WO2007020793A1

WO2007020793A1 - Insulating curable composition , cured product thereof, and printed wiring board using same

Info

Publication number: WO2007020793A1
Application number: PCT/JP2006/315164
Authority: WO
Inventors: Yoshikazu Daigo; Shigeru Ushiki
Original assignee: Taiyo Ink Mfg. Co., Ltd.
Priority date: 2005-08-12
Filing date: 2006-07-31
Publication date: 2007-02-22
Also published as: CN101238760A; KR20080035619A; TW200738075A; JP4920929B2; TWI331489B; JP2007049064A

Abstract

Disclosed is an insulating curable resin composition having excellent storage stability which exhibits thermal conductivity useful for resin insulating layers of printed wiring boards, package substrates and surface mount light-emitting diodes. Also disclosed are a cured product of such a resin composition and a printed wiring board using the same. Specifically disclosed is an insulating curable resin composition for printed wiring boards comprising spherical aluminum oxide particles (A) having a thermal conductivity of not less than 15 W/m·K, and a curable resin composition (B). This resin composition is free from problems of sedimentation and aggregation while being excellent in storage stability. In addition, a cured product of this resin composition has a volume fraction of the aluminum oxide particles (A) of not less than 60% by volume relative to the total volume of the cured product while having a thermal conductivity of not less than 2 W/m·K.

Description

Specification

Insulating curable composition, cured product thereof, and printed wiring board using the same

Technical field

TECHNICAL FIELD [0001] The present invention relates to an insulating curable resin composition excellent in thermal conductivity, a cured product thereof, and a printed wiring board using the same, and more particularly, to a package substrate or a surface-mounted light emitting diode. The present invention relates to an insulating curable resin composition having thermal conductivity useful for a fat insulating layer and the like and excellent storage stability, a cured product thereof, and a printed wiring board using the same.

Background art

In recent years, with the downsizing and high performance of electronic devices, there is a demand for higher density and higher functionality of semiconductors. For this reason, circuit boards on which semiconductors are mounted are also required to be small and dense. As a result, heat dissipation of components and circuit boards has become a major issue recently.

[0003] On the other hand, a metal plate such as copper or aluminum is used as a circuit board with good heat dissipation, and an electrical insulating layer such as a pre-preda or a thermosetting resin composition is formed on one or both sides of the metal plate. A metal base substrate on which a circuit pattern is formed via a substrate (for example, see Patent Document 1).

[0004] However, the strong metal base substrate has a poor thermal conductivity of the electrical insulating layer, and thus the insulating layer needs to be thinned. As a result, a problem of withstand voltage may occur. .

[0005] On the other hand, surface mounting has become the mainstream for mounting high-density semiconductor chips, and recently, package substrates such as BGA (ball grid array) and CSP (chip scale package) have appeared. . Solder resist compositions (see, for example, Patent Document 2) and interlayer insulating materials used for such package substrates are based on low molecular weight epoxy compounds, and the filler is also electrically insulating and chemical resistant. Silica and precipitated sodium sulfate, which have good properties, have poor heat dissipation. In addition, when alumina, which is expected to have heat dissipation, electrical insulation, and chemical resistance, is used as a filler, the sedimentation of the filler is severe. The fallen filler is agglomerated and becomes unusable, and is not practical in terms of storage stability.

[0006] On the other hand, a method in which a heat sink is attached to the upper part of the semiconductor is considered. About 50% of the released heat is accumulated in the package substrate, so that the heat dissipation property of the knock board is still a problem. It has become.

[0007] In addition, in recent mobile phones and the like in which a large number of surface-mounted light emitting diodes are used for push button display, there is a problem that most of the heat dissipated from the light emitting diodes accumulates on the substrate. Specifically, for example, a light-emitting diode chip is disposed on a resin insulating layer on which a terminal portion is formed, and is packaged with a sealing resin that also serves as a lens layer on top of the light-emitting diode chip. In the diode, the heat dissipation of the resin insulation layer becomes a problem.

