JP2004277727A - Curable resin composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition suitable as a material for an interlayer insulator for a multilayered printed wiring board which has a small thermal expansion coefficient, which is an important performance for the interlayer insulating material for the multilayered printed wiring board, and is excellent in thermal shock resistance, dimensional stability and adhesion to a copper-plated conductor (peeling strength from a copper-plated conductor). <P>SOLUTION: The curable resin composition comprises a curable resin (A), a filler (B) and a curing accelerator (C), where the filler has a volume-average particle size of 1-100 nm. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a curable resin composition and a cured product thereof. More specifically, the present invention relates to a curable resin composition suitable as an interlayer insulating material for a multilayer printed wiring board.

One of the most important performances as an interlayer insulating material of a multilayer printed wiring board is thermal shock resistance. The thermal shock resistance test is performed by applying a heat load to the test substrate by alternately immersing the test substrate in a bath (air bath or solvent bath) adjusted to a low temperature (normally −55 ° C.) and a high temperature (normally 125 ° C.). This is a durability test for testing whether a crack or break has physically occurred in the substrate material after repeating from one hundred to several thousand times. In the thermal shock resistance test, a substrate material thermally expands and contracts due to a temperature difference between a low temperature and a high temperature, respectively. If the degree of thermal expansion and thermal contraction differs between the substrate materials, stress occurs at the interface between the substrate materials. If the stress cannot be relieved by the substrate material, cracks or breaks occur. As the substrate material, an interlayer insulating resin, a copper circuit, a core substrate, a plating resist, and the like are used. Usually, the copper circuit has a relatively small coefficient of thermal expansion of about several ppm / ° C. Is a thermal expansion coefficient of about several ppm to 20 ppm / ° C. On the other hand, the thermal expansion coefficient of the interlayer insulating resin is as large as 40 ppm / ° C. or more.
In order to reduce the stress generated between the interlayer insulating resin and other materials during the thermal shock test, studies have been conducted to reduce the coefficient of thermal expansion of the interlayer insulating resin. A method of adding a filler is common (for example, Patent Documents 1 to 3).

JP-A-6-120626 JP-A-6-196856 JP-A-2000-86871

  However, when the amount of filler added increases, there is a problem that adhesion to copper plating (peeling strength with copper plating) decreases, and when the amount of filler added is small, the degree of decrease in the coefficient of thermal expansion is insufficient. There was no problem. That is, an object of the present invention is to solve these problems and to provide an insulating material having a small coefficient of thermal expansion and no decrease in peel strength.

The present inventors have conducted intensive studies to solve the above problem, and as a result, by using a filler having a specific average particle size, the coefficient of linear expansion after curing is low, and the adhesion between the cured resin and the copper plating is reduced. The present inventors have found that a curable resin composition having a large property (peeling strength) can be obtained, and have reached the present invention.
That is, the present invention provides a curable resin composition comprising a curable resin (A), a filler (B), and a curing accelerator (C), wherein the filler has a volume average particle diameter of 1 to 100 nm. And a cured product thereof.

  The curable resin composition of the present invention simultaneously imparts a small coefficient of linear expansion and a large adhesiveness (peel strength) to the cured product, and when these cured products are used, for example, as an insulating material for a printed wiring board. Has the effect of imparting large substrate strength, excellent thermal shock resistance, and high durability.

The curable resin composition of the present invention comprises a curable resin (A), a filler (B), and a curing accelerator (C).
As the filler (B) in the present invention, known inorganic fillers (B1) and organic fillers (B2) can be used.

The inorganic filler (B1) is classified into a metal oxide and a metal salt.
As the metal oxide (B1), known materials can be used, and specific examples include titanium oxide, silicon oxide, and aluminum oxide.
Known metal salts can be used, and specific examples thereof include calcium carbonate and barium sulfate.
Among these (B1), metal oxides are preferred from the viewpoints of electrical properties (wet heat reliability / dielectric properties), heat resistance and chemical resistance. More preferred are silicon oxide and titanium oxide. Particularly preferred is silicon oxide.
The melting point (° C.) of (B1) is preferably from 300 to 2,000, more preferably from 400 to 1900, and particularly preferably from 500 to 1800, from the viewpoint of the coefficient of linear expansion and availability. That is, the melting point (° C.) of (B1) is preferably at least 300, more preferably at least 400, particularly preferably at least 500, and preferably at most 2,000, more preferably at most 1,900, particularly preferably at most 1,800. .

Examples of the organic filler (B2) include fluororesin powder, polyether sulfone powder, and nylon powder.
The glass transition temperature (° C.) of (B2) is preferably from 170 to 300, more preferably from 190 to 280, and particularly preferably from 210 to 260, from the viewpoints of linear expansion coefficient and availability. That is, the glass transition temperature (° C.) of the organic filler is preferably 170 or more, more preferably 190 or more, particularly preferably 210 or more, and preferably 300 or less, more preferably 280 or less, and particularly preferably 260 or less. is there.

  Among these fillers, silicon oxide, fluorine powder, and polyether sulfone powder are preferable, and silicon oxide is more preferable, from the viewpoints of cost, electric characteristics (such as insulating property and dielectric constant), heat resistance, and chemical resistance. .

  The volume average particle diameter of the filler (B) is 1 to 100 nm, and preferably 5 to 80 nm, more preferably 10 to 70 nm, and particularly preferably 15 to 60 nm, from the viewpoint of linear expansion coefficient and adhesion. That is, the volume average particle size (nm) of the filler is 1 or more, preferably 5 or more, more preferably 10 or more, particularly preferably 15 or more, and 100 or less, preferably 80 or less, more preferably Is 70 or less, particularly preferably 60 or less.

  Further, the 90% volume cumulative particle diameter (Dv90) of the filler (B) is preferably from 2 to 200 nm, more preferably from 10 to 160, and particularly preferably from 20 to 140, from the viewpoint of adhesion and thermal expansion coefficient. It is. That is, Dv90 (nm) is 2 or more, preferably 10 or more, more preferably 20 or more, and 200 or less, preferably 160 or less, and more preferably 140 or less.

The volume average particle diameter and the particle diameter distribution are measured in accordance with a method for measuring the particle diameter distribution of a fine ceramic raw material by a laser diffraction / scattering method.
Dv90 is the particle size when the cumulative amount in the relative cumulative particle size distribution curve is 90% by weight.

  The content (% by weight) of the filler (B) is preferably from 1 to 33% by weight, more preferably from the viewpoint of the coefficient of thermal expansion of the curable resin composition after curing, based on the weight of the curable resin composition. Is 2 to 32, particularly preferably 3 to 30. That is, the content (% by weight) of the filler is preferably 1 or more, more preferably 2 or more, particularly preferably 3 or more, and more preferably 33 or less, based on the weight of the curable resin composition. Is 32 or less, particularly preferably 30 or less.

  The filler used in the present invention may have a volume average particle diameter in the above-mentioned range, and is not particularly limited to a production method. In particular, when the filler is a metal oxide, a solution containing a metal oxide precursor (D) is used. Can be produced by a sol-gel method. The sol-gel method is a normal sol-gel method, that is, a metal halide or metal alkoxide is hydrolyzed and partially polycondensed to form a hydrated metal oxide sol solution, which is then dehydrated and polycondensed. Means a method of preparing an inorganic oxide by heating the gel if necessary.

  As the metal oxide precursor (D), a metal alkoxide (D1), a metal halide (D2), an organic / metal composite alkoxide (D3), an organic / metal composite halide (D4), and a combination thereof can be used.

  As the metal alkoxide (D1), a compound represented by the general formula (1) can be used.

                  M (-OR) n (1)

  In the general formula (1), M represents an n-valent metal atom and may be used without limitation as long as it is a metal atom that can stably exist as a metal alkoxide. For example, indium, tin, zinc, aluminum, silicon, vanadium, manganese , Iron, zirconium, antimony, tungsten, titanium, and other metal atoms, and combinations thereof. Among these, silicon and titanium are preferred from the viewpoint of the availability of the metal alkoxide (D1), and more preferably silicon.

In the general formula (1), RO- represents an alkoxy group, and an alkoxy group having 1 to 30 carbon atoms or the like is used. Examples of the alkoxy group having 1 to 30 carbon atoms include methoxy, ethoxy, propoxy, n-butoxy, i-butoxy, t-butoxy, hexyloxy, 2-ethylhexyloxy, decyloxy, hexadecyloxy, eicosyloxy and tricosaoxy. And the like.
Among these, methoxy, ethoxy, propoxy, n-butoxy and t-butoxy are preferred, more preferably methoxy and ethoxy, and particularly preferably ethoxy, from the viewpoint of the availability and handleability of the metal alkoxide (D1). .
Further, in the general formula (1), n is an integer of 2 to 5, and is preferably an integer of 3 to 5, and more preferably 3 to 5, from the viewpoints of availability and handleability of the metal alkoxide (D1). An integer of 4, particularly preferably 4.

