CN106085169A - Solidification compound - Google Patents

Abstract

The problem of the present invention is to provide the solidification compound that can prepare solidfied material, and described solidfied material has sufficient peel strength, can realize low coefficient of linear thermal expansion, low dielectric loss tangent.The solution of the present invention is a kind of resin combination, it contains, and (A) has the phosphonate compound of more than 1 ethylenic unsaturated bond in intramolecular, (B) has the ethylenic unsaturated bond of more than 2 and the aromatic hydrocarbon of more than 1 or the free-radical polymerised compound of ester ring type hydrocarbon and (C) inorganic filling material in intramolecular, and (1) composition is different compounds from (2) composition.

Description

Solidification compound

Technical field

The present invention relates to solidification compound.And then the present invention relates to the insulating barrier containing said composition compositions, Lamellar laminated material containing said composition, many containing insulating barrier obtained by the solidification compound in said composition is solidified Layer printed substrate, semiconductor device containing this multilayer printed circuit board.

Background technology

In recent years, the miniaturization of electronic equipment, high performance are in development, and in multilayer printed circuit board, stack layer is by many Stratification, it is desirable to the miniaturization of distribution and densification.In order to pursue the miniaturization etc. of distribution, for multilayer printed circuit board Insulating barrier also requires that various performance.

Such as in patent documentation 1, disclosing containing specific vinyl compound and weight average molecular weight is more than 10000 High molecular body can improve the viscosity etc. when being processed into curable film as the hardening resin composition of essential component Performance (with reference to claim 1, the 0004th section etc.).But, patent documentation 1 does not disclose hardening resin composition and contains phosphonic acids Ester compounds.It addition, patent documentation 1 is for by the peel strength of solidfied material, line warm obtained by hardening resin composition solidification The coefficient of expansion is not studied.

On the other hand, for insulating barrier, it is desirable to be capable of sufficient peel strength, low coefficient of linear thermal expansion, low medium Loss factor, if but low dielectric loss tangent to be realized, then there is the tendency that peel strength dies down, on the contrary, if being intended to realize filling The peel strength divided, then have the tendency that dielectric dissipation factor uprises, therefore, it is difficult to design meets the solidfied material of these performances simultaneously.

Existing skill document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2006-83364 publication.

Summary of the invention

The problem that invention is to be solved

The present invention relates to prepare and there is sufficient peel strength, low coefficient of linear thermal expansion, low dielectric loss tangent can be realized The compositions of solidfied material.

Moreover, it relates to be suitable to prepare the compositions of the insulating barrier of multilayer printed circuit board.

And then, the present invention relates to the semiconductor device of the insulating barrier containing this multilayer printed circuit board.

Solve the means of problem

The present inventor etc. in order to solve above-mentioned problem carried out make great efforts research, found that containing (1) intramolecular have 1 with On the phosphonate compound of ethylenic unsaturated bond, (2) in intramolecular, there is the ethylenic unsaturated bond of more than 2 and more than 1 Aromatic hydrocarbon or the compositions of the free-radical polymerised compound of ester ring type hydrocarbon and (3) inorganic filling material can provide Sufficient peel strength can be kept, realize above-mentioned low coefficient of linear thermal expansion, the solidfied material of low dielectric loss tangent simultaneously, from And complete the present invention.

That is, the present invention includes following mode.

[1] compositions, it contains:

(1) there is the phosphonate compound of the ethylenic unsaturated bond of more than 1 in intramolecular；

(2) in intramolecular, there is the ethylenic unsaturated bond of more than 2 and the aromatic hydrocarbon of more than 1 or the freedom of ester ring type hydrocarbon Base polymerizable compound；And

(3) inorganic filling material,

Wherein, (1) composition and (2) composition are different compounds.

[2] according to the compositions described in above-mentioned [1], wherein, (1) composition is represented by following formula (I),

[in formula (I), R₄₁And R₄₂Being alkyl or aryl independently of one another, X is represented by following formula (X-1) or following formula (X-2).]

[in formula (X-1) and (X-2), R₃₅～R₄₀It is hydrogen, alkyl or aryl independently of one another.].

[3] according to the compositions described in above-mentioned [2], wherein, in formula (I), R₄₁And R₄₂It is carbon number independently of one another It it is the alkyl or phenyl of 1～3.

[4] according to the compositions described in above-mentioned [2] or [3], wherein, in formula (I), X is represented by formula (X-1), at formula (X- 1) in, R₃₅～R₃₇For hydrogen.

[5] according to the compositions according to any one of above-mentioned [1]～[4], wherein, the compositions of (3) composition will be removed When nonvolatile component is set to 100 mass %, (1) composition is 3～45 mass %.

[6] according to the compositions according to any one of above-mentioned [1]～[5], wherein, the nonvolatile component of compositions is set to During 100 mass %, (1) composition adds up to 1～70 mass % with (2) composition.

[7] according to the compositions according to any one of above-mentioned [1]～[6], wherein, the inorganic filling material of (3) composition is Silicon dioxide.

[8] according to the compositions according to any one of above-mentioned [1]～[7], wherein, by the inorganic filling material of (3) composition Carrying out surface process with silane coupler, described silane coupler has selected from acryloyl group (ア Network リ Le), methacryl The functional group of more than a kind in base, styryl, amino, epoxy radicals, vinyl.

[9] according to the compositions according to any one of above-mentioned [1]～[7], wherein, by the inorganic filling material of (3) composition Surface process is carried out with amino silicone methane series coupling agent, vinyl silanes system coupling agent or styryl silane series coupling agent.

[10] according to the compositions according to any one of above-mentioned [1]～[9], wherein, the nonvolatile component of compositions is set When being 100 mass %, (3) composition is 30～80 mass %.

[11] according to the compositions according to any one of above-mentioned [1]～[10], wherein, (2) composition is following formula (II) institute The free-radical polymerised compound shown,

[in formula (II), R₁～R₆Hydrogen or alkyl that carbon number is 1～4 independently of one another, A be containing aromatic hydrocarbon or The divalent group of ester ring type hydrocarbon.].

[12] according to the compositions described in above-mentioned [11], wherein, in formula (II), A is by following formula (A-1), (A-2), (A- 3) or (A-4) represent,

[in formula (A-1), (A-2), B is the divalent group containing aromatic hydrocarbon or ester ring type hydrocarbon, in formula (A-1), and E₁And E₂ It is alkylidene or alkylidene epoxide independently of one another.]

