KR100844692B1 - Photocurable resin composition and cured article - Google Patents

Abstract

The present invention provides a curable resin composition having heat dissipation useful for a resin substrate or the like in a package substrate or a surface mount light emitting diode and excellent in storage stability.

Moreover, this invention contains (A) carboxyl group-containing copolymer resin, (B) the compound which has 2 or more reactors hardened | cured by active energy ray, (C) photoinitiator, and (D) ceramic particle which radiates far infrared rays, The content rate of the ceramic particle (D) which emits the said far infrared rays is 60 volume% or more in solid content.

Light emitting diode, heat dissipation, storage stability, curable resin composition, ceramic particles

Description

Curable resin composition and its hardened | cured material {PHOTOCURABLE RESIN COMPOSITION AND CURED ARTICLE}

[Patent Document 1] Japanese Patent Laid-Open No. 9-148748 (Patent Claims)

[Patent Document 2] Japanese Unexamined Patent Application Publication No. Hei 11-288091 (claims)

[Patent Document 3] Japanese Unexamined Patent Application Publication No. 61-243869 (Patent Claims)

TECHNICAL FIELD The present invention relates to a curable resin composition having excellent heat dissipation properties and a cured product thereof, and more particularly, to a curable resin composition having excellent heat dissipation properties useful for a package substrate, a resin insulating layer of a surface mount type light emitting diode, and the like, and having excellent storage stability, and its hardness. It's about cargo.

In recent years, with the miniaturization and high performance of electronic devices, high density and high functionality of semiconductors have been required. In response to this increase in density, a resin insulating layer is formed on the core substrate, a copper foil layer is formed by electroless copper plating, or the like, and a BGA (ball, grid, etc.) for surface-mounting a semiconductor chip to be formed on the substrate is formed. Package substrates, such as an array) and a CSP (chip scale package), are emerging.

The resin composition (for example, refer patent document 1 and patent document 2) used for such a buildup board | substrate or a package board | substrate is a resin composition based on the low molecular weight epoxy compound, and is a fused silica useful for low linear expansion coefficient, and heat dissipation property It was difficult to high-charge inorganic fillers, such as aluminum oxide which improves the viscosity.

In addition, in the conventional liquid photo solder resist composition (for example, refer to Patent Document 3), the content of the inorganic filler is 50% by mass or less, and inorganic fillers such as barium sulfate, silica, talc, clay and the like are used in particular. Has been. In this system, the water absorption of the coating film was 1.2 to 1.5% by weight, which caused problems such as popcorn phenomenon due to absorption and electrocorrosion by water in the coating film. In addition, it has become a problem that polybasic acid anhydrides and photopolymerization initiators decomposed and released from a resin at high temperatures cause gasification to cause malfunction of electronic devices.

The present invention was developed in view of the above problems, and a main object thereof is to provide a curable resin composition having heat dissipation useful for a resin substrate or the like in a package substrate or a surface mount type light emitting diode and excellent in storage stability.

Moreover, it is providing the hardened | cured material excellent in the heat dissipation obtained by active energy ray irradiation and / or thermosetting the said curable resin composition.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched for the said objective, As a result, (A) carboxyl group-containing copolymer resin, (B) the compound which has two or more reactors hardened by an active energy ray, (C) photoinitiator, and (D) A curable resin composition comprising ceramic particles that emit far infrared rays, wherein the content rate of the ceramic particles (D) that emits far infrared rays is 60% by volume or more in solid content, is excellent in heat dissipation, and facilitates high thermal conductivity. The present invention was found to be able to be carried out by a dilute alkali aqueous solution and to complete the present invention.

As a more preferable aspect, the said carboxyl group-containing copolymer resin (A) is carboxyl group-containing copolymer resin (A-1) which contains the compound represented by following formula (1) or (2) as a structural component.

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a straight or branched alkylene group having 2 to 6 carbon atoms, R ³ represents an alkylene group having 3 to 10 carbon atoms, and R ⁴ represents a dibasic acid anhydride residue.