  Examples of the compound represented by the general formula (1) include tetraalkoxysilane, tetraalkoxytitanium, trialkoxyaluminum and the like. Examples of the tetraalkoxysilane include dimethoxydiethoxysilane, methoxytriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and tetraisopropoxysilane. Examples of the tetraalkoxytitanium include dimethoxydiethoxytitanium, tetraethoxytitanium, and tetraisopropoxytitanium. Examples of trialkoxy aluminum include triethoxy aluminum and triisopropoxy aluminum. Among these, from the viewpoint of availability and the like, tetraalkoxysilane and trialkoxyaluminum are preferable, more preferably tetraalkoxysilane, particularly preferably tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane. .

  As the metal halide (D2), a compound represented by the general formula (2) or the like can be used.

                  M (-X) n (2)

  In the general formula (2), M represents an n-valent metal atom and may be used without limitation as long as it is a metal atom that can be stably present as a metal halide. For example, indium, tin, zinc, aluminum, silicon, vanadium, Examples include metal atoms such as manganese, iron, zirconium, antimony, tungsten, and titanium, and combinations thereof. Among these, silicon and titanium are preferable, and silicon is more preferable, from the viewpoint of the availability of the metal halide (D2) and the like.

Further, in the general formula (2), X- represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In the general formula (2), n is an integer of 2 to 5, and is preferably an integer of 3 to 5, and more preferably an integer of 3 to 4 from the viewpoint of availability of the metal halide (D2). And particularly preferably 4.

  Examples of the compound represented by the general formula (2) include silane tetrahalide, titanium tetrahalide, and aluminum trihalide. Examples of the silane tetrahalide include silane tetrachloride, silane tetrabromide, silane tetrafluoride, and silane tetraiodide. Examples of the titanium tetrahalide include titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, titanium tetraiodide and the like. Examples of the aluminum trihalide include aluminum trichloride, aluminum tribromide, aluminum trifluoride, and aluminum triiodide. Of these, silane tetrahalide and aluminum trihalide are preferred from the viewpoint of availability and the like, more preferably silane tetrahalide, and particularly preferably silane tetrachloride and silane tetrabromide.

The organic / metal composite alkoxide (D3) is a metal alkoxide containing an organic group other than the alkoxy group.
For example, as methoxysilane, trimethoxymethylsilane, trimethoxyethylsilane, trimethoxyhexylsilane, trimethoxyphenylsilane, dimethoxydimethylsilane, dimethoxydiethylsilane, dimethoxydihexylsilane, dimethoxydiphenylsilane, bis (trimethoxysilyl) methylene, Bis (trimethoxysilyl) ethylene, bis (trimethoxysilyl) hexamethylene, o-bis (trimethoxysilyl) benzene, m-bis (trimethoxysilyl) benzene, p-bis (trimethoxysilyl) benzene, bis (dimethoxy) Methylsilyl) methylene, bis (dimethoxymethylsilyl) ethylene, bis (dimethoxymethylsilyl) hexamethylene, o-bis (dimethoxymethylsilyl) benzene, m-bis (dimethoate) (Simethylsilyl) benzene, p-bis (dimethoxymethylsilyl) benzene, bis (methoxydimethylsilyl) methylene, bis (methoxydimethylsilyl) ethylene, bis (methoxydimethylsilyl) hexamethylene, o-bis (methoxydimethylsilyl) benzene, m -Bis (methoxydimethylsilyl) benzene, p-bis (methoxydimethylsilyl) benzene and the like.
As the ethoxysilane, those in which the methoxy group of the methoxysilane described here is an ethoxy group can be used. In addition, alkoxytitanium in which the silicon element of the alkoxysilane mentioned here is a titanium element can also be used.

  The organic / metal composite halide (D4) is a metal halide containing an organic group. For example, when the alkoxy group of the compound described in the organic / metal composite alkoxide (D3) is a halogen atom (a fluorine atom, a chlorine atom) , A bromine atom and an iodine atom).

From the viewpoint of the melting point of the filler, the metal oxide precursor (D) preferably contains a metal alkoxide (D1) or a metal halide (D2),
More preferably, a combination of (D1) and (D3) and a combination of (D2) and (D4) from the viewpoint of the particle diameter of the filler, and (D1) and (D1) from the viewpoint of easy purification of the obtained filler. The combination of D3) is particularly preferred.

  As a method for producing a metal oxide filler by a sol-gel method using a solution containing the metal oxide precursor (D), for example, water, a solvent if necessary, A method of adding a part or all of the catalyst and the curable resin and / or other additives to form a uniform sol solution and then reacting and gelling (dehydration polycondensation) may be mentioned.

  The formation of the sol solution needs to involve a hydrolysis reaction and requires water. The amount (% by weight) of water is preferably 100 or more, more preferably 150 or more, and particularly preferably, based on the weight of the metal oxide precursor (A), from the viewpoint of ease of preparation of the sol solution. It is preferably at least 200, more preferably at most 1,000, further preferably at most 600, particularly preferably at most 400.

  The solvent is not particularly limited as long as the solvent can be used among (D1) to (D4), water, a catalyst, a curable resin, and / or other additives. (E.g., methanol, ethanol, isopropanol and t-butanol), ketones having 3 to 6 carbon atoms (such as acetone, methyl ethyl ketone and methyl isobutyl ketone), ethers having 4 to 8 carbon atoms (such as diethyl ether, tetrahydrofuran and diethylene glycol) and These mixtures and the like can be used. Among the solvents, alcohols having 1 to 4 carbon atoms, ketones having 3 to 6 carbon atoms and mixtures thereof are preferable from the viewpoints of affinity for water and solubility of the curable resin, and more preferably methanol, Ethanol, acetone and methyl ethyl ketone.

  When a solvent is used, the amount (% by weight) of the solvent is preferably 10 or more, more preferably 10 or more based on the total weight of the metal oxide precursor (D), from the viewpoint of easy preparation of the sol solution. Is 50 or more, particularly preferably 100 or more, and likewise preferably 1,000 or less, more preferably 500 or less, particularly preferably 200 or less.

The catalyst is added as necessary as a catalyst for accelerating solification and gelation of the metal oxide precursor (D), and includes an acid catalyst and a base catalyst.
The acid catalyst includes an inorganic acid and an organic acid (C1-7).
Examples of the inorganic acid include hydrohalic acids such as hydrochloric acid, hydrobromic acid and hydroiodic acid, nitric acid, nitrous acid, sulfuric acid and phosphoric acid.
Examples of the organic acid include monocarboxylic acids such as acetic acid, formic acid and oxalic acid; hydroxycarboxylic acids such as lactic acid; dicarboxylic acids such as adipic acid, oxalic acid and succinic acid; polycarboxylic acids such as glycerol triacetate; Alkyl phosphoric acid; and alkyl sulfonic acids such as methane sulfonic acid and paratoluene sulfonic acid.

Examples of the base catalyst include an inorganic base and an organic base (1-6 carbon atoms).
Inorganic bases include sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate and ammonia.
Examples of the organic base include methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, n-pentylamine, n-hexylamine, dimethylamine, diethylamine, trimethylamine and triethylamine.
Of these catalysts, acid catalysts are preferred, and hydrohalic acid is more preferred.

  When a catalyst is used, the amount (% by weight) of the catalyst is preferably 0.1 or more, more preferably 0.2 or more, and particularly preferably 0.1 or more, based on the weight of the metal oxide precursor (D). It is 4 or more, preferably 1 or less, more preferably 0.8 or less, particularly preferably 0.5 or less.

  In preparing the sol solution, water, a solvent, a part or all of the curable resin, and / or other additives are first added, followed by stirring and homogenization. Next, the metal oxide precursor (D) is added while stirring. When it is difficult to make the composition uniform, it is desirable to add a catalyst as needed. After homogenization, it becomes a sol solution after aging. The temperature (° C.) of the solution at this time is preferably 0 or more, more preferably 10 or more, particularly preferably 20 or more, and preferably 200 or less, more preferably 100 or less, and particularly preferably 80 or less. The aging time is preferably 30 minutes or more, more preferably 1 hour or more, particularly preferably 2 hours or more, and 12 hours or less, more preferably 8 hours or less, and particularly preferably 6 hours or less. .

The curable resin (A) includes a thermosetting resin, a photocurable resin, and the like.
Examples of the thermosetting resin include an epoxy resin (A1), a polyimide resin, and a resin having another reactive group. Examples of the thermosetting resin include an epoxy resin described in JP-A-2001-279116, and JP-A-2002-88242. A polyimide resin described in the gazette and a resin having another reactive group described in JP-A-2001-279110 can be used.
Examples of the photocurable resin include an epoxy resin and a resin having another reactive group. For example, the epoxy resin described in JP-A-2002-105117 and other resins described in JP-A-11-214815 are disclosed. Resins having a reactive group can be used.
Among these curable resins, a thermosetting resin is preferable from the viewpoint of simplicity of the curing reaction and the like, and an epoxy resin (A1) is more preferable from the viewpoint of cost and dielectric properties.

The epoxy resin (A1) as a thermosetting resin is composed of an epoxide and a curing agent.
As the epoxide, the above-mentioned known compounds can be used, and for example, glycidyl ether epoxide, glycidyl ester epoxide, glycidylamine epoxide, alicyclic epoxide and the like can be used.