[Patent Document 1] JP-A-6-224561 (Claims)

(Patent Document 2) JP-A-11 288091 (Claims)

Disclosure of the invention

[0009] The present invention was developed in view of the above-mentioned problems, and its main purpose is to have useful thermal conductivity for a resin insulating layer in a package substrate or a surface-mounted light emitting diode, and to ensure stable storage. It is providing the insulating curable resin composition excellent in property.

[ooio] Furthermore, a cured product having a thermal conductivity of 2 WZm'K or more obtained by irradiating active energy rays and Z or thermosetting the above curable resin composition, and using it as an interlayer insulating material solder resist Another object is to provide a printed wiring board.

In order to solve this problem, the present invention has the following requirements.

[0012] (1) (A) A spherical aluminum oxide particle having a thermal conductivity of 15 WZm'K or more and (B) a curable resin composition, and a cured product of the resin composition for printed wiring boards. Insulating curability for printed wiring boards in which the volume occupancy of the aluminum oxide particles (A) is 60% by volume or more and the thermal conductivity of the hardened material is 2 WZm · K or more with respect to the total capacity of A rosin composition.

[0013] (2) The insulating curable resin composition for printed wiring boards according to (1), wherein the acid aluminum particles (A) are particles having a particle size of 30 μm or less. [0014] (3) The acid oxide aluminum particles (A) have a first acid oxide particle content of 100 parts by mass of the first acid oxide aluminum particles having a particle diameter in the range of 5 m to 20 m. Insulating hardening for printed wiring boards according to (1) or (2), containing 20 to 100 parts by mass of second aluminum oxide particles in the range of 1Z2 to 1Z10 with an average particle diameter of aluminum particles! Rosin composition.

[0015] (4) The printed wiring board according to any one of (1) to (3), wherein the curable resin composition (B) is (B-1) a thermosetting resin composition. Insulating curable resin composition.

[0016] (5) The thermosetting resin composition (B-1) is an epoxy compound and a Z or oxetane compound, and the resin composition for a printed wiring board further comprises the thermosetting resin. The insulating curable resin composition for printed wiring boards according to (4), which contains a curing agent and Z or a curing catalyst of the composition (B-1).

[0017] (6) The printed wiring board according to any one of (1) to (3), wherein the curable resin composition (B) is (B-2) a photocurable resin composition. Insulating curable resin composition.

[0018] (7) The photocurable resin composition (B-2) contains (6) a compound having one or more ethylenically unsaturated bonds in one molecule and a photopolymerization initiator. The insulating curable resin composition for printed wiring boards as described.

[0019] (8) The insulating curable resin composition for printed wiring boards according to any one of (1) to (7)

Cured product with thermal conductivity of 2WZm'K or more obtained by irradiation with active energy rays and Z or thermosetting.

[0020] (9) The insulating layer is obtained by curing the insulating curable resin composition according to any one of (1) to (7) by irradiation with active energy rays and Z or heat curing. And a printed wiring board on which a Z or solder resist layer is formed.

[0021] Since the acid-aluminum particles used in the present invention are spherical, they can be highly filled without significantly increasing the viscosity of the composition, and in particular, spherical acid particles having a particle size distribution that provides close-packing. By using aluminum particles, it became possible to suppress sedimentation and aggregation, and to provide an insulating curable resin composition excellent in storage stability and thermal conductivity.

. Such a curable resin composition having excellent thermal conductivity and excellent storage stability can be suitably used for printed wiring boards equipped with semiconductors and light-emitting diodes that generate a large amount of heat. Since it is excellent in performance, it is possible to reduce the size and weight. [0022] (Definitions, etc.)

In the present invention, “spherical” of “spherical acid-aluminum particles” means a state in which the shape is rounded as a result of pulverizing a mineral or a synthetic product and then heat-treating it. It does not mean a true sphere.

