be flexible enough to withstand bending. flexibility. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 11-65117

[Problems to be solved by the invention]

That is, the solder resist must have flux resistance, that is, after applying the flux, it is not peeled from the printed circuit board during high-temperature processing of soldering, and the adhesion to the printed circuit board can be maintained. . Not only that, the solder resist must have bendability so that cracks do not occur even when the printed circuit board is bent.

However, in this regard, as described in Patent Document 1, the solder resist obtained from the conventional composition is easily degraded by the flux component, and also has insufficient flexibility, so it is not easy to achieve both the flux resistance and the bendability. . [Means for solving problems]

Then, in view of the above-mentioned problems, the present inventors studied and examined, and as a result, found a curable composition comprising an alkali-soluble resin having a structure such as bisphenol A, and a specific structure having both an isocyanurate structure and an alkylene structure. The epoxy resin can form a solder resist having both flux resistance and bending properties, and the present invention has been completed.

That is, the present invention relates to a curable composition comprising: (A) an alkali-soluble resin having at least any one of a bisphenol A structure, a bisphenol F structure, and a urethane structure, (B) a photopolymerization initiator, and (C) epoxy resins having an isocyanurate structure, The epoxy resin having the above-mentioned (C) isocyanurate structure has a structure in which a nitrogen atom and an epoxy group in the isocyanurate structure are bonded by an alkylene group having 2 or more carbon atoms. In addition, a suitable aspect of the present invention further relates to a curable composition containing a powder or a crystalline epoxy resin, preferably an epoxy resin having a biphenyl structure. In addition, a more suitable aspect of the present invention also relates to a curable composition further comprising an epoxy resin having a dicyclopentadiene structure. In addition, a more suitable aspect of the present invention also relates to a curable composition, wherein (C) the epoxy resin having an isocyanurate structure, the powder or crystalline epoxy resin, the epoxy resin having dicyclopentadiene The mass ratio of the epoxy resin for the structure is 1:2~6:1~3. In addition, a more suitable aspect of the present invention also relates to a curable composition further comprising urethane beads and/or epoxidized polybutadiene. In addition, a more suitable aspect of the present invention also relates to a curable composition further containing a cellulose resin. In addition, another aspect of the present invention also relates to a dry film having a resin layer obtained from the curable composition, and a cured product obtained by curing the curable composition or the resin layer of the dry film. and an electronic component having the hardened product. [Effect of invention]

According to the present invention, it is possible to provide a curable composition capable of forming a solder resist having excellent flux resistance and bending properties.

Hereinafter, each component which can comprise the curable composition of this invention is demonstrated.

[(A) Alkali-soluble resin] The (A) alkali-soluble resin used in the present invention is an alkali-soluble resin having at least any one of a bisphenol A structure, a bisphenol F structure, and a urethane structure. Alkali-soluble resins having structures other than these can be used in combination.

(A) Alkali-soluble resin is a resin that contains one or more functional groups among phenolic hydroxyl groups, thiol groups, and carboxyl groups, and is soluble in an alkali solution. Suitable examples include compounds having two or more phenolic hydroxyl groups, Carboxyl group-containing resins, compounds having phenolic hydroxyl groups and carboxyl groups, and compounds having two or more thiol groups. As the alkali-soluble resin, a carboxyl group-containing resin or a phenolic hydroxyl group-containing resin can be used, and a carboxyl group-containing resin is preferred.

The carboxyl group-containing resin can have alkali developability by containing the carboxyl group. In addition, from the viewpoint of photocurability or development resistance, it is preferable to have an ethylenically unsaturated group in the molecule in addition to the carboxyl group, but only a carboxyl group-containing resin having no ethylenically unsaturated group may be used. The ethylenically unsaturated group is preferably derived from acrylic acid or methacrylic acid or derivatives thereof. Among the carboxyl group-containing resins, carboxyl group-containing resins with urethane structure, carboxyl group-containing resins with bisphenol A type epoxy resin or bisphenol F type epoxy resin as starting materials, bisphenol-based epoxy resins A carboxyl group-containing resin with A or bisphenol F as the starting material is preferred. Specific examples of the carboxyl group-containing resin include the compounds listed below (either an oligomer or a polymer may be used).

(1) bisphenol A type epoxy resin or bisphenol F type epoxy resin and (meth)acrylic acid are reacted, and phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride Dibasic acid anhydrides such as these are added to the carboxyl group-containing photosensitive resin of the hydroxyl group present in the side chain. Here, it is preferable that a difunctional or higher polyfunctional epoxy resin is a solid.

(2) The hydroxyl group of bisphenol A type epoxy resin or bisphenol F type epoxy resin is further epoxidized with epichlorohydrin to form a multifunctional epoxy resin, and then reacted with (meth)acrylic acid, and the generated hydroxyl group is Carboxyl group-containing photosensitive resin obtained by adding dibasic acid anhydride. Here, the difunctional epoxy resin is preferably solid.

(3) A compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, a bisphenol A type epoxy resin or a bisphenol F type epoxy resin, and an unsaturated group-containing monolayer such as (meth)acrylic acid carboxylic acid reaction, the alcoholic hydroxyl group of the obtained reaction product is reacted with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromite anhydride, adipic acid, etc., and the obtained Carboxyl-containing photosensitive resin.

(4) The condensate of bisphenol A or bisphenol F and aldehydes is reacted with alkylene oxide such as ethylene oxide and propylene oxide, and the obtained reaction product is made to react with a non-condensing product such as (meth)acrylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a monocarboxylic acid of a saturated group and reacting the obtained reaction product with a polybasic acid anhydride.

(5) bisphenol A or bisphenol F is reacted with a cyclic carbonate compound such as ethylene carbonate and propylene carbonate, the obtained reaction product is reacted with an unsaturated group-containing monocarboxylic acid, and the obtained The carboxyl group-containing photosensitive resin obtained by reacting the reaction product with the polybasic acid anhydride.

(6) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, etc., and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyols Urethanes produced by addition polymerization of diol compounds such as olefin-based polyols, acrylic-based polyols, bisphenol A-based alkylene oxide adduct diols, and compounds having phenolic and alcoholic hydroxyl groups A urethane resin containing a terminal carboxyl group obtained by reacting the terminal of the resin with an acid anhydride.