Moreover, the compound (B) which has two or more reactors hardened | cured by the said active energy ray is a compound (B-1) which has two or more ethylenically unsaturated bonds, The said photoinitiator (C) is a photoradical polymerization initiator ( C-1) is preferable in view of photocurability. Moreover, as a 2nd aspect of curable resin composition of this invention, the photocurable thermosetting composition which further contains a thermosetting component (E) in the said composition is provided. In this preferred aspect, the thermosetting component (E) is a polyfunctional epoxy resin (E-1) having two or more oxirane rings in one molecule.

Best Mode for Carrying Out the Invention

A basic aspect of the curable resin composition of the present invention is (A) a carboxyl group-containing copolymer resin, (B) a compound having two or more reactors cured by an active energy ray, (C) a photoinitiator, and (D) far-infrared radiation It is made to contain the ceramic particle, and the content rate of the ceramic particle (D) which emits the said far infrared rays is 60 volume% or more in solid content, It is characterized by the above-mentioned. Moreover, in order to improve heat resistance, you may contain the (E) thermosetting component.

Hereinafter, each structural component of curable resin composition of this invention is demonstrated in detail.

First, the carboxyl group-containing copolymerized resin (A) can use a well-known conventional copolymerized resin which has a carboxyl group in a molecule | numerator. Moreover, the photosensitive carboxyl group-containing copolymer resin which has an ethylenically unsaturated bond in a molecule | numerator can be used more preferable from a photocurability and developability resistant point.

Specifically, the carboxyl group-containing copolymer resin enumerated below is mentioned.

(1) Carboxyl group-containing copolymerized resin obtained by copolymerizing unsaturated carboxylic acid, such as (meth) acrylic acid, and at least 1 sort (s) of the compound which has another unsaturated double bond,

(2) Glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl to a copolymer of unsaturated carboxylic acids such as (meth) acrylic acid and at least one compound having another unsaturated double bond. Photosensitive carboxyl group-containing copolymer resin obtained by adding an ethylenically unsaturated group as a pendant by the compound which has unsaturated double bonds, such as (meth) acrylate, (meth) acrylic acid chloride, etc.,

(3) A copolymer of a compound having an unsaturated double bond with an epoxy group such as glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate, and a compound having an unsaturated double bond other than that Photosensitive carboxyl group-containing copolymer resin obtained by making unsaturated carboxylic acids, such as (meth) acrylic acid, react, and making a polybasic acid anhydride react with the produced | generated secondary hydroxyl group,

(4) A hydroxyl group such as 2-hydroxyethyl (meth) acrylate and an unsaturated double bond are added to a copolymer of an acid anhydride having an unsaturated double bond such as maleic anhydride and a compound having another unsaturated double bond. Photosensitive carboxyl group-containing copolymer resin obtained by reacting a compound having

(5) carboxyl group-containing resin obtained by making polybasic acid anhydride react with hydroxyl-containing copolymers, such as a polyvinyl alcohol derivative,

(6) Furthermore, photosensitive carboxyl group-containing copolymerization obtained by making the said carboxyl group-containing resin react with compounds which have unsaturated double bonds, such as glycidyl (meth) acrylate and 3, 4- epoxycyclohexylmethyl (meth) acrylate, and the like. Resin and the like.

When the carboxyl group-containing copolymer resin (A-1) containing the compound represented by the following general formula (1) or (2) as a constituent component of these carboxyl group-containing copolymer resin (A) is highly charged with the ceramic particles (D) emitting the far infrared rays It is preferable as binder resin of the.

<Formula 1>

<Formula 2>

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a straight or branched alkylene group having 2 to 6 carbon atoms, R ³ represents an alkylene group having 3 to 10 carbon atoms, and R ⁴ represents a dibasic acid anhydride residue.

In addition, in this specification, (meth) acrylate is a term which generically mentions acrylate, methacrylate, and mixtures thereof, and it is the same also about another similar expression.

Solid acid value of the said carboxyl group-containing copolymer resin (A) is the range of 40-200 mgKOH / g, More preferably, it is the range of 80-120 mgKOH / g. If the acid value of the carboxyl group-containing copolymer resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, if the acid value exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line becomes thinner than necessary, or in some cases furnace It is not preferable because it is difficult to draw a normal resist pattern by dissolving and peeling with a developer without distinguishing between the miner and the unexposed part.