[in formula (A-3), D is following formula (D-1).]

[in formula (D-1), R₇～R₁₄Be independently of one another hydrogen, carbon number be the alkyl or phenyl of less than 6, a, b are at least one Person is not the integer of 0～the 100 of 0, and B is the divalent group containing aromatic hydrocarbon or ester ring type hydrocarbon.]

[in formula (A-4), B is the divalent group containing aromatic hydrocarbon or ester ring type hydrocarbon, E₄And E₅It is alkylidene independently of one another Or alkylidene epoxide.].

[13] according to the compositions described in above-mentioned [12], wherein, in formula (A-1), (A-2), (D-1) and (A-4), B by Any one of following formula (B-1)～(B-6) represents,

[in formula (B-1)～(B-5), R₁₅～R₃₄And R₄₃～R₅₀Be independently of one another hydrogen, carbon number be the alkyl of less than 6 Or phenyl, in formula (B-3), E is alkylidene or alkylidene epoxide.].

[14] according to the compositions according to any one of above-mentioned [1]～[10], wherein, (2) composition is containing at least 2 formulas (V) construction unit shown in and by free-radical polymerised compound obtained by construction unit atactic polymerization shown in formula (III)～(V),

[in formula (III)～(V), X is hydrogen or carbon number is the alkyl of less than 6, in formula (IV), and R₅₁For alkyl or hydroxyl Alkyl, in formula (V), R₅₂For containing ethylenic unsaturated bond and aromatic hydrocarbon or the group of ester ring type hydrocarbon.].

[15] according to the compositions described in above-mentioned [14], wherein, formula (V) is represented by formula (VI),

。

[16] composition for insulating layer of multilayer printed circuit board, it is characterised in that containing arbitrary in above-mentioned [1]～[15] Compositions described in Xiang.

[17] lamellar laminated material, it is characterised in that containing the compositions according to any one of above-mentioned [1]～[16].

[18] solidfied material, it is by the compositions according to any one of above-mentioned [1]～[16] or the sheet described in above-mentioned [17] Solidfied material obtained by shape laminated material heat cure, wherein, the dielectric dissipation factor of this solidfied material is less than 0.005.

[19] solidfied material, it is by the compositions according to any one of above-mentioned [1]～[16] or the sheet described in above-mentioned [17] Solidfied material obtained by shape laminated material heat cure, wherein, the coefficient of linear thermal expansion of this solidfied material is less than 40ppm/ DEG C.

[20] solidfied material, it is by the compositions according to any one of above-mentioned [1]～[16] or the sheet described in above-mentioned [17] Solidfied material obtained by shape laminated material heat cure, wherein, the glass transition temperature of this solidfied material is more than 170 DEG C.

[21] multilayer printed circuit board, it is characterised in that containing by the compositions according to any one of above-mentioned [1]～[16] Or insulating barrier obtained by the lamellar laminated material heat cure described in above-mentioned [17].

[22] semiconductor device, it is characterised in that containing the multilayer printed circuit board described in above-mentioned [21].

The fruit of invention

The present invention can provide the compositions that can prepare solidfied material, described solidfied material to have sufficient peel strength, can realize Low coefficient of linear thermal expansion, low dielectric loss tangent.It addition, the present invention can provide the insulation being suitable to prepare multilayer printed circuit board The compositions of layer.And then, the present invention can provide the semiconductor device of the insulating barrier containing this multilayer printed circuit board.

Detailed description of the invention

[compositions]

Compositions as a kind of mode of the present invention is following compositions, and it contains (1) and has more than 1 olefinic in intramolecular The phosphonate compound of unsaturated bond, (2) have the ethylenic unsaturated bond of more than 2 and the aromatic series of more than 1 in intramolecular Hydrocarbon or the free-radical polymerised compound of ester ring type hydrocarbon, (3) inorganic filling material and at random contain (4) other composition.Below Each composition contained in the compositions of the present invention is described in detail.

(1) there is the phosphonate compound of more than 1 ethylenic unsaturated bond in intramolecular

(1) composition that can use in the present invention be bonded with on the phosphorus atoms of compound with phosphonate ester skeleton have to The compound of the group of the ethylenic unsaturated bond of few more than 1.Preferably phosphonate compound has with the structure of following formula (I),

In formula (I), R₄₁、R₄₂Being alkyl, aryl independently of one another, X is represented by following formula (X-1) or following formula (X-2)；

In formula (X-1) and (X-2), R₃₅～R₄₀It is hydrogen, alkyl, aryl independently of one another.

The alkyl of the present invention can be any one of straight-chain or branched.The carbon number of this alkyl is preferably 1～20, more excellent Elect 1～14 and then preferably 1～12 and then more preferably 1～6, particularly preferably 1～3 as.This alkyl can be enumerated such as Methyl, ethyl, propyl group, isopropyl, butyl, sec-butyl, isobutyl group, the tert-butyl group, amyl group, hexyl, heptyl, octyl group, nonyl and the last of the ten Heavenly stems Base.

The aryl of the present invention is by the group of the hydrogen atom on aromatic hydrocarbon 1 aromatic rings of removing.As substituent group The carbon number of aryl be preferably 6～24, more preferably 6～18 and then preferably 6～14 and then more preferably 6～10.As This aryl, can enumerate such as phenyl, naphthyl and anthryl.

R₄₁、R₄₂Be the most independently of one another carbon number be the alkyl of 1～12 or aryl that carbon number is 6～24, More preferably carbon number is alkyl, phenyl, naphthyl and the anthryl of 1～6, and then preferably carbon number is the alkyl of 1～3 Or phenyl, it is most preferably selected from methyl, ethyl or phenyl.

R₃₅、R₃₆、R₃₇Be the most independently of one another hydrogen, carbon number be 1～12 alkyl or carbon number be 6～24 Aryl, more preferably hydrogen, carbon number are alkyl, the phenyl of 1～6.

And then preferably R₃₆、R₃₇At least one be hydrogen.

R₃₅～R₄₀Be the most independently of one another hydrogen, carbon number be the alkyl of 1～6, more preferably hydrogen.

As (A) composition, the most more preferably enumerate with the compound shown in following formula (8)～(21).

Should illustrate, these compounds such as can be obtained by sheet mountain chemistry (strain).

Wherein, the compound shown in preferred formula (8), (9), (10).