(7) In the synthesis of carboxyl-containing urethane resins produced by addition polymerization of carboxyl-containing diol compounds such as diisocyanate, dimethylolpropionic acid, dimethylolbutyric acid, and diol compounds, Carboxyl group-containing urethane resin obtained by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule such as hydroxyalkyl (meth)acrylate to (meth)acrylate the terminal .

(8) In the synthesis of the carboxyl-containing urethane resin produced by the addition polymerization of diisocyanate, carboxyl-containing diol compound, and diol compound, adding isophorone diisocyanate and pentaerythritol triacrylate A carboxyl group-containing urethane resin obtained by (meth)acrylating a terminal of a compound having one isocyanate group and one or more (meth)acryloyl groups in a molecule such as an ear reactant.

(9) A carboxyl group-containing photosensitive resin which is a carboxyl group-containing resin of any one of the above-mentioned (1) to (8) is added to a compound having a cyclic ether group and a (meth)acryloyl group in one molecule.

As the alkali-soluble resin having a structure other than the (A) alkali-soluble resin, compounds (any of an oligomer or a polymer may be used) as listed below are exemplified. (10) 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, and isobutylene The obtained carboxyl group-containing photosensitive resin.

(11) Dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid is reacted with a polyfunctional oxetane resin as described later, and a dibasic acid anhydride is added to the generated primary hydroxyl group The carboxyl group-containing polyester resin is further added with glycidyl (meth)acrylate, α-methyl glycidyl (meth)acrylate, etc. in one molecule having one epoxy group and one or more (methyl) Carboxyl group-containing photosensitive resin composed of acryl group compounds.

(12) A carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth)acryloyl group in one molecule to the carboxyl group-containing resin of (10) or (11).

In addition, (meth)acrylate here is a term collectively referring to an acrylate, a methacrylate, and a mixture thereof, and the following other similar expressions are also the same.

Here, the acid value of the carboxyl group-containing resin is preferably 40 to 150 mgKOH/g. By setting the acid value of the carboxyl group-containing resin to be 40 mgKOH/g or more, alkali development becomes favorable. In addition, by setting the acid value to be less than 150 mgKOH/g, it is easy to draw a normal photoresist pattern. Preferably, it is 50-130 mgKOH/g.

The blending amount of the above-mentioned (A) alkali-soluble resin is preferably 15 to 35% by mass in the entire composition. In the case of 15 to 35 mass %, the coating film strength is good, the viscosity of the composition is appropriate, and the coatability and the like are improved.

[(B) Photopolymerization Initiator] (B) The photopolymerization initiator can be used as long as it is a photopolymerization initiator known as a photopolymerization initiator or a photoradical generator. For example, bis-(2,6-di Chlorobenzyl)phenylphosphine oxide, bis-(2,6-dichlorobenzyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzyl) yl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzyl) Phenylphosphine oxide, bis-(2,6-dimethoxybenzyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzyl) bis-(2,5-dimethylphenylphosphine oxide), bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, etc.; 2,6- Dimethoxybenzyldiphenylphosphine oxide, 2,6-dichlorobenzyldiphenylphosphine oxide, methyl 2,4,6-trimethylbenzylphenylphosphonate, Monobenzyl oxidation of 2-methylbenzyldiphenylphosphine oxide, isopropyl pivaloylphenylphosphonate, 2,4,6-trimethylbenzyldiphenylphosphine oxide, etc. Phosphines; 1-Hydroxy-cyclohexylphenone, 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 -Hydroxyacetophenones such as 1-phenylpropan-1-one; Benzoin, Diphenylethanedione, Benzoin methyl ether, Benzoin ethyl ether, Benzoin n-propyl ether, Benzoin isopropyl ether, Benzoin n-butyl ether Benzoins such as ethers; Benzoin alkyl ethers; Benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis Benzophenones such as diethylaminobenzophenone; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylbenzene Ethanone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenone, 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 and other acetophenones; thioxanthone, 2 -Ethyl thioxanthone, 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-dithioxanthone Thioxanthones such as isopropyl thioxanthone; anthraquinone, chloranthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2 -Anthraquinones such as amylanthraquinone and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.; ethyl-4-dimethylamino Benzoic acid esters such as benzoate, 2-(dimethylamino)ethylbenzoate, ethyl p-dimethylbenzoate, etc.; 1,2-octanedione ,1-[4-(Phenylthio)-,2-(O-benzyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)- Oxime esters such as 9H-carbazol-3-yl]-,1-(O-acetyloxime); 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-pyrrole-1- base) ethyl) phenyl] titanocenes such as titanium; phenyl disulfide 2-nitrofluorene, butyroin, anisin ethyl ether, azobisisobutyronitrile, tetramethylthiuram Methyl disulfide, etc. The photopolymerization initiators may be used alone or in combination of two or more.

The blending amount of the (B) photopolymerization initiator is preferably 8 to 15 parts by mass relative to 100 parts by mass of the (A) alkali-soluble resin. Within this range, the surface hardening property becomes favorable, halo is less likely to occur, and favorable resolution can be obtained.

[(C) Epoxy resin with isocyanurate structure] In the curable composition of the present invention, an epoxy resin having an isocyanurate structure is contained, and the number of carbon atoms between the nitrogen atom and the epoxy group in the isocyanurate structure is two or more. The structure of the alkylene chain linkage. In particular, an epoxy resin having a structure in which the number of carbon atoms in the alkylene chain is 2 or more and 5 or less is preferred. As long as the carbon number of the alkylene chain is in the range of 2 to 5, the cured product obtained from the curable composition can achieve both effective flux resistance and bending properties. In addition to this, the original developability of the curable composition can be maintained.

(式中， R₁ 、R₂ 及R₃ 各自獨立地表示碳數2~5之伸烷基，n為0或1，但是，全部的n不會同時為0)The epoxy resin having an isocyanurate structure (C) used in the present invention preferably has a structure represented by the following formula (1).

(In the formula, R ₁ , R ₂ and R ₃ each independently represent an alkylene group having 2 to 5 carbon atoms, and n is 0 or 1, but all n are not 0 at the same time)

Among them, particularly preferred is a structure in which R ₁ , R ₂ and R ₃ simultaneously represent an alkylene group having 3 carbon atoms, and n is 1 at the same time.