Examples of the glycidyl ether type epoxide include glycidyl ether of dihydric phenol, glycidyl ether of polyhydric phenol, glycidyl ether of dihydric alcohol, and glycidyl ether of polyhydric alcohol.
Examples of the glycidyl ether of a dihydric phenol include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and bisphenol S diglycidyl ether.
Examples of the glycidyl ether of polyhydric phenol include dihydroxynaphthyl cresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, and dinaphthyltriol triglycidyl ether.
Examples of the glycidyl ether of a dihydric alcohol include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and polyethylene glycol (weight average molecular weight (hereinafter, Mw): 150 to 4,000) diglycidyl ether and polypropylene glycol (Mw: 180 to 5,000) diglycidyl ether.
Examples of the glycidyl ether of a polyhydric alcohol include trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether, and poly (polymerization degree 2 to 5) glycerin polyglycidyl ether.

As the glycidyl ester type epoxide, glycidyl ester of carboxylic acid, glycidyl ester type polyepoxide and the like are used.
Examples of the glycidyl ester of a carboxylic acid include glycidyl methacrylate, diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, and triglycidyl trimellitate.

As the glycidylamine type epoxide, glycidyl aromatic amine, glycidyl alicyclic amine, glycidyl heterocyclic amine and the like are used.
Examples of the glycidyl aromatic amine include N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl Diaminodiphenyl sulfone and N, N, N ', N'-tetraglycidyldiethyldiphenylmethane.
Glycidyl alicyclic amines include bis (N, N-diglycidylaminocyclohexyl) methane (a hydrogenated compound of N, N, N ', N'-tetraglycidyldiaminodiphenylmethane) and N, N, N', N ' -Tetraglycidyl dimethylcyclohexylenediamine (hydrogenated compound of N, N, N ', N'-tetraglycidylxylylenediamine) and the like.
Examples of the glycidyl heterocyclic amine include trisglycidylmelamine and N-glycidyl-4-glycidyloxypyrrolidone.

  Examples of the alicyclic epoxide include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxydicyclopentyl ether and 3,4-epoxy-6-methyl. Cyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate and the like.

  Among these epoxides, glycidyl ether epoxides, glycidyl ester epoxides and glycidylamine epoxides are preferred from the viewpoints of cost and heat resistance, and more preferred are glycidyl ether epoxides and glycidyl ester epoxides. As these epoxides, these may be used alone, or two or more selected from them may be used as a mixture.

  The number of epoxy groups in the epoxide is preferably at least 2 in number average, more preferably from 2 to 500, and further preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more. The number is most preferably 6 or more. The upper limit is more preferably 300 or less, particularly preferably 100 or less, still more preferably 50 or less, and most preferably 40 or less. When the number of epoxy groups is within this range, the cured product of the curable resin of the present invention tends to have better thermal shock resistance and dielectric properties.

  The weight average molecular weight (hereinafter, abbreviated as Mw) of the epoxide is preferably 300 to 10,000, more preferably 400 or more, particularly preferably 500 or more, and still more preferably 9, from the viewpoint of thermal shock resistance and the like. 000 or less, particularly preferably 5,000 or less.

Known curing agents can be used, for example, carboxylic acids, acid anhydrides, amine compounds, phenols, and the like.
As the carboxylic acid, an aromatic carboxylic acid and an alicyclic carboxylic acid are used.
Known aromatic carboxylic acids can be used, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and trimellitic acid.
As the alicyclic carboxylic acid, known ones can be used, and cyclohexane-1,2-dicarboxylic acid (aromatic hydrogenation compound of phthalic acid) and cyclohexane-1,3-dicarboxylic acid (aromatic hydrogenation of isophthalic acid) can be used. Compounds) and the like.
Known acid anhydrides can be used, and examples thereof include phthalic anhydride, maleic anhydride, and 4-methylcyclohexane-1,2-dicarboxylic anhydride.

As the amine compound, an aromatic amine compound, an aliphatic amine compound, an alicyclic amine compound, or the like is used.
As the aromatic amine compound, known compounds can be used, and examples thereof include 1,3-phenylenediamine, 1,4-phenylenediamine, and 4,4′-diphenylmethanediamine.
As the aliphatic amine compound, known compounds can be used, and examples thereof include ethylenediamine, propylenediamine, trimethylenediamine, diethylenetriamine, and iminobispropylamine.
As the alicyclic amine compound, known compounds can be used, and cyclohexylene-1,3-diamine (aromatic hydrogenated compound of 1,3-phenylenediamine) and cyclohexylene-1,4-diamine (1,4 -Hydrogenated aromatic nucleus compound of phenylenediamine), bis (aminocyclohexyl) methane (hydrogenated compound of aromatic nucleus of 4,4'-diphenylmethanediamine) and the like.
Known phenols can be used, and cresol / novolak resin (Mw: 320 to 32,000), phenol novolak resin (Mw: 360 to 36,000), naphthyl cresol, tris (hydroxyphenyl) methane, and dinaphthyl Triol, tetrakis (4-hydroxyphenyl) ethane, 4,4′-oxybis (1,4-phenylethyl) tetracresol and the like can be mentioned.

Of these curing agents, phenol is preferred from the viewpoint of reliability.
These curing agents may be used alone or as a mixture.

  The equivalent ratio of the epoxide to the curing agent (epoxide / curing agent) is preferably 0.7 to 1.3, more preferably 0.8 or more, and particularly preferably 0.9 from the viewpoint of the Tg and strength of the cured product. It is more preferably 1.2 or less, particularly preferably 1.1 or less.

A curing accelerator (C) is added to the epoxy resin as the thermosetting resin. When the curable resin is an epoxy resin, for example, a known catalyst such as an imidazole catalyst and a tertiary amine can be used as the curing accelerator (C).
When this curing accelerator (C) is used, the addition amount (% by weight) of the curing accelerator (C) is preferably 0.1 to 10 based on the total weight of the curable resin composition, and more preferably. Is 0.3 or more, particularly preferably 0.5 or more, and further preferably 7 or less, particularly preferably 5 or less.

A polyimide resin as a thermosetting resin comprises a diamine and a tetracarboxylic dianhydride.
As the diamine, the above-mentioned known ones can be used. For example, paraphenylenediamine, 2,2′-bis (4-aminophenoxyphenyl) propane, bis (2- (4-aminophenoxy) ethoxy) ethane and the like can be used. Can be used.
As the tetracarboxylic dianhydride, the above-mentioned known compounds and the like can be used. For example, pyromellitic dianhydride and benzophenonetetracarboxylic dianhydride can be used.

A curing accelerator (C) is added to the polyimide resin as the thermosetting resin. When the curable resin is a polyimide resin, a known catalyst such as an imidazole catalyst and a tertiary amine can be used as the curing accelerator (C).
When this curing accelerator (C) is used, the addition amount (% by weight) of the curing accelerator (C) is preferably 0.1 to 10 based on the total weight of the curable resin composition, and more preferably. Is 0.3 or more, particularly preferably 0.5 or more, and further preferably 7 or less, particularly preferably 5 or less.

The resin having another reactive group as the thermosetting resin includes a compound having a polymerizable double bond and the like, and the above-mentioned known compounds and the like can be used.For example, cyclooctadiene, dicyclopentadiene, methyl Tetrahydroindene, norbornadiene, 2-propenyl-2,5-norbornadiene, norbornene, propenoxyethyl vinyl ether, propenoxypropyl (meth) acrylate, propenoxypropyl vinyl ether, ethylene glycol diallyl ether and the like can be used.
In this case, as the curing accelerator (C), known thermal radical generators (such as those described in JP-A-08-134178) can be used, and for example, peroxides, azo compounds, disulfide compounds, and the like can be used.
The content (% by weight) of these curing accelerators (C) is preferably 0.1 to 10, more preferably 0.3 or more, and particularly preferably 0.1 or more, based on the total weight of the curable resin composition. It is 5 or more, more preferably 7 or less, particularly preferably 5 or less.

The epoxy resin as the photocurable resin is composed of the epoxide described above and a photocuring catalyst which is a curing accelerator (C).
As the epoxide, the same epoxide or the like as described above can be used.
As the photo-curing catalyst used as the curing accelerator (C), known cationic polymerization catalysts (such as those described in JP-A-08-134178) can be used. For example, aromatic pyridinium salts, aromatic diazonium salts, aromatic Examples thereof include an iodonium salt, an aromatic sulfonium salt, a benzylsulfonium salt, a cinnamyl sulfonium salt, and an aromatic selenium salt. As a counter ion thereof, an anion such as PF ₆ ⁻ , AsF ₆ ⁻ and BF ₄ ⁻ is used.
The content (% by weight) of these curing accelerators (C) is preferably 0.1 to 10, more preferably 0.3 or more, and particularly preferably 0.1 or more, based on the total weight of the curable resin composition. It is 5 or more, more preferably 7 or less, particularly preferably 5 or less.

Other resins having a reactive group as a photocurable resin include a compound having a polymerizable double bond and a photoradical generator as a curing accelerator (C).
As the compound having a polymerizable double bond, a compound having a polymerizable double bond similar to the above can be used.
As the photoradical generator as the curing accelerator (C), known compounds (such as those described in JP-A-08-134178) can be used, and for example, peroxides, azo compounds, disulfide compounds, and the like can be used.
The content (% by weight) of these curing accelerators (C) is preferably 0.1 to 10, more preferably 0.3 or more, and particularly preferably 0.1 or more, based on the total weight of the curable resin composition. It is 5 or more, more preferably 7 or less, particularly preferably 5 or less.