In the present compositions, the angle from the dielectric dissipation factor reducing the solidfied material obtained by compositions is examined Consider, when the nonvolatile component of the compositions by removing (3) composition is set to 100 mass %, as the phosphonate ester chemical combination of (1) composition The content of thing is preferably 3～45 mass %, more preferably 5～40 mass %, and then preferably 5～36 mass %.

(2) intramolecular have the ethylenic unsaturated bond of more than 2 and the aromatic hydrocarbon of more than 1 or ester ring type hydrocarbon from By base polymerizable compound

(2) composition that can use in the present invention is that the ethylenic unsaturated bond with more than 2 is as free-radical polymerised group Free-radical polymerised compound.(2) composition is the compound different from (1) composition.In this manual, free-radical polymerised Compound comprises the resin as curable group of the ethylenic unsaturated bond with more than 2.Ethylenic unsaturated bond is due to polymerization Without producing hydroxyl, the resin cured matter that dielectric dissipation factor is low therefore can be obtained.

As (2) composition that can use in the present invention, the free-radical polymerised chemical combination shown in the most following formula (II) Thing,

In formula (II), R₁～R₆It is hydrogen independently of one another or carbon number is 1～4, preferably 2～the alkyl of 3.R₁、R₂、R₅、R₆Excellent Elect hydrogen as.R₃、R₄It is preferably hydrogen or methyl.

In formula (II), A is the divalent group containing aromatic hydrocarbon or ester ring type hydrocarbon.A is preferably by following formula (A-1), (A- 2), (A-3) or (A-4) divalent group of representing,

In formula (A-1), (A-2), B is the divalent group containing aromatic hydrocarbon or ester ring type hydrocarbon, E₁、E₂It is alkylene independently of one another Base or alkylidene epoxide.

E₁、E₂Preferably carbon number is 1～16, preferably 1～the alkylidene of 10 or alkylidene epoxide, preferably methylene, Ethylidene, propylidene, isopropylidene, polymethylene epoxide, polyethylene epoxide (Port リ エ チ レ Application オ キ シ yl), more preferably It is methylene, isopropylidene, the polyethylene epoxide of carbon number 4～12, preferably 4～8.

In formula (A-3), D is following formula (D-1),

In formula (D-1), R₇～R₁₄Be independently of one another hydrogen, carbon number be less than 6, preferably 1～the alkyl or phenyl of 3, excellent Choosing is hydrogen or methyl.Especially, R₇、R₈、R₁₃、R₁₄More preferably methyl.A, b be at least one party be not the integer of 0～the 100 of 0, Preferably 3～80, more preferably 5～50, B is the divalent group containing aromatic hydrocarbon or ester ring type hydrocarbon.

In formula (A-4), B is the divalent group containing aromatic hydrocarbon or ester ring type hydrocarbon, E₄And E₅It is alkylene independently of one another Base or alkylidene epoxide.

B is the divalent group containing aromatic hydrocarbon or ester ring type hydrocarbon, can enumerate arlydene, inferior heteroaryl, cycloalkylidene, Bridged ring (such as adamantyl, norborny, methylnorbornyl) shape alkyl, above-mentioned bridged ring and monocycle (such as cycloheptane ring, ring Hexane ring) or the aromatic hydrocarbyl of the divalent such as multi-ring (the most decahydronaphthalene naphthalene nucleus) group of condensing or ester ring type alkyl；The virtue of divalent Fragrant race's hydrocarbon or ester ring type hydrocarbon are bonded with oxygen atom, alkylidene, alkylidene epoxide, are integrally formed the group into divalent；1 valency The group that aromatic hydrocarbyl or ester ring type alkyl become side base shape (ペ Application ダ Application ト shape) and comprised.

Preferably enumerate arlydene, cycloalkylidene, bridged cycloalkyl alkyl, bridged ring and monocycle or multi-ring condense group, arlydene The group being bonded with oxygen atom, alkylidene, alkylidene epoxide.

As preferred B, following formula (B-1)～(B-6) can be enumerated,

In formula (B-1)～(B-5), R₁₅～R₃₄And R₄₃～R₅₀Be independently of one another hydrogen, carbon number be less than 6 alkyl or Phenyl, more preferably hydrogen or methyl.In formula (B-3), E is alkylidene or alkylidene epoxide.Preferably E and the E of (A-1)₁Or E₂ Identical.

As (2) composition, and then specifically it is more preferably any one compound shown in following formula (23)～(31),

In formula (23), R₁～R₆, B, a, b as described above；

。

As the free-radical polymerised compound of commercially available (2) composition, phenylethene modified polyphenylene oxide resin (three can be enumerated Pedicellus et Pericarpium Trapae gas chemistry (strain) system " OPE-2St ", number-average molecular weight 1200, be equivalent to formula (23), wherein, B is (B-1), R₁～R₆For Hydrogen, a is 5～50, and b is 5～50), di-cresols diallyl ether (Mitsubishi Chemical's (strain) system " YL7776 (number-average molecular weight 331) ", be equivalent to formula (24)), (common prosperity chemistry (strain) system, " DCP-A ", number are all for dihydroxymethyl-tristane diacrylate Molecular weight 304, is equivalent to formula (25)), dihydroxymethyl-tristane dimethylacrylate (common prosperity chemistry (strain) system, " DCP-M ", number-average molecular weight 318, be equivalent to formula (26)), bisphenol-A EO addition diacrylate, bisphenol-A EO addition dimethyl Acrylate (common prosperity chemistry (strain) system be equivalent to formula (27)～(29))), diallyl phthalate (ダ イ ソ (strain) system " ダ イ ソ ダ ッ プ (registered trade mark) monomer (number-average molecular weight 246.3) ", be equivalent to formula (30)), isophthalic diformazan (ダ イ ソ (strain) makes " ダ イ ソ ダ ッ プ (registered trade mark) 100 monomer (number-average molecular weight 246.3) " to diallyl phthalate, phase When in formula (31)) etc..