(C) Specific products of the epoxy resin having an isocyanurate structure suitable for use in the present invention include, for example, TEPIC (registered trademark)-VL or TEPIC (registered trademark)-FL (any of them is manufactured by Nissan Chemical Industries, Ltd.).

The compounding quantity of the epoxy resin having such an isocyanurate structure (C) is preferably 5 to 15 parts by mass relative to 100 parts by mass of the (A) carboxyl group-containing resin. Within this range, not only good flux resistance and bending properties can be imparted to the cured product, but also the original developability of the curable composition can be maintained.

[Inorganic filler] In the curable composition of the present invention, an inorganic filler may be contained in order to suppress the curing shrinkage and improve characteristics such as adhesion and hardness. Such inorganic fillers are not particularly limited, and well-known and conventional fillers can be used, such as silica, crystalline silica, Neuburg silica, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, carbonic acid Inorganic fillers such as calcium, natural mica, synthetic mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, slag wool, aluminum silicate, calcium silicate, zinc fluoride, etc. In particular, silicon dioxide is preferred, and spherical silicon dioxide is preferred from the viewpoint of having a small surface area and dispersing stress as a whole so as not to become a starting point for cracks.

Inorganic fillers can also undergo photoreactive surface treatment to have vinyl, styryl, methacryloyl, and acryl groups as photohardenable reactive groups. In this case, methacryloyl, propylene Acyl and vinyl are particularly preferred. In addition, it can also be thermally reactive surface treated to have hydroxyl, carboxyl, isocyanate, amine, imine, epoxy, oxetanyl, mercapto, methoxymethyl, methoxyethyl As the thermosetting reactive group, an amine group and an epoxy group are particularly preferred. In addition, the inorganic filler may have two or more hardenable reactive groups. The inorganic filler is preferably surface-treated silica. By containing surface-treated silica, the CTE can be reduced and the glass transition temperature can be increased.

In the case of introducing a curable reactive group into the surface of the inorganic filler, the introduction method is not particularly limited, and the introduction method may be carried out by a well-known and conventional method, as long as a surface treatment agent having a curable reactive group, for example, The surface of the inorganic filler can be treated with a mixture or the like.

The surface treatment of the inorganic filler is preferably a surface treatment with a coupling agent. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent and the like can be used. In particular, a silane coupling agent is preferred.

The silane coupling agent is preferably a silane coupling agent capable of introducing a hardening reactive group into the inorganic filler. Silane coupling agents into which thermosetting reactive groups can be introduced include epoxy group-containing silane coupling agents, amine group-containing silane coupling agents, mercapto group-containing silane coupling agents, isocyanate group-containing silane coupling agents, especially epoxy group-containing silane coupling agents. based silane coupling agents are preferred. Silane coupling agents capable of introducing photohardening reactive groups include vinyl-containing silane coupling agents, styryl group-containing silane coupling agents, methacryloyl group-containing silane coupling agents, and acryl group-containing silane coupling agents. Preferably, a silane coupling agent having a methacryloyl group is particularly preferred.

In the case of surface treatment of the inorganic filler, it is only necessary to mix it with the curable resin composition of the present invention in a surface-treated state, or the inorganic filler and the surface treatment agent without surface treatment can be mixed separately, and the composition It is better to mix inorganic fillers that have been surface-treated in advance. By blending the inorganic fillers that have been surface-treated in advance, it is possible to prevent a reduction in crack resistance or the like caused by the remaining surface-treating agent that may not have been consumed during the surface treatment, in the case of separate blending. In the case of pre-surface treatment, it is better to blend a pre-dispersion liquid obtained by pre-dispersing inorganic fillers in a solvent or resin component, pre-dispersing the surface-treated inorganic fillers in a solvent, and mixing the pre-dispersion liquid with the pre-dispersed liquid. It is preferable to blend into the composition, or to sufficiently surface-treat the inorganic filler without surface treatment when pre-dispersing in a solvent, and then blend the pre-dispersed liquid into the composition.

In the curable composition of the present invention, the average particle diameter of the inorganic filler is preferably 1 μm or less from the viewpoint of more excellent crack resistance. Preferably it is 0.8 micrometer or less. Further, in the present specification, the average particle diameter D ₅₀ is a value of, for example, manufactured by Nikkiso Microtrac particle size analyzer the measured value.

In addition, the maximum particle diameter of the inorganic filler is preferably 4.0 μm or less, from the viewpoints of efficient reaction and superior crack resistance and adhesion. Preferably it is 3.0 micrometers or less. Further, in the present specification, the maximum particle diameter D ₁₀₀ is a value of, for example, using the measurement value obtained by Nikkiso Microtrac particle size analyzer manufactured by the meter.

When the curable composition of the present invention contains an inorganic filler, the blending amount of the inorganic filler is preferably 15 to 35 parts by mass relative to 100 parts by mass of the solid content of the curable composition.

[Powder or crystalline epoxy resin] In the curable composition of the present invention, it is preferable to contain epoxy resin, especially powder or crystalline epoxy resin, so that the flux resistance of the cured product can be further improved. Powder or crystalline epoxy resin refers to epoxy resin with strong crystallinity, and it means that the polymer chains are regularly arranged at a temperature below the melting point, and it is a solid resin, and when melted, it becomes equivalent to a liquid resin. Low viscosity thermosetting epoxy resin.

As the powder or crystalline epoxy resin, it is preferable to use a crystalline epoxy resin having any one of a biphenyl structure, a sulfide structure, a phenylene structure, and a naphthalene structure. Biphenyl-type epoxy resins are marketed as "jER (registered trademark) YX4000", "jER (registered trademark) YX4000H", "jER (registered trademark) YL6121H", "jER (registered trademark)" manufactured by Mitsubishi Chemical Corporation, for example. YL6640" and "jER (registered trademark) YL6677", and diphenyl sulfide type epoxy resins are commercially available as "EPOTOTE (registered trademark) YSLV-120TE" manufactured by Nippon Steel Chemical & Material Co., Ltd., Phenylene-type epoxy resins are commercially available as "EPOTOTE (registered trademark) YDC-1312" manufactured by Nippon Steel Chemical & Material Co., Ltd., and naphthalene-type epoxy resins are commercially available as "EPOTOTE (registered trademark) YDC-1312" manufactured by DIC Corporation. EPICLON (registered trademark) HP-4032", "EPICLON (registered trademark) HP-4032D", "EPICLON (registered trademark) HP-4700" are available. In addition, as the powder or crystalline epoxy resin, "EPOTOTE (registered trademark) YSLV-90C" manufactured by Nippon Steel Chemical & Material Co., Ltd., "TEPIC-S" (triglycidyl isocyanuric acid) manufactured by Nissan Chemical Co., Ltd. ester). Among them, the biphenyl type epoxy resin "jER (registered trademark) YX4000" manufactured by Mitsubishi Chemical Corporation is preferable from the viewpoint of excellent properties of soldering heat resistance. In the curable composition of the present invention, these powders or crystalline epoxy compounds may be used alone or in combination of two or more.