  These curable resins (A) may be used alone or in combination of two or more. As a combination of two or more, for example, a combination of an epoxy resin and a resin having another reactive group (for example, a combination described in JP-A-2002-80525) and a combination of an epoxy resin and a polyimide resin (for example, 2001-356519) and the like. Of these two or more combinations, it is preferable to combine the epoxy resin with another resin from the viewpoint of cost, dielectric properties, and the like.

It is desirable to add the following high molecular epoxy resin (A1-1) to these curable resins from the viewpoint of thermal shock resistance and the strength of the curable resin. Epoxy compounds having a glass transition temperature before curing of 50 to 150 ° C. and a Mw of 10,000 to 1,000,000 before curing are preferred.
The content (% by weight) of the polymer epoxy resin (A1-1) is preferably from 2 to 70, more preferably 5 or more, particularly preferably 5 or more, based on the total weight of the curable resin from the viewpoint of the strength of the curable resin. It is preferably 10 or more, more preferably 50 or less, particularly preferably 30 or less.

As the polymer epoxy resin, known resins such as those described in JP-A-2001-279116 can be used, and a styrene / glycidyl (meth) acrylate copolymer (Mw: 2,000 to 500,000, styrene: 5 to 95% by weight) %), Styrene / glycidyl (meth) acrylate / alkyl (meth) acrylate (Mw: 2,000 to 500,000, styrene: 5 to 95% by weight, alkyl (meth) acrylate: 1 to 40% by weight) copolymer And glycidyl ester type polyepoxides such as polyglycidyl (meth) acrylate.
Among these high-molecular epoxy resins, glycidyl ester type polyepoxide is preferable from the viewpoint of cost and reliability, and styrene / glycidyl methacrylate copolymer and styrene / glycidyl methacrylate / alkyl (meth) acrylate are more preferable from the viewpoint of dielectric properties. It is a copolymer.
As the curing agent and the curing accelerator for the polymer epoxy resin, the same ones as described above are used, and the respective amounts used are the same as described above.

  It is desirable to add the following thermoplastic resin (Q) to these curable resins (A) from the viewpoint of thermal shock resistance and adhesion to copper plating. That is, as the thermoplastic resin (Q), the absolute value of the difference between the solubility parameters of the polymer epoxy resins (A1-1) and (Q) is 0.5 to 3.0, and the weight average molecular weight is 5 A thermoplastic resin having a molecular weight of from 1,000 to 1,000,000 is preferred.

  The absolute value of the difference between the solubility parameters (hereinafter abbreviated as SP values) between the polymer epoxy resin (A1-1) and the thermoplastic resin (Q) is preferably 0.5 to 3.0, and Preferably 0.6-2.5, even more preferably 0.7-2.0, particularly preferably 0.8-1.8, even more preferably 0.9-1.5, most preferably 1. 0 to 1.2. When the solubility parameter is in this range, an insulator excellent in thermal shock resistance is easily obtained, and the peel strength with copper plating is improved.

The SP value is represented by the following equation.
SP value (δ) = (ΔH / V) ^1/2
In the formula, ΔH represents the heat of molar evaporation (cal), and V represents the molar volume (cm 3). ΔH and V are “POLYMER ENGINEERING AND
FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pages 151 to 153) ", the sum (V) of the molar heat of vaporization (△ ei) of the atomic group (ΔH) and the molar volume (△ vi) can be used.

  The weight average molecular weight of (Q) is preferably from 5,000 to 1,000,000, more preferably from 5,000 to 800,000, still more preferably from the viewpoint of Tg and elastic modulus of the cured product. 000 to 600,000, particularly preferably 50,000 to 400,000, most preferably 60,000 to 100,000.

Next, the chemical structure of the thermoplastic resin (Q) will be described.
As (Q), a thermoplastic resin (Q1) having a carbon-carbon double bond and a thermoplastic resin (Q2) having a carbon-nitrogen bond can be used.
Examples of the thermoplastic resin (Q1) having a carbon-carbon double bond include ring-opening polymerization of polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, and norbornene. And the like, and can be easily obtained as the following commercial products.

  Examples of commercially available products (trade names) include JSR BR series (manufactured by JSR) as polybutadiene, JSR IR series (manufactured by JSR) as polyisoprene, and JSR TR series (manufactured by JSR) as a styrene-butadiene copolymer. Examples of the styrene-isoprene copolymer include the JSR SIS series (manufactured by JSR), and examples of the norbornene ring-opening polymer include the Nosorex series (manufactured by JSR).

  Examples of the thermoplastic resin (Q2) having a carbon-nitrogen bond include polyamide, polyurethane, polyurea, polyimide, polyamino acid, and a reaction product (q) between a bifunctional epoxy (p) and a monofunctional primary amine (r). Is used.

As the polyamide, a polyamide obtained by reacting a diamine having 2 to 18 carbon atoms with a dicarboxylic acid having 6 to 20 carbon atoms or more is used.
Examples of the diamine include diamine (l) having a primary amino group and diamine (m) having a secondary amino group.

  As the diamine (l) having a primary amino group, an aliphatic diamine (2 to 18 carbon atoms) (11), an alicyclic polyamine (4 to 15 carbon atoms) (12) and the like can be used.

As the aliphatic diamine (11), an alkylenediamine having 2 to 6 carbon atoms, an aromatic diamine containing an aromatic ring (8 to 15 carbon atoms), or the like is used.
Examples of the alkylenediamine include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, and hexamethylenediamine.
Examples of the aromatic ring-containing aliphatic diamine include xylylenediamine and tetrachloro-p-xylylenediamine.

  Examples of the alicyclic diamine (12) include 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, and 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline).

  As the diamine (m) having a secondary amino group, those obtained by substituting the primary amino group (-NH2 group) in (1) with -NH-R (R is an alkyl group having 1 to 4 carbon atoms) are used. Examples thereof include di (methylamino) ethylene, di (ethylamino) hexane, and 1,3-di (methylamino) cyclohexane.

Examples of the dicarboxylic acid (n) used in the production of polyamide include divalent aromatic polycarboxylic acids (C6 to C20 or more) (n1) and divalent aliphatic or alicyclic dicarboxylic acids ( (C6-20 or more) (n2) etc. can be used.
Examples of the aromatic dicarboxylic acid (n1) include phthalic acid, isophthalic acid, and terephthalic acid.
Examples of the aliphatic or alicyclic dicarboxylic acid (n2) include hydrogenated aromatic nuclei of aromatic dicarboxylic acid (n1), dimer acid, oxalic acid, maleic acid, succinic acid, adipic acid, dodecenyl succinic acid, and the like. Can be

  In the reaction for obtaining the polyamide, an amine compound other than the diamine, a carboxyl group-containing compound other than the dicarboxylic acid, and the like can be used in addition to the diamine and the dicarboxylic acid for the purpose of adjusting the molecular weight and the like.

  Examples of the polyurethane as the thermoplastic resin (Q2) having a carbon-nitrogen bond include those obtained from the reaction of a dihydric phenol or dihydric alcohol having 2 to 100 or more carbon atoms with a diisocyanate having 6 to 20 carbon atoms. Used.

Examples of the dihydric phenol include bisphenol F, bisphenol A, bisphenol B, bisphenol AD, bisphenol S, halogenated bisphenol A (eg, tetrachlorobisphenol A, etc.), catechin, resorcinol, hydroquinone, 1,5-dihydroxynaphthalene, Dihydroxybiphenyl, octachloro-4,4′-dihydroxybiphenyl, tetramethylbiphenyl, 9,9′-bis (4-hydroxyphenyl) fluorene and the like.
Examples of the dihydric alcohol include ethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, polyethylene glycol (Mw 150 to 4,000), polypropylene glycol (Mw 180 to 5,000), and polytetramethylene glycol ( Mw 200 to 5,000), neopentyl glycol, and EO and / or PO (1 to 20 mol) adduct of bisphenol A.

  As the diisocyanate, an aromatic diisocyanate (o1) having 6 to 20 carbon atoms (excluding the carbon in the NCO group; the same applies hereinafter), an aliphatic diisocyanate (o2) having 2 to 18 carbon atoms, and a 4 to 15 carbon atoms Alicyclic diisocyanate (o3) and araliphatic diisocyanate (o4) having 8 to 15 carbon atoms can be used.

  Examples of the aromatic diisocyanate (o1) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 2,4′- or 4,4′- Diphenylmethane diisocyanate (MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, Examples thereof include 1,5-naphthylene diisocyanate.

  Examples of the aliphatic diisocyanate (o2) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and bis (2-isocyanatoethyl). ) Fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate;

  Examples of the alicyclic diisocyanate (o3) include, for example, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2 -Isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

  Examples of the araliphatic polyisocyanate (o4) include m- or p-xylylene diisocyanate (XDI).

  In the reaction for obtaining a polyurethane, an isocyanate compound other than diisocyanate can be used for the purpose of adjusting the molecular weight and the like.