[0023] The "average particle diameter" refers to a value measured using a laser particle size distribution measuring machine.

[Best Mode for Carrying Out the Invention]

The basic aspect of the insulating curable resin composition of the present invention is: (A) Thermal conductivity 15 WZm.

K or more spherical acid / aluminum particles (B) containing a curable resin composition, and the volume occupancy of the aluminum oxide particles (A) is 60% by volume with respect to the total volume of the cured product. It is characterized by including the above.

[0025] That is, coating the spherical aluminum oxide (A), which is excellent in insulation and thermal conductivity, with a thermal conductivity of 15 WZm'K or more, by setting the volume occupancy of the cured product to 60% by volume or more. It has been found that a cured product having an insulating property can be provided with a thermal conductivity of 2 WZm'K or more without impairing the properties.

[0026] Hereinafter, each component of the resin composition for printed wiring boards of the present invention will be described in detail.

[0027] First, as the spherical acid / aluminum particles (A) used in the present invention, a spherical acid / aluminum having a thermal conductivity of 15W Zm'K or more and a purity of 92% or more can be used. The average particle diameter of the aluminum oxide particles (A) is 0.01 m to 30 μm, more preferably 0.0 1 μπι to 20 / ζ m. If it is less than 0.01 μm, the viscosity of the composition becomes too high, so that it is difficult to disperse and it is difficult to apply to the object. When it is larger than 30 m, cueing to the coating film occurs, and the sedimentation speed increases and the storage stability deteriorates.

[0028] The amount of acid-aluminum particles is determined based on the cured product of the resin composition for printed wiring boards in consideration of heat dissipation characteristics and flexibility. 60 to 95 parts by volume are preferable in 100 parts by volume of the product.

[0029] Further, the aluminum oxide particles can be made to have a higher packing density by blending two or more types having an average particle size with a particle size distribution that results in the closest packing, and storage stability. The both side forces of thermal conductivity are preferable. For example, if the particle size distribution is close packed, For 100 parts by mass of the first aluminum oxide particles in the diameter range of 20-5 μm, this first

The second aluminum oxide particles having an average particle size of 1 aluminum oxide particles in the range of 1Z2 to 1Z10 are mixed with 20 to: LOO parts by mass.

[0030] As a typical commercial product of the spherical acid aluminum particles (A) used in the present invention,

DAW- 05 (Denki Kagaku Kogyo, average particle size 5 μm), DAW-10 (Denki Kagaku Kogyo, average particle size 10 μm), AS-40 (Made by Showa Denko, Average particle size 12 μm) m), AS-50 (manufactured by Showa Denko KK, average particle size 9 μm), and the like.

[0031] In general, the density of the curable resin is 1. OgZml, and the density of the acid aluminum is 4. Og / ml. Therefore, the curable resin 40 (ml) X 1.0 (g / ml) = 40 g, but oxynoreminium 60 (ml) X 4.0 (g / ml) = 240 g or more, which is about 86% by mass or more based on mass.

[0032] The curable resin composition (B) used in the present invention comprises (B-1) a thermosetting resin composition, and Z or (B-2) a photocurable resin composition! /.

[0033] Examples of the thermosetting resin composition (B-1) include a composition that is cured by heating and exhibits electrical insulation, such as an epoxy-based yarn composition, an oxetane-based yarn composition, and a melamine resin composition. In particular, in the present invention, a thermosetting resin composition comprising an epoxy compound and Z or oxetane compound, and a curing agent and Z or a curing catalyst can be preferably used. .