As the free-radical polymerised compound of other preferred (2) composition, can enumerate shown in formula (III)～(V) Construction unit atactic polymerization, number-average molecular weight is less than 30000, is preferably the macromolecule of 12000～25000.Above-mentioned high score Son contains the construction unit shown at least 2 formulas (V),

In formula (III)～(V), X is hydrogen or carbon number is less than 6, preferably 1～the alkyl of 3, preferably hydrogen or methyl.? In formula (IV), R₅₁For alkyl or hydroxy alkyl.In formula (V), R₅₂Containing ethylenic unsaturated bond and aromatic hydrocarbon or ester ring type Hydrocarbon.Formula (V) is preferably represented by formula (VI)；

。

For macromolecule obtained by the construction unit atactic polymerization shown in formula (III), (IV) and (VI), as commercially available product, Can enumerate acrylic oligomers (contest road (ダ イ セ Le) chemical industry (strain) system " サ イ Network ロ マ P Z230AA "), Acrylic oligomers (contest road chemical industry (strain) system " サ イ Network ロ マ P Z251 ", " サ イ Network ロ containing carboxylic acid group マ P Z254F ") etc..

Volatilization in time preventing the resin varnish prepared by the compositions of the present invention to be dried, prevent the melt viscosity of compositions From the point of view of excessively raising, the number-average molecular weight of free-radical polymerised compound is preferably less than 30000, and more preferably 100 ～the scope of 28000, the scope of more preferably 200～25000.Should illustrate, the number-average molecular weight in the present invention utilizes gel Permeation chromatography (GPC) method (polystyrene conversion) measures.The number-average molecular weight that have employed GPC method specifically can be as following Calculate: use (strain) Shimadzu Seisakusho Ltd. LC-9A/RID-6A as determinator, use Showa electrician (strain) society Shodex K-800P/K-804L/K-804L as flowing phase as pillar, use chloroform etc., measures under the column temperature of 40 DEG C, uses standard The standard curve of polystyrene calculates.

In the present compositions, from the point of view of the compatibility of compositions improves, non-volatile by said composition When becoming to be divided into 100 mass %, the content as the free-radical polymerised compound of (2) composition is preferably 1～65 mass %, more excellent Elect 5～65%, and then more preferably 10～65 mass % as.

The compositions of the present invention is by containing free-radical polymerised compound, reducing the solidfied material formed by compositions Coefficient of linear thermal expansion.

In the present compositions, the free-radical polymerised compound as (2) composition can only use one, it is also possible to It is used in combination of two or more.

The compositions of the present invention, by the combination of (1) composition with (2) composition, can be formed and have sufficient peel strength Solidfied material.When nonvolatile component is set to 100 mass %, the total content of (1) composition and (2) composition is preferably 1～70 mass %, More preferably 5～70%, and then more preferably 10～70 mass %.

(3) inorganic filling material

The compositions of the present invention is by possibly together with inorganic filling material, and the medium that can reduce the solidfied material formed by compositions damages Consumption factor and coefficient of linear thermal expansion.As inorganic filling material, such as silicon dioxide, aluminium oxide, barium sulfate, cunning can be enumerated Stone, clay, mica powder, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, Alborex M 12, Barium metatitanate., titanium Acid strontium, calcium titanate, magnesium titanate, bismuth titanates, titanium oxide, barium zirconate, calcium zirconate etc..Wherein, preferably silicon dioxide.It addition, it is excellent Choosing is amorphous silica, pulverizes silicon dioxide, fused silica, crystalline silica, synthetic silica, hollow two The silicon dioxide such as silicon oxide, mesoporous silicon oxide, more preferably fused silica.It addition, as silicon dioxide, the most spherical two Silicon oxide.They can use a kind or two or more are applied in combination.As commercially available spheroidal fused silicon dioxide, can enumerate (strain) Admatechs system " SOC2 ", " SOC1 ", " SOC4 ".

The mean diameter of inorganic filling material is not particularly limited, but from carrying out the formation of fine distribution on the insulating layer Angle considers, above-mentioned mean diameter is preferably below 5 μm, below more preferably 3 μm and then below preferably 1 μm and then more excellent Elect below 0.7 μm as.On the other hand, in time making compositions be formed as varnish, prevent the angle that varnish viscosity raises, operability reduces Degree considers, more than preferably 0.01 μm, more than more preferably 0.05 μm, and then more than preferably 0.1 μm.Above-mentioned inorganic fill material The mean diameter of material can be measured by laser diffraction-scattering method based on Michaelis (Mie) scattering theory.Specifically, can make The particle size distribution of inorganic filling material is made with volume reference, by its intermediate value of laser diffraction and scattering formula particle size distribution device Particle diameter measures as mean diameter.Measure sample preferably use utilize ultrasound wave to make inorganic filling material be dispersed in water and The sample become.As laser diffraction and scattering formula particle size distribution device, (strain) hole field can be used to make made LA-950 etc..

The content of inorganic filling material is not particularly limited, and reduces from making dielectric dissipation factor and prevents scratching of film form Property reduce from the point of view of, when the nonvolatile component of resin combination is set to 100 mass %, described inorganic filling material Content is preferably 30～80 mass %, more preferably 40～75 mass %, and then preferably 45～70 mass %.

Inorganic filling material can be with having selected from acryloyl group, methylacryloyl, styryl, amino, epoxy radicals, second The silane coupler of more than a kind functional group in thiazolinyl carries out surface process.Such as, inorganic filling material preferably uses amino silane It is coupling agent, ureido silane system coupling agent, epoxy radicals silicone hydride system coupling agent, hydrosulphonyl silane system coupling agent, silane series coupling agent, second Alkenyl silanes system coupling agent, styryl silane series coupling agent, acrylate silane system coupling agent, the coupling of isocynate silane system The surface conditioning agents such as agent, sulfidesilane system coupling agent, organic silazane hydride compounds, titanate esters system coupling agent carry out surface Reason so that it is moisture-proof, dispersibility improve.They can use a kind or two or more are applied in combination.