In addition, the weight average molecular weight of such carboxyl group-containing copolymer resin (A) is 2,000-50,000, Preferably it is the range of 5,000-20,000. When the weight average molecular weight is less than 2,000, it is not preferable because the touch-drying property of the coating film is lowered and the impact resistance of the cured product becomes difficult to be obtained. On the other hand, when weight average molecular weight exceeds 50,000, since developability falls, it is not preferable.

Subsequently, as a compound (B) which has two or more reactors hardened | cured by the said active energy ray, the compound which has two or more ethylenically unsaturated bonds, cationically polymerizable cyclic ether compounds, such as an oxirane ring and an oxetane ring, a chalcone or a shin Light dimerization compounds, such as a nam acid ester, etc. are mentioned. Among these, the compound (B-1) which has two or more ethylenically unsaturated bonds from a viewpoint of photocurability and storage stability is preferable.

Compound (B-1) which has 2 or more of said ethylenically unsaturated bonds is used in order to photo-cure and insolubilize the said carboxyl group-containing copolymer resin (A) with respect to a diluted alkali aqueous solution. Typical examples thereof include 2-hydroxyethyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentylglycol di (meth). ) Acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, Caprolactone modified dicyclopentanyl di (meth) acrylate, EO modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri ( Meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, PO side Trimethylolpropane tri (meth) acrylate, tris (acryloyloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone Modified dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Among them, (meth) acrylates are preferably bifunctional or more, preferably trifunctional or more, in terms of development resistance.

As a compounding quantity of the compound (B-1) which has 2 or more of these ethylenically unsaturated bonds, 5-100 mass parts is preferable with respect to 100 mass parts of said carboxyl group-containing copolymerization resin (A), and 10-50 mass parts is especially preferable. When (B-1) a component is less than 5 mass parts, sufficient sclerosis | hardenability will not be obtained and the shape as designed will not be obtained. On the other hand, when it exceeds 100 mass parts, the touch-drying property is bad and it is unpreferable.

As said photoinitiator (C) used for this invention, the compound which generate | occur | produces an active group by active energy ray irradiation, for example, a photoradical polymerization initiator, a photocationic polymerization initiator, a photoanionic polymerization initiator, etc. are mentioned. Of these, the radical photopolymerization initiator (C-1) is preferred from the photocurability, storage stability, electrical properties of the cured product, and the like.

As said radical photopolymerization initiator (C-1), benzoin and benzoin alkyl ether, such as a well-known and common thing, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc. Acetophenones; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone- Aminoacetophenones such as 1; Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone; Thioxanthones, such as 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, and 2, 4- diisopropyl thioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone; Or xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphineoxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine jade Phosphine oxides, such as a seed and ethyl-2,4,6-trimethylbenzoylphenyl phosphinate, etc. are mentioned, These known conventional radical photopolymerization initiators (C-1) are independent or it combines 2 or more types Can be used.

The compounding quantity of these radical photopolymerization initiators (C-1) is contained in the ratio of 0.1-30 mass parts with respect to 100 mass parts of said carboxyl group-containing copolymer resin (A), Preferably it is 2-20 mass parts. When the compounding quantity of radical photopolymerization initiator (C-1) is less than 0.1 mass part with respect to 100 mass parts of carboxyl group-containing copolymerization resin (A), since photocurability and workability fall, it is unpreferable. On the other hand, when it exceeds 30 mass parts, since a coating film characteristic falls, it is not preferable.

Materials that can be used for the ceramic particles (D) that emit far-infrared rays used in the curable resin composition of the present invention are known conventional far-infrared ceramics, for example, aluminum oxide (Al ₂ O ₃ ), silica (SiO ₂ ), zirconia (ZrO ₂ ), titanium oxide (TiO ₂ ), magnesium oxide (MgO), mullite (3Al ₂ O ₃ ㆍ 2SiO ₂ ), zircon (particularly ZrO ₂ ㆍ SiO ₂ ), cordierite (2MgO · 2Al ₂ O ₃ 5SiO ₂ ), silicon nitride (Si ₃ N ₄ ), silicon carbide (SiC), manganese oxide (MnO ₂ ), iron oxide (Fe ₂ O ₃ ), and cobalt oxide (CoO). Among them, aluminum oxide is chemically stable and excellent in insulation, and in particular, by using spherical aluminum oxide, the increase in viscosity at the time of high charge can be alleviated. The average particle diameter of the aluminum oxide particles is 0.01 μm to 30 μm, more preferably 0.01 μm to 20 μm. When smaller than 0.01 micrometer, the viscosity of a composition becomes high too much and dispersion | distribution is difficult and application | coating to a to-be-coated object also becomes difficult. When larger than 30 micrometers, convex parts to a coating film generate | occur | produce, a sedimentation speed | rate becomes high, and storage stability worsens. Moreover, by mix | blending two or more types of average particle diameters which have the particle size distribution which is filled most closely, it can be made high filling and it is preferable at both sides of storage stability and thermal conductivity.