[0034] As the above-mentioned epoxy compound, known compounds can be used as long as they have one or more, preferably two or more epoxy groups in one molecule. For example, bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, tri Methylolpropane triglycidyl ether, phenol—; L, 3 -diglycidyl ether, biphenyl 4,4'-diglycidyl ether, 1,6-hexane diol diglycidyl ether, ethylene glycol or propylene glycol Examples include compounds having two or more epoxy groups in one molecule such as sidyl ether, sorbitol polyglycidyl ether, tris (2,3-epoxypropyl) isocyanurate, triglycidyltris (2-hydroxyethyl) isocyanurate, etc. . Further curing Mono-epoxy compounds such as butyl daricidyl ether, ferric glycidyl ether, and glycidyl (meth) acrylate can be added as long as the coating properties are not deteriorated! ,.

[0035] These can be used singly or in combination of two or more according to the demand for improving the properties of the coating film.

[0036] The oxetane compound is represented by the following general formula (I):

[Chemical 1]

(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

It is a compound containing an oxetane ring. Specific examples of the compound include 3-ethyl-3-hydroxymethyloxetane (trade name OXT-101, manufactured by Toagosei Co., Ltd.), 3 ethyl 3- (phenoxymethyl) oxetane (trade name OXT-211, manufactured by Toagosei Co., Ltd.). , 3 ethyl 3- (2-ethylhexyloxymethyl) oxetane (trade name OXT 212, manufactured by Toagosei Co., Ltd.), 1,4 bis {[((3 ethyl 3-oxeta-l) methoxy] methyl} benzene (Dongguan Examples thereof include trade name OXT-121) manufactured by Synthetic Co., Ltd., and bis (3-ethyl-3-oxeta-rumethyl) ether (trade name OXT-221 manufactured by Toagosei Co., Ltd.). In addition, a phenolic novolak-type oxetane compound is also included.

[0038] The oxetane compound can be used in combination with the epoxy compound or used alone. However, since the reactivity is lower than that of the epoxy compound, care should be taken to increase the curing temperature. is necessary.

[0039] Next, polyfunctional phenol compounds, polycarboxylic acids and acid anhydrides thereof, aliphatic or aromatic primary or secondary amines, polyamide resins, polymercapto are used as curing agents. Compound etc. are mentioned. Of these, polyfunctional phenolic compounds, and polycarboxylic acids and acid anhydrides thereof are preferably used from the viewpoint of workability and insulating properties.

[0040] The polyfunctional phenolic compound has two or more phenolic hydroxyl groups in one molecule. Any known compound can be used. Specifically, phenol novolac resin, cresol novolac resin, bisphenol A, arylated bisphenol A, bisphenol? Bisphenol A novolak resin, vinylphenol copolymer resin, and the like are preferable, and phenol novolac resin is particularly preferable because of its high reactivity and high heat resistance effect.

[0041] Such a polyfunctional phenol compound is subjected to an addition reaction with the epoxy compound and Z or oxetane compound in the presence of a suitable curing catalyst.

[0042] The polycarboxylic acid and the acid anhydride thereof are a compound having two or more carboxyl groups in one molecule and an acid anhydride thereof, such as a copolymer of (meth) acrylic acid, maleic anhydride, and the like. Examples thereof include copolymers and dibasic acid condensates. Commercially available products include Jonkrill (product group name) manufactured by Johnson Polymer Co., Ltd., SMA resin (product group name) manufactured by Arco Chemical Co., and polyazeline acid anhydride manufactured by Shin Nippon Science Co., Ltd.

[0043] Examples of the curing catalyst include a compound serving as a curing catalyst for the reaction of an epoxy compound and Z or oxetane compound, a polyfunctional phenol compound and Z or polycarboxylic acid and an acid anhydride thereof, or a curing agent. Examples of compounds that can be used as polymerization catalysts in the absence of benzene, such as tertiary amines, tertiary amine salts, quaternary onium salts, tertiary phosphines, crown ether complexes, and phospho-muylides. Any of these can be selected, and these can be used alone or in combination of two or more.