Specifically, 3-TSL 8330, APTES, 3-aminopropan can be enumerated Base diethoxymethylsilane, N-phenyl-3-TSL 8330, N-dimethylaminopropyl trimethoxy silane, N-2 (-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyldimethoxy methyl silicon Ureido silane system coupling agent, the 3-glycidyl oxygen such as amino silicone methane series coupling agent, 3-ureidopropyltriethoxysilane such as alkane Base propyl trimethoxy silicane, 3-glycidyloxypropyl triethoxysilane, 3-glycidyloxypropyl methyl Diethoxy silane, 3-glycidyloxypropyl (dimethoxy) methyl-monosilane, glycidyl butyl trimethoxy silicon Epoxy radicals silicone hydride system coupling agent, the 3-mercaptopropyi trimethoxies such as alkane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane Silane, 3-Mercaptopropyltriethoxysilane, 3-mercaptopropyi methyl dimethoxysilane, 11-mercapto-undecanoic base trimethoxy The hydrosulphonyl silane system coupling agents such as base silane, MTMS, octadecyl trimethoxysilane, phenyl trimethoxy silicon The silane such as alkane, methacryloxypropyl trimethoxy silane, imidizole silane, triazine silane, tert-butyl trimethoxy silane It is the vinyls such as coupling agent, vinyltrimethoxy silane, VTES, vinyl methyl diethoxy silane Silane series coupling agent, to styryl silane series coupling agent, 3-acryloyl group epoxide propyl group such as styryl trimethoxy silanes Trimethoxy silane, 3-methylacryloyl epoxide propyl trimethoxy silicane, 3-methylacryloyl epoxide dimethylamine oxygen Base silane, 3-methylacryloyl epoxide propyl-triethoxysilicane, 3-methylacryloyl epoxide propyl group diethoxy silane Deng the isocynate silane system coupling agents such as acrylate silane system coupling agent, 3-isocyanates propyl trimethoxy silicane, double (three Triethoxysilyl propyl group) disulphide, double (triethoxysilylpropyltetrasulfide) tetrasulfide sulfides silane system be even Connection agent, hexamethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyl-disilazane, hexaphenyl disilazane, three silicon nitrogen Alkane, ring three silazane, 2,2,4,4,6,6-pregnancy basic ring three silazane, octamethylcyclotetrasilazane, six butyl disilazanes, six Octyl group disilazane, 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyl tetramethyl-disilazane, 1,3-diphenyl four Methyl disilazane, 1,3-dimethyl tetraphenyl disilazane, 1,3-diethyltetramethyldisilazane, 1,1,3,3-tetra-benzene Base-1,3-dimethyl disilazane, 1,3-dipropyl tetramethyl-disilazane, pregnancy basic ring three silazane, dimethylamino three The organic silazane hydride compounds such as methylsilazane, tetramethyl-disilazane, tetra-n-butyl titanate dimer, isopropoxy ethohexadiol Double (triethanolamine acid esters) (the ジ イ ソ プ ロ Port キ シ チ タ Application of titanium, tetra-n-butyl titanate, ethohexadiol titanium, diisopropoxy titanium PVC ス (ト リ エ タ ノ Le ア ミ ネ ト)), titanium dihydroxide dilactic acid ester, double (DL-Lactic acid ammonium salt .) titanium of dihydroxy, double (pyrophosphoric acid two is pungent Ester) ethylene titanate, double (dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, metatitanic acid four just Butyl ester, metatitanic acid four (2-ethylhexyl) ester, double (dioctyl phosphite) tetraisopropyl titanate, double (phosphorous acid two (tridecyl) Ester) metatitanic acid four monooctyl ester, double (phosphorous acid two (tridecyl) ester) metatitanic acid four (2,2-diene propoxy methyl-1-butyl) ester, three Caprylyl isopropyl titanate, isopropyl tricumylphenyltitanate, isopropyl triisostearoyltitanate, isostearoyl base two acryloyl Isopropyl titanate, Dimethylacryloyl isostearoyl isopropyl titanate, isopropyl tri(dioctyl phosphate)titanate, three (12 Benzene sulfonamide acyl group) isopropyl titanate, isopropyl tris(dioctyl pyrophosphate)titanate, three (N-amide ethyl-amino ethyl) titanium The titanate esters system coupling agents etc. such as isopropyl propionate.As commercially available product, SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM403 " (3-ring can be enumerated Oxygen the third oxygen propyl trimethoxy silicane), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM803 " (3-mercaptopropyi trimethoxy silane), letter More chemical industry (strain) system " KBE903 " (APTES), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM573 " (N-phenyl-3-TSL 8330), SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM1403 " are (to styryl trimethoxy Base silane) etc..Wherein, by inorganic filling material amino silicone methane series coupling agent, vinyl silanes system coupling agent or styryl When silane series coupling agent carries out surface process, it is excellent for making dielectric dissipation factor reduce, thus preferably.

(4) other composition

In the resin combination of the present invention, in addition to mentioned component, as other composition, it is also possible to suitably coordinate solidification Agent, heat-curing resin, thermoplastic resin, polymerization initiator, curing accelerator, organic filler, organic solvent, thickening agent, Defoamer, adaptation imparting agent, coloring agent, additive etc..These other compositions can at least use a kind, such as can by 2 kinds with On be used in mixed way.

(i) firming agent

As the firming agent used in the present invention, it is not particularly limited, activity ester type firming agent, cyanic acid ester type can be enumerated admittedly Agent, phenol-ing fixed agent, benzimidazole dihydrochloride type firming agent etc., more reduce from making surface roughness and make dielectric dissipation factor From the point of view of reduction, activity ester type firming agent and/or cyanic acid ester type firming agent are preferably used, more preferably use activity ester type solid Agent.They can use a kind or two or more are applied in combination.

As activity ester type firming agent, it is not particularly limited, phenolic ester class (Off ェ ノ Le エ ス generally can be preferably used テ Le), thiophenol esters (チ オ Off ェ ノ Le エ ス テ Le), N-hydroxylamine esters, the esters of heterocycle hydroxyl compound Deng the compound in 1 molecule with more than 2 the high ester groups of reactivity.This activity ester type firming agent is preferably by Carboxylation Compound and/or thiocarboxylic acid compound obtain with the condensation reaction of hydroxy compounds and/or mercaptan compound.

Especially from the point of view of improving thermostability, the activity that preferably can be obtained by carboxylic acid compound and hydroxy compounds Ester type firming agent, the active ester type that more preferably can be obtained by carboxylic acid compound and oxybenzene compound and/or naphthol compound is solid Agent.As carboxylic acid compound, can enumerate such as benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, M-phthalic acid, p-phthalic acid, PMA etc..As oxybenzene compound or naphthol compound, hydroquinone, isophthalic can be enumerated Diphenol, bisphenol-A, Bisphenol F, bisphenol S, phenolphthalin, the bisphenol-A that methylates, the Bisphenol F that methylates, the bisphenol S that methylates, phenol, adjacent first Phenol, metacresol, paracresol, catechol, alpha-Naphthol, betanaphthol, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene, 2,6-dihydroxy naphthlene, Dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene-type biphenyl Phenol, linear phenol-aldehyde resin (phenol novolac) etc..As activity ester type firming agent, preferably containing dicyclopentadiene-type two The active ester type firming agent of phenol structure, the active ester type firming agent containing naphthalene structure, the acetylation as linear phenol-aldehyde resin The active ester type firming agent of thing, the active ester type firming agent of benzoylate as linear phenol-aldehyde resin are wherein strong from peeling off The excellent aspect that improves of degree is set out, and more preferably contains the active ester type firming agent of dicyclopentadiene-type biphenol structure, contains The active ester type firming agent of naphthalene structure, and then preferably contain the active ester type firming agent of dicyclopentadiene-type biphenol structure.