Moreover, since the refractive index of the said ceramic particle (D) is 1.4-2.0 near the refractive index of a resin composition, More preferably, the refractive index of 1.5-1.8 does not impair light transmittance. Specifically, silica and aluminum oxide are mentioned.

As a compounding quantity of the ceramic particle (D) which emits such far infrared rays, it is 60 volume% or more in solid substance (hardened | cured material). When the compounding quantity of the said ceramic particle (D) which emits far infrared rays is less than 60 volume%, since the excellent heat dissipation, high thermal conductivity, etc. which arise by high charge of the ceramic particle which emits far infrared rays which are the objective of this invention become difficult, it is unpreferable.

Curable resin composition of this invention can also mix | blend the thermosetting component (E) in order to improve the heat resistance of hardened | cured material. As said thermosetting component, the polyfunctional epoxy resin which has two or more oxirane rings in a molecule | numerator, the polyfunctional oxetane compound which has two or more oxetane rings in a molecule | numerator, a thermosetting polyimide resin, a melamine resin, etc. are mentioned.

Of these, polyfunctional epoxy resins (E-1) are preferably used in terms of curability, storage stability, and cured coating film characteristics.

As said polyfunctional epoxy resin (E-1), a well-known conventional epoxy compound, for example, bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, brominated bisphenol A-type epoxy resin, hydrogenated bisphenol A Glycids such as epoxy resins, biphenol epoxy resins, bixylenol epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, brominated phenol novolac epoxy resins, and novolac epoxy resins of bisphenol A. Dilether compounds; Glycidyl ester compounds such as terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, and dimeric acid diglycidyl ester; Triglycidyl isocyanurate, N, N, N ', N'-tetraglycidylmethacylenediamine, N, N, N', N'-tetraglycidyl bisaminomethylcyclohexane, N, N- Glycidylamine compounds such as diglycidyl aniline; And epoxidized polybutadiene obtained by oxidizing a resin having an unsaturated bond such as polybutadiene. Moreover, the copolymer resin of glycidyl (meth) acrylate, etc. can be used.

These polyfunctional epoxy resins (E-1) can be used individually or in combination of 2 or more types. The compounding quantity is 0.6-2.0 equivalent, Preferably it is 0.8-1.5 equivalent with respect to 1 equivalent of carboxyl groups of the said carboxyl group-containing copolymer resin (A). When the compounding quantity of a polyfunctional epoxy resin is less than the said range, since a carboxyl group remains and heat resistance, alkali resistance, electrical insulation, etc. fall, it is unpreferable. On the other hand, when the said range is exceeded, since the low molecular weight polyfunctional epoxy resin remains, since the intensity | strength of a coating film, etc. fall, it is unpreferable.

It is preferable that the curable resin composition of this invention further adds (F) wet-and-dispersing agent in order to make high filling easy. As such a wetting and dispersing agent (F), acid containing compounds, such as a compound which has affinity with a far-infrared ceramic particle (D), such as a carboxyl group, a hydroxyl group, and acid ester, a high molecular compound, for example, phosphate ester, and an acidic group Copolymers, hydroxyl group-containing polycarboxylic acid esters, polysiloxanes, salts of long-chain polyaminoamides and acid esters, and the like can be used. Particularly preferred examples of commercially available wetting and dispersing agents (F) include Disperbyk (registered trademark) -101, -103, -110, -111, -160, -171, -174, -190, -300, Bykumen (registered trademark), BYK-P105, -P104, -P104S, -240 (all manufactured by BIC Chemi Co., Ltd.), EFKA-polymer 150, EFKA-44, -63, -64, -65, -66, -71 , -764, -766, N (all are manufactured by Efca Co., Ltd.).