Among these, preferred are imidazoles such as trade names 2E4MZ, C11Z, C17Z and 2PZ, AZINE compounds of imidazoles such as trade names 2MZ-A and 2E4MZ-A, and trade names 2MZ—OK. , 2PZ—OK, etc. isocyanurate of imidazole, trade name 2PH Z, 2P4MHZ and other imidazole hydroxymethyl compounds (the trade name is also made by Shikoku Chemicals Co., Ltd.), dicyandiamide and its derivatives, melamine and its derivatives , Diaminomaleonitrile and its derivatives, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, bis (hexamethylene) triamine, triethanolamine, amines such as diaminodiphenylmethane, organic acid dihydrazide, 1,8-diazabicyclo [ 5, 4, 0] Undecen 7 (trade name DBU, manufactured by Sanya Pro), 3, 9-bis (3-aminopropi) ) One 2, 4, 8, 10-tetra Okisasupiro [5, 5] Undekan (trade name ATU, Ajinomoto Co.), or bird whistle - sulfo And organic phosphine compounds such as sulphine, tricyclohexylphosphine, tributylphosphine, and methyldiphenylphosphine.

[0045] The blending amount of these curing catalysts is sufficient in the usual quantitative ratio, for example, 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass in total of the epoxy compound and Z or oxetane compound. Is appropriate.

[0046] When this thermosetting resin composition (B-1) is applied to a composition for a flexible substrate, in the present invention, as an epoxy compound, a product manufactured by Japan Epoxy Resin Co., Ltd. Use hydrogenated biphenyl type epoxy resin such as YL6800, and use rubbery compound with functional group that reacts with epoxy group as curing agent, for example, carboxyl group-terminated butadiene acrylonitrile called CTBN. be able to.

[0047] As the photocurable resin composition (B-2), any resin composition that is cured by irradiation with active energy rays and exhibits electrical insulation can be used. A resin composition containing a compound having at least one ethylenically unsaturated bond and a photopolymerization initiator is preferred because of excellent heat resistance and electrical insulation.

[0048] As the compound having one or more ethylenically unsaturated bonds in one molecule, known and commonly used photopolymerizable oligomers, photopolymerizable vinyl monomers, and the like are used.

[0049] Examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers. Examples of (meth) acrylate oligomers include phenol novolak epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate.

, Epoxy (meth) acrylate, such as bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate And polybutadiene-modified (meth) acrylate.

[0050] In the present specification, "(meth) atalylate" is a term that collectively refers to talate, metatalate, and a mixture thereof, and other similar expressions! The same is true.

[0051] Examples of the photopolymerizable butyl monomer include known and commonly used monomers such as 2-ethyl hexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isopolo -Le (meth) acrylate, ferrule (meth) acrylate, phenoxychetyl Esters of (meth) acrylic acid such as (meth) acrylate; hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate Rates; alkoxyalkylene glycol mono (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxy shetyl (meth) acrylate; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, 1, 6 hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hex (meth) acrylate Alkylenepolyol poly (meth) acrylate, such as dirate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol 200 di (meth) acrylate, ethoxylated trimethylolpropane triatalylate, propoxy Poly (oxyalkylene glycol) poly (meth) acrylates such as trimethylolpropane tri (meth) acrylate; poly (meth) acrylates such as neopentyldarlicol ester di (meth) acrylate, hydroxybivalate; tris [(Meth) Atari-mouthed Kichetil] Isocyanurate-type poly (meth) atalylates such as isocyanurate.

[0052] These may be used singly or in combination of two or more according to the requirements on the properties of the coating film.