The blending amount of such powder or crystalline epoxy resin is preferably 20 to 40 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin on the basis of solid content. When the blending amount of the powder or the crystalline epoxy resin is within the above-mentioned range, the developability and the flux resistance will become more favorable.

In addition, in the curable composition of the present invention, in order to improve heat resistance, it goes without saying that epoxy resins other than powders or crystalline epoxy resins may be further contained. Such epoxy resins include, for example, amorphous cresol novolac epoxy resins (specific examples are EPICLON N-695 manufactured by DIC Co., Ltd.), amorphous phenol novolac epoxy resins (specific examples The products are EPICLON N-775 manufactured by DIC Co., Ltd.), amorphous bisphenol A novolac epoxy resin (specific example is EPICLON N-865 manufactured by DIC Co., Ltd.), amorphous bisphenol A Type epoxy resin (specifically, product jER 1001 manufactured by Mitsubishi Chemical Corporation), amorphous bisphenol F-type epoxy resin (specifically, product jER 4004P manufactured by Mitsubishi Chemical Corporation), amorphous bisphenol S type epoxy resin (specific example is the product EPICLON EXA-1514 made by DIC Corporation), amorphous bisphenol AD type epoxy resin, amorphous hydrogenated bisphenol A type epoxy resin, Amorphous biphenyl novolac epoxy resin and amorphous special bifunctional epoxy resin (specific examples are YL7175-500 and YL7175-1000 manufactured by Mitsubishi Chemical Co., Ltd.; products manufactured by DIC Co., Ltd. Amorphous epoxy resins like EPICLON TSR-960, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA-4850, EPICLON EXA-4816, EPICLON EXA-4822 and EPICLON EXA-9726 ).

Alternatively, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, or a phenol novolac type epoxy resin can be mentioned. Specific examples of liquid epoxy resins include "EXA4032SS", "HP4032SS", "EXA-7311G4S" (naphthalene-type epoxy resin) manufactured by DIC Corporation, and "jER 828EL manufactured by Mitsubishi Chemical Corporation. "(bisphenol A epoxy resin), "jER 807" (bisphenol F epoxy resin), "jER152" (phenol novolac epoxy resin), "YL7223", "YL7723" (bisphenol AF epoxy resin) Oxygen resin) like liquid epoxy resin.

Alternatively, for example, tetrafunctional naphthalene type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol epoxy resin, naphthol novolac epoxy resin, biphenyl type epoxy resin can be mentioned. , or solid epoxy resin like naphthyl ether type epoxy resin. Among them, tetrafunctional naphthalene type epoxy resin, biphenyl type epoxy resin or naphthyl ether type epoxy resin are preferred, and biphenyl type epoxy resin is more preferred. Specific examples of such solid epoxy resins include "HP-4710" (tetrafunctional naphthalene type epoxy resin), "EXA7311", "EXA7311-G3", and "HP6000" (naphthalene ether) manufactured by DIC Co., Ltd. type epoxy resin), "EPPN-502H" (trisphenol epoxy resin), "NC7000L" (naphthol novolac epoxy resin), "NC3000H", "NC3000", "NC3000L" manufactured by Nippon Kayaku Co., Ltd. , "NC3100" (biphenyl type epoxy resin), "ESN475", "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd., cresol-type epoxy resin).

Here, in the curable composition of the present invention, it is preferable to contain an epoxy resin having a dicyclopentadiene structure as a powder or an epoxy resin other than a crystalline epoxy resin. As such an epoxy resin, "HP7200", "HP7200H", "HP7200K", or "HP7200L" by DIC Co., Ltd. are mentioned, for example. In particular, the mass ratio of the above-mentioned (C) epoxy resin having an isocyanurate structure, the above-mentioned powder or crystalline epoxy resin, and an epoxy resin having a dicyclopentadiene structure is 1:2 to 6 : 1~3 is better. Within this numerical range, the curable composition of the present invention can exhibit optimum flux resistance and bending properties.

The mixing ratio of the above-mentioned powder or crystalline epoxy resin and other epoxy resins is preferably in the range of 5:1 to 1:5 in terms of mass ratio.

[Urethane beads/epoxidized polybutadiene] In the curable composition of the present invention, in order to improve flexibility, it is preferable to contain urethane beads and/or epoxidized polybutadiene. In particular, by containing epoxidized polybutadiene, the bendability of the cured product becomes more favorable. The blending amount of the urethane beads is preferably 20 parts by mass to 35 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. The blending amount of the epoxidized polybutadiene is preferably 8 parts by mass or more and 12 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin.

[cellulose resin] In the curable composition of the present invention, it is preferable to contain a cellulose resin. By containing the cellulose resin, the amount of liquid components (for example, liquid epoxy resin or monomer components) can be increased, so that it is easy to ensure flux resistance. In addition, the effect of suppressing tack at the time of exposure is exhibited. The blending amount of the cellulose resin is preferably 5 parts by mass to 10 parts by mass relative to 100 parts by mass of the (A) alkali-soluble resin.

[Colorant] The curable composition of the present invention may contain a colorant. Specific examples of the colorant include phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, leuco crystal violet, carbon black, naphthalene black, solvent blue, and the like. The coloring agent may be used alone or in combination of two or more.

The addition amount of the colorant is not particularly limited, but ideally, a ratio of 7 to 15 parts by mass relative to 100 parts by mass of the (A) alkali-soluble resin is sufficient.