As for the compounding quantity of such a wet-and-dispersing agent (F), 0.01-5 mass parts is suitable for 100 mass parts of said far-infrared ceramic particles (D). If the blending amount of the wet / dispersant (F) is too small than the above range, the wet / dispersant addition effect is not obtained, and it is difficult to high-fill the composition. On the other hand, when it mixes excessively than the said range, since the ratio of the component which is not photocured increases, since the intensity | strength of a coating film falls or it becomes a factor of the thixotropy increase of a composition, it is unpreferable.

You may add an organic solvent to curable resin composition of this invention for viscosity adjustment as needed. As said organic solvent, For example, ketones, such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether Glycol ethers such as these; 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; Organic solvents, such as petroleum solvents, such as petroleum ether, petroleum naphtha, and solvent naphtha, can be used. These organic solvents can be used individually or in combination of 2 or more types.

The compounding quantity of these organic solvents is not specifically limited, Although it is preferable to adjust suitably according to a coating method, it is generally 50 mass% or less in a composition, Preferably it is 30 mass% or less. When the content of the organic solvent is large, the settling speed of the far-infrared ceramic particles (D) increases, and storage stability is not preferable.

Curable resin composition of this invention is phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, hydroquinone, hydroquinone mono, as needed. Well-known and commonly used thermal polymerization inhibitors such as methyl ether, t-butyl catechol, pyrogallol and phenothiazine, finely-known conventional thickeners such as finely divided silica, organic bentonite and montmorillonite, and antifoaming agents such as silicone, fluorine and polymer. Or known conventional additives such as silane coupling agents such as leveling agents, imidazole series, thiazole series, and triazole series.

Curable resin composition of this invention is adjusted to the viscosity suitable for the application | coating method with the said organic solvent, for example, and it is immersion coating method, flow coating method, roll coating method, bar coating method, screen printing method, curtain coating method on a base material. The coating film without adhesion can be formed by apply | coating by the method of these etc., and carrying out volatilization (temporary drying) of the organic solvent contained in a composition at the temperature of about 60-100 degreeC. Moreover, the resin insulating layer can be formed by apply | coating the said composition on a plastic film, drying, and bonding what wound up as a film on a base material. Thereafter, by contact (or non-contact method), selectively exposed to the active light through a patterned photomask, the unexposed portion to a dilute alkali aqueous solution (for example, 0.3 to 3% aqueous solution of sodium carbonate) By developing to form a resist pattern. Moreover, the polyfunctional epoxy resin (E-1) which has a carboxyl group of the said carboxyl group-containing copolymer resin (A) and two or more oxirane rings in a molecule | numerator by heating at the temperature of about 140-180 degreeC, and thermosetting, for example. The epoxy group reacts to form a cured coating film excellent in various properties such as heat resistance.

As the irradiation light source for photocuring the coating film, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, or a metal halide lamp is suitable. In addition, laser beam etc. can also be used as an active light source for exposure, and can be drawn directly.

As the diluted aqueous alkali solution used for the above development, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, ammonia, amines can be used, and sodium carbonate is particularly preferable.

In addition, the three-dimensional insulating structure can also be formed by repeating application and volatilization drying two or more times and laminating the coating film. In addition, heat of Tg or more may be applied to the coated film after development to thermally deform the pattern sidewalls into a smooth tapered shape by heat flow. Here, exposure and image development may be performed every time application | coating and volatilization drying, and may be performed collectively.

<Example>

Next, although an Example and a comparative example of this invention are given and this invention is demonstrated concretely, it cannot be overemphasized that this invention is not limited to the following Examples. In addition, unless otherwise indicated, the thing "part" and "%" below shows a "mass part" and the "mass%" all.