[0053] Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether and their alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenol. -Luacetophenone, 2-hydroxy-2-methyl 1-phenolpropane 1-one, diethoxyacetophenone, 2, 2-diethoxy 2-phenylacetophenone, 1, 1-dichloroacetophenone, 1— Hydroxycyclohexyl phenyl ketone, 2-methyl 1

[4 (Methylthio) phenol] Acetophenones such as 2 morpholinopropane 1-one; methylanthoraquinone, 2-ethyl anthoraquinone, 2-tertiarybutyl anthraquinone, 1-claw anthraquinone, 2-amino Anthoraquinones, such as leansoraquinone; thixanthone, 2,4 jetylthioxanthone, 2 cyclodithioxanthone, 2,4-dicyclodithioxanthone, 2-methylthioxanthone, 2,4 diisopropylthioxa Thixanthones such as nton; acetophenone dimethyl ketal, benzyl dimethyl ketal

-Ketals such as benzene; benzophenones such as benzophenone and 4, 4-bismethylaminominobenzophenone. These can be used alone or in admixture of two or more kinds. Further, tertiary amines such as trihetanolamine, methyljetanolamine and the like; 2 dimethylaminoethylbenzoic acid, 4 dimethylaminobenzoic acid and other benzoic acids It can be used in combination with a photoinitiator aid such as a derivative.

[0054] In the insulating curable resin composition of the present invention, a wet 'dispersing agent can be added as necessary to facilitate high filling. Examples of such a wet dispersing agent include compounds having a polar group such as a carboxyl group, a hydroxyl group, and an acid ester, polymer compounds such as acid-containing compounds such as phosphate esters, and copolymers containing an acid group. Hydroxyl group-containing polycarboxylic acid esters, polysiloxanes, salts of long-chain polyaminoamides and acid esters, and the like can be used. Examples of commercially available wetting / dispersing agents that can be used particularly favorably include Disperbyk (registered trademark) 1 101, 1 103, 1 110, 1 111, 1 160, 1 17 1, —174, — 190, -300, Bykumen (registered trademark), BYK-P 105,-P104,-P 104S, one 240 (all manufactured by Bic 'Kemiichi' Japan), EFKA-polymer 150, EF KA-44, -63 , -64, -65, -66, -71, -764, -766, N (all manufactured by F-Power Co., Ltd.).

[0055] The insulating curable resin composition of the present invention may contain an organic solvent for adjusting the composition and adjusting the viscosity. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methylcetosolve, butylcetosolve, carbitol, and methylcarbitol. Glycol ethers such as ethyl, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol jetyl ether, tripropylene glycol monomethyl ether; ethyl acetate, butylacetate, butyl lactate, cellosolve acetate, butylcetosolve Acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetates, esters such as propylene carbonate; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha Organic solvents such as petroleum solvents such as solvent naphtha can be used. These organic solvents can be used alone or in combination of two or more.

[0056] The insulating curable resin composition of the present invention may further include phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and the like, if necessary. Known conventional colorants, known conventional thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, known conventional thickeners such as fine silica, organic bentonite, montmorillonite, silicone And conventional additives such as Z-leveling agents, Z-leveling agents, imidazole-type, thiazole-type, triazole-type silane coupling agents, etc. it can.

[0057] The insulating curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method with the organic solvent, and coated on the substrate by a method such as screen printing.

[0058] When the insulating curable resin composition is a thermosetting resin composition (B-1), after application, it is heated to a temperature of about 140 ° C to 180 ° C and thermally cured. Thus, a cured coating film can be obtained.

[0059] Further, when the insulating curable resin composition is a photocurable resin composition (B-2), after coating, the composition is irradiated with ultraviolet rays using a high pressure mercury lamp, a metal halide lamp, a xenon lamp, etc. A cured coating can be obtained.

[0060] (Example)

EXAMPLES Next, the present invention will be described in detail with reference to examples and comparative examples of the present invention. However, the present invention is not limited to the following examples. In the following, “parts” and “%” represent “parts by mass” and “% by mass” unless otherwise specified.

The components of Example 1 and Comparative Examples 1, 3, and 4 shown in Table 1 below were kneaded with a three-roll mill to obtain a thermosetting resin composition. Table 3 shows the storage stability evaluation results of the obtained thermosetting resin composition, and Table 4 shows the characteristics evaluation results.