As the polyurea as the thermoplastic resin (Q2) having a carbon-nitrogen bond, those obtained from the reaction of a diamine having 2 to 18 carbon atoms and a diisocyanate having 6 to 20 carbon atoms are used.
Examples of the diamine include the diamines described above.
Examples of the diisocyanate include the aforementioned diisocyanates.

  In the reaction for obtaining polyurea, an amine compound other than diamine or an isocyanate group-containing compound other than diisocyanate can be used for the purpose of adjusting the molecular weight and the like.

As the polyimide as the thermoplastic resin (Q2) having a carbon-nitrogen bond, a polyimide obtained by reacting a diamine having 2 to 18 carbon atoms with a dicarboxylic acid having 6 to 20 or more carbon atoms is used.
Examples of the diamine include the diamines described above.
Examples of the dicarboxylic acid include the dicarboxylic acids described above.
In the reaction for obtaining the polyimide, an amine compound other than diamine or a carboxyl group-containing compound other than dicarboxylic acid can be used for the purpose of adjusting the molecular weight and the like.

Examples of the polyamino acid as the thermoplastic resin (Q2) having a carbon-nitrogen bond include a condensate of an aminocarboxylic acid having 2 to 12 carbon atoms and a ring-opening polymer of a lactam having 6 to 12 carbon atoms.
Examples of the aminocarboxylic acid include, for example, amino acids (glycine, alanine, valine, leucine, isoleucine, phenylalanine, etc.), ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocaprin Acids, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Examples of the lactam include caprolactam, enantholactam, laurolactam, and undecanolactam.
In the reaction for obtaining a polyamino acid, the above-mentioned diamine compound, another amino compound, the above-mentioned dicarboxylic acid, another carboxyl group-containing compound, or the like can be used for the purpose of adjusting the molecular weight or the like.

Examples of the thermoplastic resin (Q2) having a carbon-nitrogen bond include a reaction product (q) of a bifunctional epoxy (p) and a monofunctional primary amine (r).
Examples of the bifunctional epoxy (p) include diglycidyl ether (p1) of dihydric phenol (C6 to C30); dihydric alcohol [alkylene glycol having 2 or more carbon atoms or dihydric phenol having 6 or more carbon atoms] Diglycidyl ether (p2); divalent glycidyl ester (p3); divalent glycidylamine (p4); divalent alicyclic epoxide ( p5) and the like.
In the following description, alkylene oxides having 2 to 4 carbon atoms are abbreviated as AO; ethylene oxide as EO; and propylene oxide as PO.

  Examples of the diglycidyl ether (p1) of dihydric phenol (C6 to C30) include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, and bisphenol S diglycidyl. Ether, halogenated bisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalenediglycidyl ether, dihydroxybiphenyldiglycidyl ether, octachloro -4,4'-dihydroxybiphenyldiglycidyl ether, tetramethylbiphenyldiglyci Ether, 9,9'-bis (4-hydroxyphenyl) furo diglycidyl ether and diglycidyl ether obtained from bisphenol A2 moles and 3 moles of epichlorohydrin in the reaction, and the like.

  Examples of the diglycidyl ether (p2) of a dihydric alcohol [alkylene glycol having 2 or more carbon atoms or an AO of 1 to 90 mol adduct of dihydric phenol having 6 or more carbon atoms] include ethylene glycol diglycidyl ether and propylene glycol diglycidyl. Ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol (Mw 150 to 4,000) diglycidyl ether, polypropylene glycol (Mw 180 to 5,000) diglycidyl ether, polytetramethylene glycol ( Mw 200-5,000) Diglycidyl ether, neopentyl glycol diglycidyl ether, and a jig of EO and / or PO (total 1-20 mol) adduct of bisphenol A Glycidyl ether and the like.

As the divalent glycidyl ester (p3), for example, the following (p31) to (p32) can be used.
(P31) Diglycidyl esters of divalent aromatic polycarboxylic acids (C6 to C20 or more) such as diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate.
(P32) Diglycidyl esters of divalent aliphatic or alicyclic carboxylic acids (C6 to C20 or more).
(P31) Aromatic nucleus water additive, diglycidyl dimer acid ester, diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimerate and the like.

As the divalent glycidylamine (p4), for example, the following (p41) to (p43) can be used.
(P41) Examples of the diglycidyl aromatic amine having two glycidyl groups (aromatic amine having 6 to 20 or more carbon atoms) include N, N-diglycidylaniline and N, N-diglycidyltoluidine.

(P42) Examples of the polyglycidyl alicyclic amine having two glycidyl groups (alicyclic amine having 6 to 20 or more carbon atoms) include N, N, N ′, N′-tetraglycidylxylylenediamine. Hydrogenated compounds and the like.
(P43) Examples of the diglycidyl heterocyclic amine having two glycidyl groups (heterocyclic amine having 6 to 20 carbon atoms or more) include N-glycidyl-4-glycidyloxypyrrolidone.

As the divalent alicyclic epoxide (p5), for example, an alicyclic epoxide having 6 to 50 or more carbon atoms, Mw of 98 to 5,000, and 2 epoxy groups can be used, and for example, vinylcyclohexene Dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, and the like.
Of these (p), (p2) is preferable from the viewpoint of reducing the elastic modulus of the reactant (q), and (p1) and (p2) from the viewpoint of adjusting the glass transition temperature of the reactant (q). Particularly preferred is the combination of

As a reactant (q) as a thermoplastic resin (Q2) having a carbon-nitrogen bond, as a monofunctional primary amine (r) as a reaction partner of a bifunctional epoxy (p), for example, one having 1 to 18 carbon atoms Examples thereof include an aliphatic amine (r1) and an aromatic amine (r2) having 6 to 18 carbon atoms.
Examples of the aliphatic amine (r1) include methylamine, dimethylamine, methylbutylamine, undecylamine, decalylamine, and octadecylamine.
Examples of the aromatic amine (r2) include aniline, p-methylaniline, p-undecylaniline, m-methoxyaniline, and naphthylamine.
(R) is preferably (r1) from the viewpoint of lowering the elastic modulus of the reactant (q).

As a reaction product (q) of the bifunctional epoxy and the monofunctional primary amine, one or more of (p1) and (p2) is used as the bifunctional epoxy (p), and (r1) is used as the monofunctional primary amine. Are preferred.
In the reaction between the bifunctional epoxy and the monofunctional primary amine, an epoxy group-containing compound other than those described above, an amine compound, and the like can be used for the purpose of adjusting the molecular weight and the like.

  Among these thermoplastic resins (Q), from the viewpoint of the dielectric constant, the thermoplastic resin (Q1) having a carbon-carbon double bond and the reaction product (q) of a bifunctional epoxy and a monofunctional primary amine are: preferable. More preferred are polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, norbornene ring-opening polymer, and reaction product of bifunctional epoxy and monofunctional primary amine.

The content of the carbon-carbon double bond or carbon-nitrogen bond in (Q) is from 5 × 10 ^{−5 to} 3.5 × 10 ⁻² mol / g per 1 g of (Q) from the viewpoint of adhesion and the like. g is preferable, and 1.0 × 10 ^{−4 to} 3.5 × 10 ⁻² mol / g is more preferable in the case of a carbon-carbon double bond, and 1 × 10 ^{−4 to} 3.5 × in the case of a carbon-nitrogen bond. 10 ^-2 mol / g is more preferred. In particular, from the viewpoint of the dielectric constant, it is preferably 1.0 × 10 ^{−3 to} 2.5 × 10 ⁻² mol / g in the case of a carbon-carbon double bond, and 5 × 10 ⁻⁴ to 2.times.2 in the case of a carbon-nitrogen bond. 5 × 10 ^-2 mol / g is preferred.

When the content of the carbon-carbon double bond or carbon-nitrogen bond is within this range, the thermoplastic resin on the surface of the insulating layer is easily eluted by the oxidizing agent, and fine irregularities are formed, and the adhesiveness to electroless plating is obtained. Becomes better. On the other hand, if it exceeds this range, the heat resistance of the cured product tends to decrease.
The carbon-carbon double bond or carbon-nitrogen bond may be present in either the main chain skeleton or the side chain skeleton of the resin as long as it is present in (Q), but is present in the main chain skeleton of the resin. Is preferred.

  The weight ratio of (A1-1) to (Q) is preferably from 40/60 to 98/2 as a weight ratio in terms of pure content excluding the solvent, and more preferably from 50/50 to from the viewpoint of resin strength. 96/4, from the viewpoint of heat resistance, particularly preferably 55/45 to 90/10, most preferably 60/40 to 85/15.

  When the curable resin contains (Q), it is preferable that (Q) is uniformly dispersed in (A1-1).

When (Q) is dispersed in (A1-1), the dispersion average particle size of (Q) is not particularly limited, but is preferably 0.001 to 50 μm, and further from the viewpoint of resin strength, It is preferably from 0.005 to 20 μm, particularly preferably from 0.01 to 10 μm, and particularly preferably from 0.05 to 5 μm, most preferably from 0.1 to 2 μm from the viewpoint of adhesion.
The dispersion average particle diameter is obtained by subjecting the curable resin composition to a curing treatment at 180 ° C. for 3 hours, observing the cross section with a scanning electron microscope, and calculating the arithmetic average of the particle diameters of at least 10 (Q) particles. Desired.