As activity ester type firming agent, the active ester type disclosed in Japanese Unexamined Patent Publication 2004-277460 publication can be used solid Agent, additionally can also use commercially available material.Specifically, as the active ester type containing dicyclopentadiene-type biphenol structure Firming agent, can enumerate EXB9451, EXB9460, EXB9460S-65T, HPC-8000, HPC-8000-65T (DIC (strain) system, Active group equivalent about 223), HPC8000L-65M (DIC (strain) system, nonvolatile component 65 mass % of active group equivalent about 220 MEK solution)；As the active ester type firming agent containing naphthalene structure, EXB9416-70BK (DIC (strain) system, active group can be enumerated Equivalent about 274), the active ester type firming agent as the acetylate of linear phenol-aldehyde resin can enumerate DC808 (Mitsubishi Chemical (strain) system, active group equivalent about 149)；Active ester type firming agent as the benzoylate of linear phenol-aldehyde resin can be enumerated (Mitsubishi Chemical's (strain) system, active group equivalent are about for YLH1026 (Mitsubishi Chemical's (strain) system, active group equivalent about 200), YLH1030 201), YLH1048 (Mitsubishi Chemical's (strain) system, active group equivalent about 245) etc..

Particularly preferred active ester resin be containing the dicyclopentadiene-type biphenol structure shown in following formula (32), It is respectively provided with X-base and the resin compound of XO-base (wherein X is the phenyl or naphthyl can with substituent group) at end,

(in formula, m is 0 or 1, and n is 0.25～1.5 as meansigma methods, is preferably 0.4～1.2).The weight average of this active ester resin divides Son amount is preferably 1500～4000, more preferably 2000～3000.

Especially preferred active ester resin is HPC-8000, and it is to have the dicyclopentadiene-type shown in below formula (33) Biphenol structure, is respectively provided with X-base and XO-base (wherein X is the naphthyl can with substituent group) at end, and weight average molecular weight is The active ester resin of about 2700,

(in formula, m is 0 or 1, and n is 0.4～1.2 as meansigma methods).

As cyanic acid ester type firming agent, it is not particularly limited, phenolic resin type (ノ ボ ラ ッ Network type) (line style can be enumerated Phenolic resin type, alkyl novalac-type etc.) cyanic acid ester type firming agent, dicyclopentadiene-type cyanic acid ester type firming agent, double Phenolic (bisphenol A-type, bisphenol-f type, bisphenol S type etc.) cyanic acid ester type firming agent and the part quilt of these cyanic acid ester type firming agent The prepolymer etc. of triazine.The weight average molecular weight of cyanic acid ester type firming agent is not particularly limited, and preferably 500～4500 are more excellent Elect 600～3000 as.As the concrete example of cyanic acid ester type firming agent, such as bisphenol A dicyanate, polyphenol cyanate can be enumerated (oligomeric (3-methylene-1,5-phenylenecyanate)), 4,4' methylene bis (2,6-3,5-dimethylphenyl cyanate), 4,4'-Asia Double (4-cyanate) phenyl-propane of ethyl diphenyl dicyanate, hexafluoro bisphenol-a dicyanate, 2,2-, double (the 4-cyanate of 1,1- Phenylmethane), double (4-cyanate-3,5-3,5-dimethylphenyl) methane, 1,3-double (4-cyanate phenyl-1-(methyl ethylidene)) Benzene, double (4-cyanate phenyl) thioether, double (4-cyanate phenyl) ether etc. 2 official can cyanate ester resin, by linear phenol-aldehyde resin, first The derivative multifunctional cyanate ester resin such as phenol phenolic resin, phenolic resin containing bicyclopentadiene structure, these cyanate resins A part for fat is by the prepolymer etc. of triazine.They can use a kind or two or more are applied in combination.As commercially available cyanogen Acid ester resin, can enumerate novalac-type multifunctional cyanate ester resin (Lonza Japan (strain) system, PT30, cyanate Equivalent 124), bisphenol A dicyanate part or all formed prepolymer (the Lonza Japan of trimer by triazine (strain) system, BA230, cyanate equivalent 232), cyanate ester resin containing bicyclopentadiene structure (Lonza Japan (strain) system, DT-4000, DT-7000) etc..

As preferred cyanic acid ester type firming agent PT30 structural formula as shown below,

[in formula, n represents Arbitrary Digit (preferably 0～20, more preferably 1～10) as meansigma methods.].

As phenol-ing fixed agent, it is not particularly limited, preferably biphenyl type firming agent, naphthalene type firming agent, line style phenolic aldehyde Resin type firming agent, naphthylene ether type firming agent, phenol-ing fixed agent containing triazine skeleton.Specifically, can enumerate as connection MEH-7700, MEH-7810, MEH-7851 of benzene-type firming agent (bright and chemical conversion (strain) system), as naphthalene type firming agent NHN, CBN, GPH (Japan's chemical medicine (strain) system), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (new day Ferrum chemistry (strain) system), EXB9500 (DIC (strain) system), as novalac-type firming agent TD2090 (DIC (strain) system), As the EXB-6000 (DIC (strain) system) of naphthylene ether type firming agent, as the phenol-ing fixed agent containing triazine skeleton LA3018, LA7052, LA7054, LA1356 (DIC (strain) system) etc..

As benzimidazole dihydrochloride type firming agent, being not particularly limited, as concrete example, (four countries are melted into can to enumerate F-a, P-d (strain) makes), HFB2006M (Showa macromolecule (strain) system) etc..

In the present compositions, examine from the angle making the dielectric dissipation factor of the solidfied material formed by compositions reduce Considering, when the nonvolatile component in compositions is set to 100 mass %, the content of firming agent is preferably 1～30 mass %, more preferably 2～20 mass %, and then preferably 3～10 mass %.