[Organic solvents] In addition, the curable composition of the present invention may contain an organic solvent for the purpose of preparing the composition or adjusting the viscosity at the time of coating on a substrate or a carrier film. As the organic solvent, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, Dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether, etc. Alcohol ethers; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, diethyl ether Esters such as propylene glycol monomethyl ether acetate and propylene carbonate; aliphatic hydrocarbons such as octane and decane; and well-known and usual organic solvents such as petroleum-based solvents such as petroleum ether, naphtha, and mineral spirits. These organic solvents may be used alone or in combination of two or more.

[Compounds with ethylenically unsaturated groups] The curable composition of the present invention further preferably contains a compound having an ethylenically unsaturated group as a reactive diluent. As a compound which has an ethylenically unsaturated group, the compound which has a (meth)acryloyl group, such as a monofunctional or a difunctional, is mentioned.

Compounds having a monofunctional (meth)acryloyl group include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylate base) 4-hydroxybutyl acrylate, hydroxypropyl (meth)acrylate, butoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, ( Aliphatic (meth)acrylates such as isodecyl meth)acrylate, glycerol mono(meth)acrylate, cyclohexyl (meth)acrylate, 4-(meth)acryloyloxytricyclo[5.2 .1.02,6] Alicyclic (meth)acrylates such as decane, isobornyl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylate ) Modified (meth)acrylates such as aromatic (meth)acrylates such as phenyl acrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate, and modified (meth)acrylates such as aliphatic epoxy modified (meth)acrylates base) acrylate, tetrahydrofuran methyl (meth)acrylate, 2-(meth)acryloyloxyalkyl phosphate, 2-(meth)acryloyloxyethyl phosphate, (meth)acryloyl phosphate Oxyethyl phthalate monoester, γ-(meth)acryloyloxyalkyltrialkoxysilane, etc.

In addition, specific examples of the compound having a bifunctional (meth)acryloyl group include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, and 1,9-nonanediol diacrylate. Acrylates, diacrylates of diols such as 1,10-decanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate Addition of at least one of acrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, ethylene oxide and propylene oxide Diacrylate of glycol obtained from neopentyl glycol, diacrylate of glycol such as caprolactone-modified hydroxypivalate neopentyl glycol diacrylate, bisphenol A EO adduct diacrylate Esters, bisphenol A PO adduct diacrylate, tricyclodecane dimethanol diacrylate, hydrogenated dicyclopentadienyl diacrylate, cyclohexyl diacrylate and other cyclic structure diacrylates, etc. . In addition, specific examples of the compound having a trifunctional or higher (meth)acryloyl group include pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Alkylene polyol poly(meth)acrylates such as acrylates, dipentaerythritol hexa(meth)acrylate, etc.; polyoxyalkylene diacrylates such as propoxylated trimethylolpropane tri(meth)acrylate Alcohol poly(meth)acrylates, etc.

The blending amount of the compound having an ethylenically unsaturated group is preferably 20 parts by mass to 40 parts by mass relative to 100 parts by mass of the (A) alkali-soluble resin.

[Thermosetting catalyst] The curable composition of the present invention may contain a thermosetting catalyst in order to improve its storage stability and heat resistance. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano Imidazole derivatives of ethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.; dicyandiamine, benzyldimethylamine, 4- (Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine Amine compounds such as amines, hydrazine compounds such as adipic acid dihydrazine, lipoic acid dihydrazine, etc.; phosphorus compounds such as triphenylphosphine, and the like. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2 ,4-Diamino-S-triazine, 2-Vinyl-4,6-diamino-S-triazine･Isocyanuric acid adduct, 2,4-Diamino-6-methyl S-triazine derivatives such as acryloyloxyethyl-S-triazine/isocyanuric acid adducts.

The blending amount of the thermosetting catalyst is preferably 2.0 to 4.5 parts by mass relative to 100 parts by mass of the (A) alkali-soluble resin.

[other ingredients] In the curable composition of the present invention, other additives known and commonly used in the field of electronic materials may be further blended. Other additives include thermal polymerization inhibitor, ultraviolet absorber, silane coupling agent, plasticizer, flame retardant, antistatic agent, antiaging agent, antibacterial and antifungal agent, leveling agent, tackifier, adhesion imparting agent Agents, shake modifiers, photoinitiating aids, sensitizers, photobase generators, thermoplastic resins, and even organic fillers such as elastomers, mold release agents, surface treatment agents, dispersants, dispersing aids, surface Modifiers, stabilizers, phosphors, etc.

[Dry film] The curable composition of the present invention can also be used after being dried. The dry film of the present invention has a resin layer obtained by coating the curable composition of the present invention on a carrier film and drying it. When forming a dry film, first, the curable composition of the present invention is diluted with the above-mentioned organic solvent, adjusted to an appropriate viscosity, and then passed through a comma-shaped blade coater, a blade coater, a lip coater, Rod coater, extrusion coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc., coat the carrier film with uniform thickness. Then, the applied composition is usually dried at a temperature of 40 to 130° C. for 1 to 30 minutes to form a resin layer. The coating film thickness is not particularly limited, and generally, it can be appropriately selected so that the film thickness after drying is 3 to 150 μm, preferably 5 to 60 μm.

The carrier film can be a plastic film, such as a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyimide film, a polypropylene film, a polystyrene film, etc. . The thickness of the carrier film is not particularly limited, and can generally be appropriately selected within the range of 10 to 150 μm. The range of 15-130 micrometers is preferable.

After the resin layer is formed from the curable composition of the present invention on the carrier film, it is preferable to further laminate a peelable protective film on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. As the peelable protective film, for example, polyethylene film or polytetrafluoroethylene film, polypropylene film, surface-treated paper and the like can be used. The protective film should just be a protective film smaller than the adhesive force between the resin layer and the carrier film when the protective film is peeled off.

Moreover, in this invention, the curable composition of this invention is apply|coated on the said protective film, it is made to dry, a resin layer is formed, and a carrier film can also be laminated|stacked on the surface. That is, in this invention, at the time of manufacture of a dry film, the film to which the curable composition of this invention is apply|coated can use any of a carrier film and a protective film.