[table 1] table 1

Note) The volume occupancy of acid aluminum was determined from the volume V0 of the components excluding aluminum oxide and the volume VI after the addition of acid aluminum as follows.

The volume occupancy of Sani匕aluminum (volume ^{_{0/0) = (V1 -V0}} ) / V1 X 100

Similarly, the volume occupancy of the spherical silica was determined from the volume VO of the components excluding the spherical silica and the volume VI after adding the spherical silica force as follows.

Volume fraction of spherical silica (capacity%) = (V1 -V0) / V1 X 100

The blending components of Example 2 and Comparative Examples 2, 5, and 6 shown in Table 2 below were kneaded with a three-roll mill to obtain a photocurable resin composition. Table 3 shows the storage stability evaluation results of the obtained photocurable resin composition, and Table 4 shows the characteristics evaluation results.

[Table 2] Table 2

Note) The volume occupancy of acid aluminum was determined from the volume V0 of the components excluding acid aluminum and the volume VI after addition of acid aluminum as follows.

Volume fraction of aluminum oxide (capacity%) = (V1 -V0) / V1 X 100

Similarly, the volume occupancy of the spherical silica was determined from the volume V0 of the components excluding the spherical silica and the volume VI after adding the spherical silica force as follows.

Volume fraction of spherical silica (capacity%) = (V1 -V0) / V1 X 100

[Table 3]

Table 3

[Table 4] Table 4

[0064] The evaluation methods in Tables 3 and 4 are as follows.

[0065] Storage stability evaluation:

The thermosetting compositions of Example 1 and Comparative Examples 1, 3, and 4 were stored in a sealed black container made of polyethylene at 5 ° C. The sedimentation state was evaluated after 2, 7, 30, and 90 days. Further, the photocurable compositions of Example 2 and Comparative Example 2 were put in a polyethylene sealed black container and stored in a dark place at 20 ° C. The sedimentation state was evaluated after 2, 7, 30, and 90 days.

No settling

○: Slightly settled, but no problem in use by stirring without agglomeration

X: Sedimented and aggregated. Even if stirred, it becomes useless and unusable

Characterization:

(1) Thermal conductivity

The thermosetting compositions of Example 1 and Comparative Examples 1, 3, and 4 were applied onto the test substrate by screen printing so that the cured coating film was about 40 m, and cured at 150 ° C. for 60 minutes. . In addition, the photocurable compositions of Example 2 and Comparative Examples 2, 5, and 6 were applied onto the test substrate by screen printing so that the cured coating film was about 40 m, and a wavelength of 350 nm was applied using a metal halide lamp. in was cured by irradiation with integrated light quantity of 2jZcm ^2. At 25-125 ° C The thermal conductivity of was measured by the laser flash method.

[0066] (2) Solvent resistance

The thermosetting compositions of Example 1 and Comparative Examples 1, 3, and 4 were pattern-printed on a circuit-formed FR-4 substrate by screen printing so that the dry coating thickness was about 40 m, at 150 ° C. Cured for 60 minutes. In addition, the photocurable compositions of Example 2 and Comparative Examples 2, 5, and 6 were subjected to screen printing on a FR-4 substrate on which a circuit was formed so that the dried coating film had a thickness of about 40 μm, and a metal halide was formed. The lamp was cured by irradiating an integrated light amount of 2j / cm ² at a wavelength of 350 nm. The obtained substrate was immersed in propylene glycol monomethyl ether acetate for 30 minutes, dried, and then subjected to a peel test using a cellophane adhesive tape to evaluate the peeling and discoloration of the coating film.

○: No peeling or discoloration

X: Those with peeling or discoloration

(3) Heat resistance

Substrates obtained in the same manner as solvent resistance using the thermosetting compositions of Example 1 and Comparative Examples 1, 3, and 4 and the photocurable compositions of Examples 2 and Comparative Examples 2, 5, and 6. Apply rosin-based flux to a solder bath at 260 ° C for 10 seconds, wash with propylene glycol monomethyl ether acetate, dry, perform a peel test with cellophane adhesive tape, and peel off the coating! And evaluated.