  The content (% by weight) of the curable resin is preferably 25 to 66, more preferably 30 to 62, and particularly preferably 40 to 57 based on the weight of the curable resin composition from the viewpoint of mechanical strength and the like. It is. That is, the content (% by weight) of the curable resin is preferably 25 or more, more preferably 30 or more, particularly preferably 40 or more, and preferably 66 or less, based on the weight of the curable resin composition. It is more preferably 62 or less, particularly preferably 57 or less.

  Additives added as needed include, for example, flame retardants, thickeners, defoamers, leveling agents, and adhesion promoters. As the flame retardant, known flame retardants such as phosphorus-based flame retardants and halogen-based flame retardants (the above-mentioned patent publications) can be used. When a flame retardant is used, the addition amount (% by weight) of the flame retardant is preferably from 0.5 to 30 based on the total weight of the curable resin composition, and more preferably from the viewpoint of exhibiting flame retardancy. 1 to 15, particularly preferably 2 to 10. That is, in this case, the addition amount (% by weight) of the flame retardant is preferably 0.5 or more, more preferably 1 or more, particularly preferably 2 or more, based on the total weight of the curable resin composition. It is preferably 30 or less, more preferably 15 or less, and particularly preferably 10 or less.

  As the thickener, known thickeners such as asbestos and benton (the above patent publications and the like) can be used. When a thickener is used, the amount (% by weight) of the thickener is preferably 0.01 to 5, more preferably 0.1 to 4, and particularly preferably 0.1 to 4, based on the total weight of the curable resin composition. Preferably it is 0.5-3. That is, in this case, the addition amount (% by weight) of the thickener is preferably 0.01 or more, more preferably 0.1 or more, and particularly preferably 0.5 or more, based on the total weight of the curable resin composition. The number is preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less.

  As the antifoaming agent, known antifoaming agents such as silicone-based antifoaming agents, polyether-based antifoaming agents, alcohol-based antifoaming agents, and oil-based antifoaming agents can be used. When an antifoaming agent is used, the amount (% by weight) of the antifoaming agent is preferably from 0.01 to 5, more preferably from 0.1 to 4, based on the total weight of the curable resin composition. Preferably it is 0.5-3. That is, in this case, the amount (% by weight) of the defoaming agent is preferably 0.01 or more, more preferably 0.1 or more, and particularly preferably 0.5 or more, based on the total weight of the curable resin composition. The number is preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less.

  As the leveling agent, known leveling agents such as a silicone leveling agent, a polyether-based leveling agent, and an alcohol-based leveling agent (the above-mentioned patent publications) can be used. When a leveling agent is used, the amount (% by weight) of the leveling agent is preferably from 0.01 to 10, more preferably from 0.1 to 7, and particularly preferably based on the total weight of the curable resin composition. 0.5 to 5. That is, in this case, the amount (% by weight) of the leveling agent is preferably 0.01 or more, more preferably 0.1 or more, and particularly preferably 0.5 or more, based on the total weight of the curable resin composition. And preferably 10 or less, more preferably 7 or less, particularly preferably 5 or less.

As the adhesion-imparting agent between the curable resin and the cured product and the substrate or the copper plating, a known adhesion-imparting agent such as a silane coupling agent (the above-mentioned patent publication) can be used.
When the adhesion-imparting agent is used, the amount (% by weight) of the adhesion-imparting agent is preferably from 0.01 to 10, more preferably from 0.1 to 7, based on the total weight of the curable resin composition. Particularly preferably, it is 0.5 to 5. That is, in this case, the addition amount (% by weight) of the adhesion promoter is preferably 0.01 or more, more preferably 0.1 or more, and particularly preferably 0.5 or more, based on the total weight of the curable resin composition. The number is preferably 10 or less, more preferably 7 or less, and particularly preferably 5 or less.

The curable resin composition can be obtained by uniformly mixing a filler, a curable resin, and additives to be added as necessary with a known mixing device or the like.
The temperature (° C.) for uniform mixing is usually 0 to 150, preferably 10 to 130, more preferably 20 to 110, and particularly preferably 30 to 100. That is, the temperature (° C.) is usually 0 or higher, preferably 10 or higher, more preferably 20 or higher, particularly preferably 30 or higher, and usually 150 or lower, preferably 130 or lower, and further preferably It is 110 or less, particularly preferably 100 or less. As the mixing device, any device can be used as long as it can mix the filler with the liquid material. For example, a planetary mixer, a bead mill, a three-roller, a two-roller and the like can be used. The stirring and mixing time is, for example, a time until most of the aggregates contained in the filler are eliminated (for example, determined while measuring the particle size distribution) and the like, and is appropriately determined. If necessary, the curable resin composition may remove coarse particles and the like by filtration.

The curable resin composition of the present invention may be used as it is, or may be used by applying it to a substrate as a curable resin composition solution or a curable resin composition dispersion, or It can be used after being processed into a resin film.
When processing into a curable resin film, the curable resin composition is dissolved and / or dispersed in a solvent to form a resin solution (resin dispersion solution), and the resin solution is supported by a known film manufacturing apparatus such as a roll coater. It can be manufactured by coating on a film.
When applied to a substrate, or when producing a curable resin film, it can be used as a curable resin composition solution or a curable resin composition dispersion. There is no particular limitation as long as the composition can be dissolved and / or dispersed and the resin solution can be adjusted to physical properties (viscosity and the like) applicable to coating and film production equipment. For example, N-methylpyrrolidone, N, Known solvents such as N-dimethylformamide, dimethylsulfoxide, toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, acetone and xylene can be used. Among these solvents, those having a boiling point of 200 ° C. or less (toluene, ethanol, cyclohexane, methanol, methyl ethyl ketone, ethyl acetate, acetone, and xylene) are preferable from the viewpoint of the drying temperature of the film.

  The support film used in processing the curable resin film is a support used for the purpose of facilitating the handling of the curable resin film, and may have a certain strength, and a known support film or the like can be used. For example, a polyethylene terephthalate (PET) film, a polypropylene film, a polyethylene film, and the like can be used.

  The thickness (μm) of the curable resin film is preferably from 1 to 100, more preferably from 5 to 80, and particularly preferably from 10 to 60. That is, the thickness (μm) of the curable resin film is preferably 1 or more, more preferably 5 or more, particularly preferably 10 or more, and preferably 100 or less, more preferably 80 or less, and particularly preferably 60 or less. It is.

The cured product of the present invention can be easily produced by thermally curing the curable resin composition or the curable film described above.
The conditions for the heat curing are as follows: 80 to 250 ° C (preferably 120 to 200 ° C, more preferably 150 to 200 ° C) for 0.1 to 15 hours (preferably 0.2 to 5 hours, more preferably 0.1 to 5 hours). 5 to 3 hours).

The boiling water absorption of the cured product of the present invention is 3.00 to 0.001%, preferably 2.50 to 0.005%, more preferably 2.00 to 0.01%, and particularly preferably 1. 0 to 0.05%.
The boiling water absorption is measured in accordance with JIS K7209 (2000) 6.3B method.
The volume resistivity of the cured product of the present invention is 10 ¹⁰ to 10 ¹⁹ Ω / cm, preferably 10 ^{12 to} 5 × 10 ¹⁸ Ω / cm, more preferably 10 ¹⁴ to 10 ¹⁸ Ω / cm, and particularly preferably 10 10 to 10 ¹⁸ Ω / cm. ^{It is 16 to} 5 × 10 ¹⁷ Ω / cm, and is excellent in electrical insulation as compared with conventionally used insulating materials such as epoxy resin and polyimide resin.
The volume resistance is measured according to JIS K6011 (1995).

The heat resistance of the cured product of the present invention is the same as that of a conventional insulator, and even if it is brought into contact with a solder at 300 ° C. for 1 minute, no abnormality such as sagging of the pattern, breakage and blistering is observed, and it is resistant to various solvents. The chemical resistance is also very good.
The cured product of the present invention is also excellent in 10% sulfuric acid resistance, 10% hydrochloric acid resistance, 10% nitric acid resistance and 10% sodium hydroxide resistance as measured by the method specified in JIS K6911 (1995) 5.32. .

As a method of using the curable resin composition of the present invention as an insulator, for example, (1) when using the curable resin composition solution or the curable resin composition dispersion of the present invention on a base material when used as an interlayer insulating material, After coating, drying and heat-curing, if necessary, processing such as roughening and formation of a conductive circuit is performed, and this operation is repeated. 2) After laminating a resin film of the curable resin composition of the present invention on a substrate, hot press and pressure bonding. Thereafter, only the support film is peeled off and cured by heating. After heat-curing, if necessary, roughening, conductive circuit formation, etc. are performed, and further, a substrate is laminated, this operation is repeated, and further, if necessary, heat-curing to form a multilayer, etc. .
When the curable resin composition is used as a part of a substrate material of a multilayer substrate, (3) a curable resin solution or a curable resin dispersion is applied to a substrate, dried, and then, if necessary, a hole is formed. A process such as opening is performed, and this operation is repeated. Finally, a method of forming a multilayer by heating and curing is used, or (4) a curable film is bonded to a substrate, and then hot pressed and pressed. Thereafter, only the support film is peeled off and removed. A method of forming a multilayer by performing processing such as drilling as necessary, repeating this operation, and finally heat-curing.
In addition, it can also be used as a printed wiring board as it is, without using a base material.