[hardened product] When the curable composition of the present invention is used to form a cured product, the composition is applied to a substrate, the solvent is volatilized and dried, and then the obtained resin layer is exposed (illuminated), and the exposed part (the part that receives the illumination) is exposed. will harden. Specifically, in a contact or non-contact manner, through a patterned photomask, selectively exposed to active energy rays or directly exposed to a pattern by a laser direct exposure machine, with an alkaline aqueous solution (such as 0.3 to 3 mass % sodium carbonate aqueous solution) to develop the unexposed portion to form a photoresist pattern. By further heating to a temperature of about 100 to 180°C and thermally curing it (post-curing), a cured film (cured) excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties can be formed. thing).

The curable composition of the present invention, for example, is adjusted to a viscosity suitable for the coating method using the above-mentioned organic solvent, by dip coating method, flow coating method, roll coating method, bar coating method, screen printing method, curtain coating method, etc. After being coated on the substrate by a method such as a formula coating method, the organic solvent contained in the composition is volatilized and dried (preliminary drying) at a temperature of about 60 to 100° C. to form a non-sticking resin layer. In addition, in the case of applying the above curable composition on a carrier film or a protective film, drying it and winding it into a dry film of a film roll, the resin layer of the dry film of the present invention and the resin layer of the dry film of the present invention are formed by a laminator or the like. The substrate is attached to the substrate in a way of contacting the substrate, and then the carrier film is peeled off, and the resin layer can be laminated on the substrate.

In addition to the printed circuit board or flexible printed circuit board in which the circuit is formed by copper or the like, the substrate can also be made of phenolic paper, epoxy paper, epoxy glass cloth, glass polyimide, glass cloth/ All materials such as epoxy non-woven fabric, glass cloth/epoxy paper, epoxy synthetic fiber, fluororesin, polyethylene, polyphenylene ether, polyphenylene ether, cyanate, etc., and copper-clad laminates for high-frequency circuits Grade (FR-4, etc.) copper-clad laminates, other metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, etc. .

For the above-mentioned volatilization drying or thermal curing, hot air circulation type drying furnace, IR furnace, hot plate, convection oven, etc. can be used (the method of contacting the hot air in the dryer countercurrently using a device equipped with an air heating type heat source using steam, and the method of blowing to a support).

The exposure machine used for the above-mentioned active energy ray irradiation may 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. to irradiate active energy rays in the range of 350 to 450 nm. A drawing device (eg, a laser direct imaging device that draws an image directly with a laser by means of CAD data from a computer). The light or laser light source of the direct drawing machine can be a light source with a maximum wavelength in the range of 350~410nm. The exposure amount used to form the image will vary according to the film thickness, etc., but generally can be set in the range of 20~1000mJ/cm ² , preferably 20~800mJ/cm ² .

The above-mentioned developing methods can use dipping method, rinsing method, spraying method, brushing method, etc. The developing solution can use potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amine Aqueous alkaline solutions such as

The curable composition of the present invention is suitably used for forming a surface protection film such as a solder resist on a flexible printed wiring board. In addition, the curable composition of the present invention can also be used as an interlayer insulating layer of a multilayer printed wiring board.

[electronic parts] The present invention also provides an electronic component having a cured product obtained by curing the curable composition of the present invention. By using the curable composition of the present invention, electronic parts with high quality, durability and reliability can be provided. In addition, in the present invention, electronic parts mean parts used in circuits, including resistors, capacitors, inductors, connectors, in addition to active elements such as printed circuit boards, transistors, light-emitting diodes, laser diodes, etc. (connector) and the like, the cured product of the present invention exhibits the effect of the present invention as its insulating cured coating film.

In addition, the hardened product of the present invention exhibits good resistance to all the fluxes of the conventional composition and formulation mainly composed of rosin, and some examples of such fluxes include SF-270, SF- 360PF-1, SRM-800G (all are manufactured by Sanwa Chemical Co., Ltd.), JS-E-15X, JS-EU-31 (all are manufactured by Honghui Corporation), NS-F850-8, NS -F901, NS-334, NS-316F-8 (made by Japan Superior Co., Ltd.), etc.

One aspect of the present invention is specifically described below by means of embodiments, of course, the purpose is not to limit the scope of the invention related to the claims of the present invention. [Example]

<Synthesis example 1. Preparation of carboxyl group-containing acrylate resin (bisphenol A structure)> 456 parts of bisphenol A, 228 parts of water, and 649 parts of 37% formalin were placed in a flask equipped with a condenser tube and a stirrer, the temperature was kept below 40°C, and 228 parts of a 25% aqueous sodium hydroxide solution was added. The reaction was carried out at °C for 10 hours. After the completion of the reaction, it was cooled to 40°C, and neutralized to pH 4 with a 37.5% phosphoric acid aqueous solution while maintaining the temperature below 40°C. It was then left to stand and the aqueous layer was separated. After separation, 300 parts of methyl isobutyl ketone was added and uniformly dissolved, and then washed three times with 500 parts of distilled water, and water, solvent, and the like were removed at a temperature of 50° C. or lower and under reduced pressure. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanol solution of the polymethylol compound. When a part of the methanol solution of the obtained polymethylol compound was dried at room temperature in a vacuum dryer, the solid content was 55.2%.

500 parts of the methanol solution of the obtained polymethylol compound and 440 parts of 2,6-xylenol were put into a flask equipped with a condenser and a stirrer, and were uniformly dissolved at 50°C. After uniform dissolution, methanol was removed under reduced pressure at a temperature of 50° C. or lower. Then, 8 parts of oxalic acid was added, and the reaction was carried out at 100° C. for 10 hours. After completion of the reaction, distillate components were removed at 180° C. under a reduced pressure of 50 mmHg to obtain 550 parts of phenol resin A. 130 parts of phenolic resin A, 2.6 parts of 50% sodium hydroxide aqueous solution, toluene/methyl isobutyl ketone (mass ratio= 2/1) 100 parts, nitrogen-substitute the inside of the system with stirring, then heat up and raise the temperature, and slowly introduce 60 parts of propylene oxide ^{at 150° C. and 8 kg/cm 2 to react.} After the reaction was continued for about 4 hours until the gauge pressure became 0.0 kg/cm ² , it was cooled to room temperature. To this reaction solution, 3.3 parts of a 36% hydrochloric acid aqueous solution was added and mixed to neutralize sodium hydroxide. The neutralization reaction product was diluted with toluene, washed three times with water, and removed the solvent with an evaporator to obtain a propylene oxide adduct of phenolic resin A having a hydroxyl value of 189 g/eq. This is an adduct of 1 mole of propylene oxide added to an average of 1 equivalent of phenolic hydroxyl group.