(ii) heat-curing resin

As the heat-curing resin that can use in the present invention, such as epoxy resin can be enumerated.Wherein, as asphalt mixtures modified by epoxy resin Fat, can enumerate such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol AF type asphalt mixtures modified by epoxy resin Fat, novolac type epoxy resin, tert butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, Asia Naphthyl ether type epoxy, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, CF type asphalt mixtures modified by epoxy resin Fat, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resins, there is the epoxy resin of butadiene structure, fat Ring type epoxy resin, hetero ring type epoxy resin, the epoxy resin containing volution, cyclohexanedimethanol type epoxy resin, trihydroxy methyl Type epoxy resin, halogenated epoxy resin etc..They can use a kind or two or more are applied in combination.

Wherein, from the point of view of reducing surface roughness, the most also making peel strength improve, it is preferably used selected from bis-phenol A type epoxy resin, bisphenol f type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene In ether type epoxy, glycidyl ester type epoxy resin and anthracene type epoxy resin more than a kind.Specifically, example can be enumerated As bisphenol A type epoxy resin (Mitsubishi Chemical's (strain) system " エ ピ U ト 828EL ", " YL980 ")), fluorination bisphenol type epoxy tree Fat (Mitsubishi Chemical's (strain) system " YL7760 "), bisphenol f type epoxy resin (Mitsubishi Chemical's (strain) system " jER806H ", " YL983U "), Naphthalene type 2 functional epoxy resins (DIC (strain) makes " HP4032 ", " HP4032D ", " HP4032SS ", " EXA4032SS "), naphthalene type 4 official Can epoxy resin (DIC (strain) makes " HP4700 ", " HP4710 "), naphthol type epoxy resin (Nippon Steel's chemistry (strain) system " ESN- 475V "), have biphenyl structural epoxy resin (Japan chemical medicine (strain) system " NC3000H ", " NC3000L ", " NC3100 ", Rhizoma Sparganii Chemistry (strain) system " YX4000 ", " YX4000H ", " YX4000HK ", " YL6121 "), anthracene type epoxy resin (Mitsubishi Chemical's (strain) make " YX8800 "), naphthylene ether type epoxy (DIC (strain) system " EXA-7310 ", " EXA-7311 ", " EXA-7311L ", " EXA7311-G3 "), glycidyl ester type epoxy resin (Na ガ セ ケ system テ ッ Network ス (strain) system " EX711 ", " EX721 ", (strain) プ リ Application テ ッ Network system " R540 " etc..Especially, biphenyl type epoxy resin owing to playing low roughness and high-peeling strength, because of This is preferred.

As preferred epoxy resin NC3000L structural formula as shown below.

It addition, as other preferred epoxy resin EXA4032SS structural formula as shown below.

In the present compositions, from improving the mechanical strength of solidfied material, the angle of resistance to water formed by compositions Considering, when the nonvolatile component in compositions is set to 100 mass %, the content of epoxy resin is preferably 1～30 mass %, more excellent Elect 2～20 mass %, and then preferably 3～10 mass % as.

(iii) thermoplastic resin

As the thermoplastic resin that can use in the present invention, can enumerate such as phenoxy resin, polyvinyl acetal resin, Polyimide resin, polyamide-imide resin, polyethersulfone resin, cyclic olefin polymer, polyacrylate resin and polysulfones tree Fat etc., preferably phenoxy resin, polyacrylate resin.They can use a kind or two or more are applied in combination.Thermoplastic The weight average molecular weight of the polystyrene conversion of property resin is preferably the scope of 8000～1000000, more preferably 10000～ The scope of 80000, and then the scope of preferably 20000～500000.The weight average molecular weight of the polystyrene conversion of thermoplastic resin Gel permeation chromatography (GPC) method can be utilized to measure.Specifically, the weight average molecular weight of the polystyrene conversion of thermoplastic resin can To calculate as following: use (strain) Shimadzu Seisakusho Ltd. LC-9A/RID-6A as determinator, use Showa electrician (strain) society Shodex K-800P/K-804L/K-804L, as post, uses the conduct flowing phases such as chloroform, at the bar of column temperature 40 DEG C Measure under part, calculate with the standard curve of polystyrene standard.During it addition, thermoplastic resin is phenoxy resin, this phenoxy group The epoxide equivalent of resin for example, 10000～20000 (g/ equivalent).

(iv) polymerization initiator

Polymerization initiator may be used for effectively carrying out the solidification of free-radical polymerised compound.The kind of polymerization initiator does not has It is particularly limited to, cyclohexanone peroxide, peroxidized t-butyl perbenzoate, methyl ethyl ketone peroxide, peroxidating two can be enumerated different Propyl benzene, t-butylcumylperoxide, di-t-butyl peroxide, diisopropyl benzene hydroperoxides, cumyl hydroperoxide, uncle The free-radical generating agent such as butyl hydroperoxides, 2,3-dimethyl-2,3-diphenyl butane.They can use a kind or by 2 kinds Combination of the above uses.As preferred polymerization initiator, (day is oily can to enumerate dialkyl peroxide system organic peroxide (strain) makes " パ ヘ キ シ Application 25B ", (Kayaku Akzo (strain) makes " Trigonox to cyclic peroxide system organic peroxide 311”)。

Coordinate content during polymerization initiator to be not particularly limited, the nonvolatile component in compositions is set to 100 mass % Time, preferably 0.1～3 mass %, more preferably 0.2～2 mass %.If within the range, be then possible to prevent dielectric loss because of The rising of number.

(v) curing accelerator

As curing accelerator, such as phosphorus system curing accelerator, amine system curing accelerator, the solidification promotion of imidazoles system can be enumerated Agent, guanidine system curing accelerator etc..

As phosphorus system curing accelerator, such as triphenylphosphine, boronic acid compounds, tetraphenyl tetraphenyl boron can be enumerated Hydrochlorate, normal-butyl tetraphenyl borate salts, tetrabutyl caprate, (4-aminomethyl phenyl) triphenyl rhodanate, tetraphenyl Rhodanate, butyl triphenyl rhodanate etc..

As amine system curing accelerator, the such as trialkylamine such as triethylamine, tri-butylamine, 4-dimethylamino can be enumerated Yl pyridines, benzyldimethylamine, 2,4,2,4,6 ,-three (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0)-ten one Alkene etc..