  When used as an interlayer insulating material such as a multilayer circuit board of an electronic circuit, one interlayer insulating layer may be composed of a single layer or multiple layers, and its thickness (after curing) is preferably 1 to 100 μm, more preferably 15 to 100 μm. 50 μm.

The conditions of the hot press include a temperature of 25 to 180 ° C. (preferably 50 to 150 ° C.), a pressure of 0.01 MPa to 10 MPa (preferably 0.1 to 1 MPa), and a time of 1 to 1200 seconds (preferably 10 to 300 seconds). Are preferred.
Holes (via holes, through holes, etc.) for conducting between the layers of the multilayer substrate can be formed by a usual method, and for example, a method using a laser (carbon dioxide, YAG, excimer, etc.), a drill or the like can be used.
Roughening can be performed by a usual method, for example, a method described in JP-B-6-49852 can be used.
The conductive circuit can be formed by an ordinary method, for example, a sputtering method, an electroless method, or the like can be used.

[Example]
Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, parts mean parts by weight and% means% by weight.

Production Example <Synthesis Example 1> Production of Styrene / Glycidyl Methacrylate Copolymer Solution (X1) 5 parts of methyl ethyl ketone (hereinafter referred to as MEK) were charged into a reaction vessel purged with nitrogen, and heated to 80 ° C. 20 parts of glycidyl methacrylate (hereinafter, referred to as GMA) uniformly dissolved in another nitrogen-purged container, 20 parts of styrene (hereinafter, referred to as St), 5 parts of 2-ethylhexyl acrylate (hereinafter, referred to as 2EHA), MEK20 Of azobisisobutyronitrile and 1.5 parts of azobisisobutyronitrile was dropped into the reaction vessel over 4 hours.
After completion of the dropwise addition, the mixture was aged at 100 ° C. for 5 hours to obtain a GMA / St / 2EHA copolymer.
The Mw (molecular weight in terms of polystyrene measured by GPC) of this copolymer was 30,000, and the glass transition temperature was 58 ° C. The calculated SP value of the GMA / St / 2EHA copolymer having this ratio is 10.7. The epoxy equivalent (measured according to JIS K7236) of this copolymer was 320.
This copolymer was diluted with MEK so that the solid content became 50%, to obtain a polymer epoxy resin solution (X1) of the present invention.

<Synthesis Example 2> Production of styrene / glycidyl methacrylate copolymer solution (X2) in which SBS resin is dispersed Further, a styrene-butadiene copolymer (JSR-TR2250 manufactured by JSR; hereinafter abbreviated as SBS resin) is added to the mixture to be dropped. A GMA / St / 2EHA copolymer in which an SBS resin was dispersed was obtained in the same manner as in Synthesis Example 1 except that 30 parts was added.
The epoxy equivalent of the GMA / St / 2EHA copolymer in which the obtained SBS resin was dispersed was 527 (measured according to JIS K7236). The Mw of the SBS resin, which is a thermoplastic resin used here, is 115,000 (molecular weight in terms of polystyrene measured by GPC), and the calculated SP value is 9.3. The calculated SP value of the GMA / St / 2HEA copolymer having this ratio is 10.7.
The resulting styrene / glycidyl methacrylate copolymer in which the SBS resin is dispersed is diluted using MEK so that the solid content becomes 50%, and a polymer epoxy resin solution in which the thermoplastic resin of the present invention is dispersed. (X2) was obtained.

<Synthesis Example 3> Production of phenol novolak epoxy resin (Y1) in which silicon oxide was dispersed In a glass container, 19.66 parts of tetraethoxysilane and 75.63 parts of ion-exchanged water were added and stirred until uniform. . To this, 0.25 parts of octylate of diazabicycloundecene (manufactured by San-Apro Co., Ltd., SA-102) was added, and the mixture was reacted at 25 ° C. for 2 hours with stirring. Further, 5.24 parts of a glycidyl ether type epoxy resin (Epicoat 154, manufactured by Japan Epoxy Resin Co., Ltd.) was added, and the mixture was stirred until the mixture became uniform. From the obtained mixture, methanol and water were distilled off at 80 ° C. under reduced pressure to obtain a phenol novolak epoxy resin (Y1) in which the silicon oxide fine particles of the present invention were dispersed.
The volume average particle diameter of the silicon oxide fine particles measured according to JIS R1629 was 80 nm, and Dv90 was 222 nm. The silicon oxide content of the obtained (Y1) measured by the method described later was 52%.

<Synthesis Example 4> Production of phenol novolak epoxy resin (Y2) in which silicon oxide was dispersed In Synthesis Example 3, except that tetraethoxysilane and ion-exchanged water were added, 20.00 parts of methanol was further added. In the same manner as in Example 3, a phenol novolak epoxy resin (Y2) in which the silicon oxide fine particles of the present invention were dispersed was obtained.
The volume average particle diameter of the silicon oxide fine particles measured according to JIS R1629 was 10 nm, and Dv90 was 28 nm. The silicon oxide content of the obtained (Y2) measured by the method described later was 52%.

<Synthesis Example 5> Production of phenol novolak epoxy resin (Y3) in which silicon oxide is dispersed In Synthesis Example 3, 10.00 parts of tetraethoxysilane and 11.20 parts of phenyltriethoxysilane were used instead of tetraethoxysilane. A phenol novolak epoxy resin (Y3) in which the silicon oxide fine particles of the present invention were dispersed was obtained in the same manner as in Synthesis Example 3 except that 10.30 parts of methyl ethyl ketone was further used when adding ion-exchanged water. The volume average particle diameter of the silicon oxide fine particles measured according to JIS R1629 was 50 nm, and Dv90 was 114 nm. The silicon oxide content of the obtained (Y3) measured by the method described later was 52%.

<Synthesis Example 6> Production of phenol novolak epoxy resin (Y4) in which titanium oxide is dispersed In Synthesis Example 3, 4.70 parts of tetraethoxytitanium and 5.00 parts of phenyltriethoxytitanium were used instead of tetraethoxysilane. A phenol novolak epoxy resin (Y4) in which titanium oxide fine particles of the present invention were dispersed was obtained in the same manner as in Synthesis Example 3 except that 10.30 parts of methyl ethyl ketone was further used when adding ion-exchanged water. The volume average particle diameter of the titanium oxide fine particles measured according to JIS R1629 was 52 nm, and Dv90 was 120 nm. The content of titanium oxide in the obtained (Y4) measured by the method described later was 52%.

<Example 1>
11 parts of the resin solution (X1) obtained in Synthesis Example 1, 25 parts of a phenol novolak epoxy resin (Y1) in which the silicon oxide fine particles obtained in Synthesis Example 3 are dispersed, and a phenolic curing agent (phenol novolak resin, Gunei) 8 parts of PSM-4326 manufactured by Kagaku Kogyo Co., 8 parts of a flame retardant (brominated epoxy resin, YDB-500 manufactured by Toto Kasei Co., Ltd.) and 1 part of an epoxy ring-opening catalyst (SA-102 manufactured by San Apro Co.) were used for 6.5 parts of methyl ethyl ketone. To obtain a curable resin composition of the present invention.
Next, this resin solution was applied to a 50 μm-thick PET film (600 mm × 600 mm) by a roll coater so that the resin thickness after drying became 50 μm, and then dried at 90 ° C. for 7 minutes to obtain a curable resin. A film was obtained.
The curable resin film was cured by heating at 170 ° C. for 90 minutes to obtain a cured product (A-1) of the present invention. Table 1 shows values obtained by measuring the linear expansion coefficient of the cured product (A-1).
Further, a curable resin film was coated on a copper-clad BT resin substrate (manufactured by Mitsubishi Gas Chemical Industry Co., Ltd., trade name: CCL-HL830, size 30 mm square) using a pressurized vacuum laminator (Nichigo Morton V130). Vacuum compression bonding was performed at a temperature of 0.8 ° C., a pressure of 0.8 kgf / cm ² and a degree of vacuum of ² mmHg or less. After allowing the substrate on which the film was pressed to cool to 30 ° C., the PET film was peeled off. The substrate was cured at 170 ° C. for 90 minutes to obtain a substrate for peel strength evaluation (B-1).
The peel strength (adhesion) of this substrate (B-1) was measured by the method described later. The results are shown in Table 1.

<Example 2>
In the same manner as in Example 1, except that 6.6 parts were used instead of 11 parts of the resin solution (X1), the cured product (A-2) and the substrate for peel strength evaluation (B- 2) was obtained.
Table 1 shows the values obtained by measuring the linear expansion coefficient of the cured product (A-2) and the results of measuring the peel strength of the substrate (B-2).
<Example 3>
In the same manner as in Example 1 except that 11 parts of the resin solution (X2) obtained in Synthesis Example 2 was used instead of 11 parts of the resin solution (X1), the cured product (A-3) was used. ) And a peel strength evaluation substrate (B-3) were obtained.
Table 1 shows the values obtained by measuring the linear expansion coefficient of the cured product (A-3) and the results of measuring the peel strength of the substrate (B-3).