Synthesis Example 1 (Synthesis of Carboxyl Group-Containing Copolymer Resin A)

900 g of diethylene glycol dimethyl ether, and t-butylperoxy 2-ethylhexanoate [Nipbon Yushi] in a two-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube ) 21.4 g of manufactured perbutyl O] was heated to 90 ° C., and then 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and lactone-modified 2-hydroxyethyl methacrylate represented by the formula (1) 109.8 g of Kakushi Kogyo Co., Ltd.-produced Fraccel FM1] was used for 2 hours in diethylene glycol dimethyl ether with 21.4 g of bis (4-t-butylcyclohexyl) peroxy dicarbonate [Nipbon Yushi Co., Ltd. perroyl TCP]. It dripped over, and further aged for 6 hours, and obtained the carboxyl group-containing copolymer resin solution. The reaction was carried out in a nitrogen atmosphere.

Subsequently, 363.9 g of 3,4-epoxycyclohexyl methyl methacrylate (manufactured by Daicel Chemical Corporation, Cyclomer A200), 3.6 g of dimethylbenzylamine, and 1.80 g of hydroquinone monomethyl ether were added to the carboxyl group-containing copolymer resin solution. The ring-opening addition reaction of epoxy was performed by adding and heating at 100 degreeC, and stirring. After 16 hours, a solution containing 53.8% by weight (nonvolatile content) of a carboxyl group-containing copolymerized resin having a solid dispersion value of 108.9 mgKOH / g and a weight average molecular weight of 25,000 (styrene equivalent) was obtained. Hereinafter, this reaction solution is called A-1 varnish.

<Comparative Synthesis Example 1> (Synthesis of carboxyl group-containing resin)

210 g of cresol novolac-type epoxy resins (Epiclon N-680, manufactured by Dainippon Ink Chemical Co., Ltd., epoxy equivalent = 210) and 96.4 g of carbitol acetate in a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux cooler. Was weighed and dissolved by heating. Subsequently, 0.1 g of hydroquinone as a polymerization inhibitor and 2.0 g of triphenylphosphine were added as a reaction catalyst. The mixture was heated to 95 to 105 ° C, and 72 g of acrylic acid was slowly added dropwise and reacted for about 16 hours until the acid value became 3.0 mgKOH / g or less. The reaction product was cooled to 80-90 ° C., and 76.1 g of tetrahydrophthalic anhydride was added to react for about 6 hours until the absorption peak (1780 cm ⁻¹ ) of the acid anhydride disappeared by infrared absorption analysis. 96.4 g of aromatic solvent Ifsol # 150 manufactured by Idemitsu Seki Oil Co., Ltd. was added to this reaction solution, and the mixture was diluted. The carboxyl group-containing photosensitive polymer solution thus obtained had a nonvolatile content of 65% by weight and an acid value of 78 mgKOH / g of a solid. Hereinafter, this reaction solution is called R-1 varnish.

<Example 1 and Comparative Example 1>

The compounding component shown in Table 1 using A-1 varnish and R-1 varnish obtained by the said synthesis example was kneaded with the triaxial roll mill, and the curable resin composition was obtained. The evaluation results of the properties of each curable composition are shown in Table 2 below.

In addition, the method of the performance test of the said Table 2 is as follows.

Characteristic evaluation:

(1) solvent resistance

The composition of each said Example and the comparative example was apply | coated whole surface by screen printing so that a dry coating might be about 40 micrometers, and it dried at 80 degreeC for 20 minutes. After cooling to room temperature, after exposing at full exposure to about 6 steps with Kodak Tablet's step tablet No. 2 under reduced pressure with an exposure apparatus (metal halide lamp 7 KW) manufactured by Oak Seisakusho Co., Ltd. The aqueous solution of wt% Na ₂ CO ₃ was developed for 60 seconds under a spray pressure of 0.2 MPa, followed by thermosetting at 150 ° C. for 60 minutes. After the obtained board | substrate was immersed in propylene glycol monomethyl ether acetate for 30 minutes, and dried, the peeling test with the cellophane adhesive tape was done and the peeling and discoloration of the coating film were evaluated.

○: no peeling or discoloration

X: peeling or discoloration

(2) heat resistance

Using the compositions of the above Examples and Comparative Examples, a rosin-based flux was applied to a substrate obtained by the same method as solvent resistance, flowed in a solder bath at 260 ° C. for 10 seconds, washed and dried with propylene glycol monomethyl ether acetate, followed by cellophane adhesion. Peeling test with a tape was performed and the peeling of a coating film was evaluated.