○: No peeling

X: Exfoliation

(4) Pencil hardness

Substrates obtained in the same manner as solvent resistance using the thermosetting compositions of Example 1 and Comparative Examples 1, 3, and 4 and the photocurable compositions of Examples 2 and Comparative Examples 2, 5, and 6. Then, the pencil core from B to 9H was sharpened so that the tip was flat and pressed at an angle of about 45 ° to record the hardness of the pencil that did not peel off.

[0067] (5) Electrical insulation

The thermosetting compositions of Example 1 and Comparative Examples 1, 3, and 4 were screen printed on the FR-4 substrate on which the IPC standard B pattern comb-shaped electrode was formed, so that the dry film thickness was about 40 μm. To Turn printed and cured at 150 ° C for 60 minutes. In addition, the photocurable compositions of Example 2 and Comparative Examples 2, 5, and 6 were screen-printed on a FR-4 substrate on which an IPC standard B pattern comb-shaped electrode was formed. The pattern was printed in such a way that it was cured by irradiating an integrated light quantity of 2j / cm ² at a wavelength of 350 nm with a metalno and ride lamp. The insulation resistance value between the electrodes of the obtained substrate was measured at an applied voltage of 500V.

As is apparent from the results shown in Table 3 and Table 4, according to the curable insulating composition of the present invention, the thermal conductivity exceeds 2 WZm′K in both thermosetting and photocuring, and A cured product having sufficient characteristics as a heat-resistant insulating material for printed wiring boards can be obtained.

Claims

The scope of the claims

[1] (A) Spherical aluminum oxide particles having a thermal conductivity of 15 WZm′K or more, and (B) a curable resin composition, the total capacity of the cured product of the resin composition for printed wiring boards On the other hand, the volume occupancy of the aluminum oxide particles (A) is 60% by volume or more, and the thermal conductivity of the cured product is 2 WZm · K or more. Fat composition.

[2] The insulating curable resin composition for printed wiring boards according to claim 1, wherein the acid aluminum particles (A) have a particle force of 30 μm or less.

[3] The acid / aluminum particles (A) have an average of the first acid / aluminum particles with respect to 100 parts by mass of the first aluminum oxide particles having a particle diameter of 5 to 20 m. The insulating curable resin composition for printed wiring boards according to claim 1 or 2, wherein 20 to 100 parts by mass of second aluminum oxide particles having a particle size in the range of 1Z2 to 1Z10 are combined.

[4] The insulating curable resin for printed wiring boards according to any one of claims 1 to 3, which is the curable resin composition (B) force (B-1) thermosetting resin composition. Composition.

[5] The thermosetting resin composition (B-1) is an epoxy compound and a Z or oxetane compound, and the resin composition for a printed wiring board further includes the thermosetting resin composition. 5. The insulating curable resin composition for printed wiring boards according to claim 4, comprising a curing agent (B-1) and Z or a curing catalyst.

[6] The insulating curable resin for printed wiring boards according to any one of claims 1 to 3, wherein the curable resin composition is (B) force (B-2) a photocurable resin composition. Composition.

[7] The photocurable resin composition (B-2) according to claim 6, comprising a compound having one or more ethylenically unsaturated bonds in one molecule and a photopolymerization initiator. An insulating curable resin composition for printed wiring boards.

[8] The thermal conductivity obtained by irradiating with active energy rays and Z or thermosetting the insulating curable resin composition for printed wiring boards according to any one of claims 1 to 7 is 2 WZm · Hardened product of K or higher.

[9] The insulating layer and the Z or solder resist by the cured product obtained by irradiating the insulating curable resin composition according to any one of claims 1 to 7 with active energy irradiation and Z or heat curing. A printed wiring board formed with layers.