<Example 4>
In the same manner as in Example 1 except that (Y2) obtained in Synthesis Example 4 was used instead of the phenol novolak epoxy resin (Y1) in which silicon oxide fine particles were dispersed, a cured product ( A-4) and a substrate for peel strength evaluation (B-4) were obtained.
Table 1 shows the value obtained by measuring the coefficient of linear expansion of the cured product (A-4) and the result of measuring the peel strength of the substrate (B-4).

<Example 5>
In the same manner as in Example 3 except that (Y2) obtained in Synthesis Example 4 was used instead of the phenol novolak epoxy resin (Y1) in which silicon oxide fine particles were dispersed, the cured product ( A-5) and a substrate for peel strength evaluation (B-5) were obtained.
Table 1 shows the values obtained by measuring the linear expansion coefficient of the cured product (A-5) and the results of measuring the peel strength of the substrate (B-5).

<Example 6>
A cured product (Example 3) was prepared in the same manner as in Example 3 except that (Y3) obtained in Synthesis Example 5 was used instead of the phenol novolak epoxy resin (Y1) in which silicon oxide fine particles were dispersed. A-6) and a substrate for peel strength evaluation (B-6) were obtained.
Table 1 shows the values obtained by measuring the linear expansion coefficient of the cured product (A-6) and the results of measuring the peel strength of the substrate (B-6).

<Example 7>
Example 3 was repeated except that the phenol novolak epoxy resin (Y4) in which the titanium oxide particles obtained in Synthesis Example 6 were dispersed was used instead of the phenol novolak epoxy resin (Y1) in which the silicon oxide particles were dispersed in Example 3. In the same manner as in Example 3, a cured product (A-7) and a substrate for peel strength evaluation (B-7) were obtained.
Table 1 shows the values obtained by measuring the coefficient of linear expansion of the cured product (A-7) and the results of measuring the peel strength of the substrate (B-7).

<Comparative Example 1>
In Example 1, in place of the phenol novolak epoxy resin (Y1) in which silicon oxide fine particles were dispersed, 12 parts of a glycidyl ether type epoxy resin (Epicoat 154, manufactured by Japan Epoxy Resin Co., Ltd.) and silica powder ("Admafine" manufactured by Admatech, Inc.) SO-C2 ") A cured product (A-8) and a substrate for peel strength evaluation (B-8) were obtained in the same manner as in Example 1 except for using 13 parts. The silica powder used had a volume average particle diameter of 420 nm and a Dv90 of 1530 nm.
Table 1 shows the value obtained by measuring the coefficient of linear expansion of the cured product (A-8) and the result of measuring the peel strength of the substrate (B-8).

<Comparative Example 2>
In Example 3, in place of the phenol novolak epoxy resin (Y1) in which silicon oxide fine particles were dispersed, 12 parts of a glycidyl ether type epoxy resin (Epicoat 154, manufactured by Japan Epoxy Resins Co., Ltd.), and silica powder (manufactured by Admatech) A cured product (A-9) and a peel strength evaluation substrate (B-9) were obtained in the same manner as in Example 1 except for using 13 parts of "Admafine SO-C2").
Table 1 shows the values obtained by measuring the linear expansion coefficient of the cured product (A-9) and the results of measuring the peel strength of the substrate (B-9).

<Comparative Example 3>
In Comparative Example 1, a cured product (A-10) and a substrate for peel strength evaluation (B-) were prepared in the same manner as in Comparative Example 1 except that 46 parts of silicon oxide powder ("Admafine SO-C2" manufactured by Admatech) was used. 10) was obtained.
Table 1 shows the values obtained by measuring the coefficient of linear expansion of the cured product (A-10) and the results of measuring the peel strength of the substrate (B-10).

<Measurement of silicon oxide and titanium oxide contents>
About 8 mg of a measurement sample was weighed in a sample container (platinum pan). The sample container was heated to 800 ° C in air using a TG-DTA measuring device. From the weight of the heating residue after heating at 800 ° C. for 1 hour, the content (% by weight) of silicon oxide or titanium oxide was calculated by the following equation.
Silicon oxide (or titanium oxide) content (% by weight) = heat residue weight (mg) / measurement sample weight (mg) × 100

<Measurement of linear expansion coefficient>
The cured film was cut at 25 ° C. so as to have a size of (length) 15 mm × (width) 2 mm × (thickness) 0.040 mm. The length and width of the cut sample were measured with a vernier caliper, and the thickness was measured with a film thickness meter, each measuring to the order of 0.001 mm.
Using TMA / SS6100 manufactured by Seiko Instruments Inc., a load of 49 mN was applied to the measurement sample, and the inside of the measurement cell was held at 30 ° C. for 30 minutes. Then, the measurement cell temperature was increased from 30 ° C. to 230 ° C. at 10 ° C./min. The temperature rose.
The length at 30 ° C. is (A) [mm], the length at 100 ° C. is (B) [mm], and the coefficient of linear expansion (X) = ((B) − (A)) × 10 ⁶ / ｛140 × It was determined by A｝ [ppm].

<Measurement of peel strength>
The prepared substrate for peel strength evaluation was immersed in a swelling aqueous solution (sodium hydroxide: 3 g / L, diethylene glycol monobutyl ether: 250 g / L) at 80 ° C. for 5 minutes, washed with water, and then subjected to a roughened aqueous solution (permanganic acid) at 80 ° C. : 60 g / L, sodium hydroxide: 40 g / L) for 15 minutes to perform a roughening treatment. Then, after immersing in a 40 degreeC neutralization aqueous solution (hydroxylamine sulfate 16g / L, sulfuric acid: 48g / L) for 5 minutes, it wash | cleaned with water. Furthermore, it was immersed in an alkaline cleaner solution (sodium hydroxide: 5 g / L) at 60 ° C for 5 minutes, washed with water, and dried at 25 ° C for 12 hours.
After the above treatment, immersion in an electroless plating solution (copper sulfate 12 g / L, formaldehyde 7.5 g / L) at 32 ° C. for 20 minutes using a palladium catalyst (manufactured by ATOTEC, trade name: Neoganth 834) as an electroless plating catalyst. Then, an electroless plating layer having a plating film thickness of 2 μm was formed. Thereafter, electrolytic plating having a thickness of 50 μm was further performed in a copper sulfate electrolytic plating bath. With respect to the substrate thus formed, the adhesion between the substrate and the copper plating film was measured by the peel strength measuring method described in JIS C6481.

In the results shown in Table 1, the cured products of Examples all show sufficiently low linear expansion coefficients of around 20 ppm, whereas Comparative Examples 1 and 2 are insufficient, being around 40 ppm.
Comparative Example 3 was insufficient in peel strength. From these comparisons, it is clear that all of the examples of the present invention can simultaneously achieve a sufficiently small linear expansion coefficient and a sufficiently large peel strength, and are superior to the comparative examples.

The cured product comprising the curable resin composition of the present invention has a low coefficient of linear expansion and a large peel strength at the same time, and when used as an insulating material for a printed wiring board, the substrate strength and thermal shock Excellent durability and high durability.
For example, it is suitable as an overcoat material, an interlayer insulating material, a printed circuit board, and the like, and particularly suitable as an overcoat material and an interlayer insulating material. It is most suitable as an overcoat material or an interlayer insulating material for electronic devices (semiconductor devices, light emitting diodes, various memories, etc.), hybrid ICs, MCMs, electric wiring circuit boards, display components, and the like.
Further, the curable resin composition of the present invention is suitable for uses such as a printed wiring board by a build-up method. And the printed wiring board by such a build-up method is suitably used for electrical products such as personal computers, camera-integrated VTRs, digital video cameras, mobile phones, car navigation systems, and digital cameras.

Claims (11)

  A curable resin composition comprising a curable resin (A), a filler (B), and a curing accelerator (C), wherein the filler has a volume average particle diameter of 1 to 100 nm.   The curable resin composition according to claim 1, wherein the (B) has a 90% volume cumulative particle diameter (Dv90) of 2 to 200 nm.   3. The curable resin composition according to claim 1, wherein (A) is an epoxy resin (A1).   (A) a high-molecular epoxy resin having at least two epoxy groups in a molecule, a glass transition temperature before curing of 50 to 150 ° C., and a weight average molecular weight of 10,000 to 1,000,000 The curable resin composition according to any one of claims 1 to 3, comprising (A1-1).   5. The curable resin composition according to claim 4, comprising (A1-1) in an amount of 2 to 70% by weight based on the total weight of (A).   It further contains a thermoplastic resin (Q), the absolute value of the difference between the solubility parameter of the (A1-1) and the solubility parameter of the (Q) is 0.5 to 3.0, and the weight average of the (Q) The curable resin composition according to claim 4, wherein the molecular weight is 5,000 to 1,000,000.   The curable resin composition according to claim 6, wherein (Q) is dispersed in the curable resin composition, and the average dispersed particle size is 0.01 to 10 µm.   The curable resin composition according to any one of claims 1 to 7, wherein (B) is silicon oxide or titanium oxide.   The curable resin composition according to any one of claims 1 to 8, wherein the content of (B) is 1 to 33% by weight based on the weight of the curable resin composition.   A cured product obtained by curing the curable resin composition according to claim 1. An insulator comprising the cured product according to claim 10.