○: no peeling

X: thing with peeling

(3) pencil hardness

Using the compositions of each of the above Examples and Comparative Examples, the pencil hardness of B-9H was changed so that the tip was flattened at an angle of about 45 ° to the substrate obtained by the same method as solvent resistance, and the pencil hardness was not peeled off.

(4) electrical insulation

Using the composition of each of the above Examples and Comparative Examples to prepare a substrate using the comb-shaped electrode B coupon of the IPC B-25 test pattern in the same manner as the solvent resistance, the substrate is subjected to a bias of DC 500 V to the comb-shaped electrode. The insulation resistance value was measured by applying.

(5) heat dissipation test

Using the composition of each of the above examples and comparative examples, a 60 W heater serving as a heat source was applied to each of the substrates obtained by the same method as solvent resistance for 10 minutes, and the substrate temperature was 3 mm from the heater. It measured with the K-type thermocouple attached.

As is clear from the results shown in Table 2, according to the curable composition of the present invention, a curable resin composition having excellent heat dissipation properties and capable of obtaining a cured product having sufficient characteristics as a heat-resistant insulating material for a printed wiring board, and which can be developed by a dilute alkali aqueous solution. It is possible to provide.

Since the carboxyl group-containing copolymerized resin (A) used in the curable resin composition of the present invention is a copolymerized resin, even when diluted with an organic solvent or the like, proper viscosity can be maintained, thereby enabling high filling of ceramic particles emitting far-infrared rays, resulting in heat dissipation. It is possible to provide a resin composition which is excellent in high thermal conductivity and can be easily developed and which can be developed by a dilute alkali aqueous solution.

Curable resin composition which is excellent in such a heat dissipation property and can easily perform high thermal conductivity etc. is preferably used as a soldering resist of the thin-plate buildup board | substrate or the package board | substrate with many heat generating semiconductor chips which tend to generate | occur | produce a bending problem. Can be used. In addition, by using an inorganic filler having high visible light reflectivity or an organic filler having light shielding properties, it is possible to impart light reflectivity, light diffusivity, or light shielding property to the solder resist, and to provide an optical function in addition to insulation. It can use suitably for an optical apparatus.

Claims (10)

(A) carboxyl group-containing copolymer resin, (B) a compound having two or more reactors cured by active energy rays, (C) photoinitiator, and (D) ceramic particles emitting far infrared rays Containing a compound, wherein the carboxyl group-containing copolymerized resin (A) is a carboxyl group-containing copolymerized resin (A-1) containing a compound represented by the following formula (1) or (2) as a constituent component and cured by the active energy ray: The compound (B) which has 2 or more of is a compound (B-1) which has 2 or more of ethylenically unsaturated bonds, The said photoinitiator (C) is an optical radical polymerization initiator (C-1), The compounding quantity of the compound (B-1) which has 2 or more of said ethylenically unsaturated bonds is 5-100 mass parts with respect to 100 mass parts of said (A) carboxyl group-containing copolymer resins, The said radical radical polymerization initiator (C-1) The compounding quantity of is 0.1-30 mass parts, and the content rate of the said ceramic particle (D) which radiates said far infrared rays is 60 volume% or more in solid content, The curable resin composition which can develop alkali is possible. <Formula 1>

<Formula 2>

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a straight or branched alkylene group having 2 to 6 carbon atoms, R ³ represents an alkylene group having 3 to 10 carbon atoms, and R ⁴ represents a dibasic acid anhydride residue. delete delete delete delete The curable resin composition according to claim 1, wherein the ceramic particles (D) that emit far infrared rays are aluminum oxide. (E) Curable resin composition of Claim 1 which further contains a thermosetting component. The curable resin composition according to claim 7, wherein the thermosetting component (E) is a polyfunctional epoxy resin (E-1) having two or more oxirane rings in one molecule. Hardened | cured material obtained by active energy ray irradiation and thermosetting of the curable resin composition in any one of Claims 1-6. Hardened | cured material obtained by irradiating an active energy ray or thermosetting the curable resin composition of any one of Claims 1-6.