189 parts of the propylene oxide adduct of the obtained phenolic resin A, 36 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 part of hydroquinone monomethyl ether, and 140 parts of toluene were put into a mixer equipped with a mixer, a thermometer and an air blower. The reactor was heated up to 115° C. while stirring while blowing air to carry out the reaction, and the produced water and toluene were distilled off as an azeotrope, and the reaction was further allowed to react for 4 hours, and then cooled to room temperature. The obtained reaction solution was washed with water using a 5% NaCl aqueous solution, and toluene was removed by distillation under reduced pressure, and then diethylene glycol monoethyl ether acetate was added to obtain an acrylate resin solution with a solid content of 67%.

Next, 322 parts of the previously obtained acrylate resin solution, 0.1 part of hydroquinone monomethyl ether, and 0.3 part of triphenylphosphine were placed in a four-necked flask equipped with a stirrer and a reflux condenser, and the mixture was heated to At 110° C., 60 parts of tetrahydrophthalic anhydride was added, and it was made to react for 4 hours, and it was taken out after cooling. The photosensitive carboxyl group-containing resin solution obtained in this way had a solid content of 70% and an acid value of the solid content of 81 mgKOH/g.

<Synthesis example 2. Preparation of carboxyl group-containing resin for comparative example> Into a 2-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, 900 g of diethylene glycol dimethyl ether as a solvent and tert-butylperoxide as a polymerization initiator were added 2-ethylhexanoate (PERBUTYL O by NOF Corporation) 21.4 g, and heated to 90 degreeC. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (PLACCEL FM1 by Daicel Chemical Industry Co., Ltd.) were added dropwise over 3 hours. , and 21.4 g of bis(4-tert-butylcyclohexyl) peroxydicarbonate (PEROYL TCP manufactured by NOF Corporation) as a polymerization initiator was further aged for 6 hours to obtain a carboxyl group-containing copolymer resin. In addition, the reaction was carried out under nitrogen atmosphere. Next, 363.9 g of 3,4-epoxycyclohexyl methacrylate (CYCLOMER A200 manufactured by DAICEL Chemical Co., Ltd.) and dimethyl as a ring-opening catalyst were added to the obtained carboxyl group-containing copolymer resin. 3.6 g of benzylamine and 1.80 g of hydroquinone monomethyl ether as a polymerization inhibitor were heated to 100° C. and stirred to perform a ring-opening addition reaction of epoxy. After 16 hours, a solution containing 53.8% by weight (non-volatile content) of a carboxyl group-containing resin having a solid content of 108.9 mgKOH/g, a weight average molecular weight of 25,000 and no aromatic ring was obtained.

<Examples 1 to 7 and Comparative Examples 1 to 2> Each component was premixed with a mixer according to the components and blending amounts shown in Table 1 below, and then kneaded with a three-roll mill to obtain curable compositions of Examples 1 to 7 and Comparative Examples 1 to 2. In addition, the numerical value of the compounding quantity in a table|surface represents the mass part of solid content, unless otherwise specified.

*1 雙酚F型酸改質環氧丙烯酸酯樹脂、具有雙酚F構造的鹼可溶樹脂(固體成分65%)；ZFR-1401H；日本化藥公司製 *2 複合系酸改質環氧丙烯酸酯樹脂、具有胺基甲酸酯構造的鹼可溶樹脂(固體成分52%)；UXE-3000；日本化藥公司製 *3 上述合成例1、具有雙酚A構造的鹼可溶樹脂 *4 上述合成例2、(A)鹼可溶樹脂以外的鹼可溶樹脂 *5 CAP504-0.2；EASTMAN CHEMICAL公司製 *6 二氰二胺(Dicyandiamide)；三菱化學公司製 *7 Paliogen Red K3580；BASF Japan公司製 *8 Fastogen Blue 5380；DIC股份有限公司製 *9 Plast Yellow 8025；有本化學工業公司製 *10 Black CK-T/SD-TT2259；Resino Color工業股份有限公司製 *11 BYK-180；BYK-Chemie Japan股份有限公司製 *12 Silicone KS-66；信越聚矽氧公司製 *13 JMT-784；DKSH Japan公司製 *14 Omirad 379；IGM Resins公司製 *15 Exolit(註冊商標)OP935；Clariant公司製 *16 AEROSIL #R974；東新化成公司製 *17 三聚氰胺；日產化學公司製 *18 UCN-5050D CLEAR；大日精化工業公司製 *19 DOWANOL DPM；Dow Chemical公司製 *20 Epolead PB3600；DAICEL公司製 *21 NK Ester APG-700；新中村化學工業公司製 *22 BPE-900；新中村化學工業公司製 *23 HP-7200L；DIC公司製 *24 jER YX-4000；三菱化學公司製 *25 TEPIC(註冊商標)-VL；日產化學公司製 *26 TEPIC(註冊商標)-HP；日產化學公司製

*1 Bisphenol F type acid-modified epoxy acrylate resin, alkali-soluble resin with bisphenol F structure (solid content 65%); ZFR-1401H; manufactured by Nippon Kayaku Co., Ltd. *2 Composite acid-modified epoxy resin Acrylate resin, alkali-soluble resin with urethane structure (solid content 52%); UXE-3000; manufactured by Nippon Kayaku Co., Ltd. *3 Synthesis example 1 above, alkali-soluble resin with bisphenol A structure* 4 Synthesis example 2 above, (A) Alkali-soluble resin other than alkali-soluble resin *5 CAP504-0.2; EASTMAN CHEMICAL Co., Ltd. *6 Dicyandiamide; Mitsubishi Chemical Co., Ltd. *7 Paliogen Red K3580; BASF *8 Fastogen Blue 5380 manufactured by Japan Corporation; *9 Plast Yellow 8025 manufactured by DIC Co., Ltd.; *10 Black CK-T/SD-TT2259 manufactured by Arimoto Chemical Co., Ltd.; *11 BYK-180 manufactured by Resino Color Industry Co., Ltd.; BYK-Chemie Japan Co., Ltd. *12 Silicone KS-66; Shin-Etsu Polysiloxane Co., Ltd. *13 JMT-784; DKSH Japan Co., Ltd. *14 Omirad 379; IGM Resins Co., Ltd. *15 Exolit (registered trademark) OP935; Clariant Company *16 AEROSIL #R974; Toshin Chemical Co., Ltd. *17 Melamine; Nissan Chemical Co., Ltd. *18 UCN-5050D CLEAR; Dainissei Chemical Co., Ltd. *19 DOWANOL DPM; Dow Chemical Co., Ltd. *20 Epolead PB3600; DAICEL Corporation *21 NK Ester APG-700; *22 BPE-900, manufactured by Shin-Nakamura Chemical Industries, Ltd.; *23 HP-7200L, manufactured by Shin-Nakamura Chemical Industries, Ltd.; *24 jER YX-4000 manufactured by DIC Corporation; *25 TEPIC manufactured by Mitsubishi Chemical Corporation (registered trademark)-VL; manufactured by Nissan Chemical Corporation*26 TEPIC (registered trademark)-HP; manufactured by Nissan Chemical Corporation

As shown in Table 1 above, a cured coating film (solder resist) was produced from the obtained curable compositions of Examples 1 to 7 and Comparative Examples 1 to 2, and this cured coating film was subjected to flux resistance as described below. , imaging and bending tests.

<Test example 1. Evaluation of flux resistance> The entire surface of the copper foil plate with a thickness of 1.6 mm after pretreatment (a 0.20 vol% sulfuric acid-hydrogen peroxide solution) was screen-printed and allowed to dry. The curable compositions of Examples 1 to 7 and Comparative Examples 1 to 2 were applied respectively so that the film thickness would be 20±5 μm. Next, after drying at 80° C. for 30 minutes in a hot air circulating drying furnace, exposure was performed in a grid pattern of 1 mm square and 5×5 grids (150 mJ/cm ² ) using 1 wt% Na ₂ CO ₃ The alkali developing solution (30°C) was developed for 60 seconds, and then thermally hardened at a temperature of 150°C or higher for 60 minutes to obtain the cured coating films of Examples 1 to 7 and Comparative Examples 1 to 2, respectively. Next, flux (manufactured by SANWA Chemical Co., Ltd.; SF-270) was applied to the entire surface of each hardened coating film formed, and placed on a test piece (dummy wafer) in a conveyor-type heating furnace with air at 230°C at the top. Heat treatment was performed once for 5 minutes at a speed of 1.5 m/min, and then peeling was performed with a cellophane tape of 1.18 N/cm or more specified in JIS Z 1522:2009 to evaluate the degree of peeling of the hardened coating film. The evaluation method is as follows. After the peel test, the peeled area is less than 10% ◎ After the peel test, the peeled area exceeds 10% and is less than 50% ○ After the peel test, the peeled area exceeds 50% and reaches 100% ×

<Test Example 2. Developability> The entire surface of the copper foil plate with a thickness of 1.6 mm after pretreatment (a 0.20 vol% sulfuric acid-hydrogen peroxide solution) was screen-printed and the film thickness was allowed to dry. The curable compositions of Examples 1 to 7 and Comparative Examples 1 to 2 were applied so as to be 20±5 μm, respectively, and then dried at 80° C. for 30 minutes in a hot air circulation drying furnace to obtain Examples 1 to 7, respectively. and the dry coating films of Comparative Examples 1-2. _{Next, a 1 wt % Na 2} CO ₃ solution (30° C.) was sprayed with a spray at a pressure of 0.1 MPa, the dried coating film was developed, and the developing time (dissolution time) was measured to evaluate developability. The evaluation method is as follows. Development time is less than 20 seconds ◎ Development time is more than 20 seconds ~ less than 25 seconds ○ Development time is more than 25 seconds ×

<Test Example 3. Bendability> On the entire surface of a 25 μm-thick polyimide film, Examples 1 to 7 and the comparison were applied by screen printing so that the film thickness after drying was 20±5 μm. The curable compositions of Examples 1 to 2. Next, after drying at 80°C for 30 minutes in a hot air circulating drying oven, exposure (150 mJ/cm ² ) was performed, and an alkali developing solution (30° C.) of _{1 wt% Na 2} CO _{3 was used for development for 60 seconds, and then} The cured coating films of Examples 1 to 7 and Comparative Examples 1 to 2 were obtained by thermosetting for 60 minutes at a temperature of 150° C. or higher. Next, it was folded 180°, and a weight of 500 g was applied for 10 seconds, and the number of folds until cracks occurred on the surface of the cured coating film was measured. The evaluation method is as follows. Bending more than 5 times ◎ Bending more than 2 times ○ Bending less than 2 times ×

The test results of the above-mentioned Test Examples 1 to 3 are shown in Table 2 below.

Claims (10)

A sclerosing composition comprising: (A) an alkali-soluble resin having at least any one of a bisphenol A structure, a bisphenol F structure, and a urethane structure, (B) photopolymerization initiator and (C) an epoxy resin having an isocyanurate structure, and The epoxy resin having the above-mentioned (C) isocyanurate structure has a structure in which a nitrogen atom and an epoxy group in the isocyanurate structure are bonded by an alkylene group having 2 or more carbon atoms. The curable composition according to claim 1, further comprising powder or crystalline epoxy resin. The curable composition according to claim 2, wherein the powder or crystalline epoxy resin is an epoxy resin having a biphenyl structure. The curable composition according to any one of claims 1 to 3, further comprising an epoxy resin having a dicyclopentadiene structure. The curable composition according to claim 4, wherein (C) the mass of the epoxy resin having an isocyanurate structure, the powder or crystalline epoxy resin, and the epoxy resin having a dicyclopentadiene structure The ratio is 1:2~6:1~3. The curable composition according to any one of claims 1 to 5, further comprising urethane beads and/or epoxidized polybutadiene. The curable composition according to any one of claims 1 to 6, further comprising a cellulose resin. A dry film having a resin layer obtained from the curable composition according to any one of claims 1 to 7. A cured product obtained by curing the curable composition according to any one of claims 1 to 7 or the resin layer of the dry film according to claim 8. An electronic part having the hardened product as claimed in claim 9.