As imidazoles system curing accelerator, such as 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl can be enumerated Imidazoles, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2- Methylimidazole., 1-benzyl-2-phenylimidazole, 1-cyano ethyl-2-methylimidazole, 1-cyano ethyl-2-undecyl imidazole, 1- Cyano ethyl-2-ethyl-4-methylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-cyano ethyl-2-undecyl imidazole Trimellitate, 1-cyano ethyl-2-phenylimidazole trimellitate, 2,4-diaminourea-6-[2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diaminourea-6-[2'-undecyl imidazole base-(1')]-ethyl-s-triazine, 2,4-diamino Base-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diaminourea-6-[2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid addition product, 2-phenylimidazole isocyanuric acid addition product, 2-phenyl-4,5-dihydroxy first Base imidazoles, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo-[1,2-a] benzimidazole, 1-12 Imidazolium compounds and the imidazoles such as alkyl-2-methyl-3-benzyl imidazole chloride, 2-methylimidazole quinoline, 2-benzylimidazoline Compound and the adduct of epoxy resin.

As guanidine system curing accelerator, such as cyanoguanidines, 1-methylguanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-can be enumerated Guanidines, 1-(o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethyl guanidine, tetramethyl guanidine, pentamethyl guanidine, 1,5,7-tri-nitrogen Miscellaneous dicyclo [4.4.0] decyl-5-alkene, 7-methyl isophthalic acid, 5,7-tri-azabicyclo [4.4.0] decyl-5-alkene, 1-methyl biguanide, 1-second Base biguanide, 1-normal-butyl biguanide, 1-n-octadecane base biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-pi-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide etc..

Curing accelerator can be used alone a kind, maybe can also two or more be applied in combination.

In the case of compositions contains epoxy resin, preferably curing accelerator in the solidification compound of the present invention Content, when total metering of the nonvolatile component of epoxy resin and firming agent is set to 100 mass %, with 0.05 mass %～3 matter Use in the range of amount %.

As the organic filler that can use in the present invention, can enumerate such as Si powder, nylon powder, fluorine powder, Rubber particles etc..

As the organic solvent that can use in the present invention, acetone, methyl ethyl ketone (MEK) and Ketohexamethylene etc. can be enumerated The acetass such as ketone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether, carbitol acetate Aromatic hydrocarbon, the dimethyl formyls such as carbitol class, solvent naphtha, toluene, dimethylbenzene such as class, cellosolve, butyl carbitol The amide series solvents etc. such as amine, dimethyl acetylamide, N-Methyl pyrrolidone.

As the thickening agent that can use in the present invention, such as オ Le ベ Application, ベ Application ト Application etc. can be enumerated.

As the defoamer that can use in the present invention, such as silicon-type defoamer, fluorine system defoamer, height can be enumerated Molecule system defoamer etc..

As the adaptation imparting agent that can use in the present invention, can enumerate such as imidazoles system, thiazole system, triazole system, Silane coupler etc..

As the coloring agent that can use in the present invention, can enumerate that such as phthalocyanine blue, phthalocyanine green, iodine is green, azophosphine, charcoal Black etc..

Compositions containing above-mentioned each composition sets in the nonvolatile component of the compositions by removing above-mentioned inorganic filling material When being 100 mass %, phosphorus content be 0.2～5 mass %, preferably 0.5～4 mass %, more preferably 0.5～3 mass % be suitable.As Really phosphorus content is more than 0.2 mass %, then can play sufficient anti-flammability, the most preferably, if it addition, phosphorus content is 5 matter Amount below %, then can improve glass transition temperature, it is also possible to reduces coefficient of linear thermal expansion, the most preferably.

[preparation of compositions]

The compositions of the present invention can use three rollers, ball mill, bead mill by suitably mixing mentioned component according further to needs The mixing plants such as the mixing facilities such as machine, sand mill or high speed rotating mixer, super mixer, planetary-type mixer carry out mixing Or mixing prepare.It addition, pass through and then add above-mentioned organic solvent, it is also possible to prepare as resin varnish.

For the compositions of the present invention, can be formed and be capable of low coefficient of linear thermal expansion, low dielectric loss tangent, high glass The solidfied material of glass transition temperature, therefore in the manufacture of multilayer printed circuit board, can be suitable as multilayer printed circuit board Composition for insulating layer.And then, can be suitably as stack layer, the compositions that formed conductor layer by plating (that is, layer insulation compositions) uses.

As the form of the compositions of the present invention, it is not particularly limited, goes for the lamellar such as adhesive film, prepreg and fold Layer material, circuit substrate (laminated plate purposes, multilayer printed circuit board purposes etc.).The compositions of the present invention can also be with varnish shape State is coated circuit substrate and is formed insulating barrier, but the most generally preferably with the lamellar laminated material such as adhesive film, prepreg Mode use.The softening point of compositions is preferably 40～150 DEG C from the point of view of the plyability of lamellar laminated material.

[multilayer printed circuit board]

The compositions of the present invention can serve as the composition for insulating layer of multilayer printed circuit board.

The multilayer printed circuit board that can use in the present invention is to enter containing by the compositions of the present invention, lamellar laminated material The multilayer printed circuit board of insulating barrier obtained by row heat cure.

Wherein, the condition of heat cure can be according to the kind of epoxy resin, content etc. when compositions contains epoxy resin Suitably select, such as by being 90～220 DEG C, preferably 160 DEG C～210 DEG C in solidification temperature, hardening time be 10 minutes～ Heat under conditions of 180 minutes, preferably 20～120 minutes and carry out.It addition, 2 stages can be divided into carry out heat cure.

[lamellar laminated material]

The lamellar laminated material used in the present invention is the flaky material before compositions has carried out the solidification that layer is formed.This sheet Shape laminated material can be by well known to a person skilled in the art that method, the most following method are folded as the lamellar with supporter Layer material manufactures, and described method is dissolved composition in above-mentioned organic solvent, will in the case of compositions is the most resinous Monomer polymerization in compositions, and prepare resin varnish, use chill coating machine etc. that this resin varnish is coated supporter On, and then make organic solvent be dried by heating or blowing hot-air etc. and on supporter, form resin composition layer (lamellar lamination Material).It addition, utilize hot melt or solvent method to make resin varnish be soaked in the flake reinforcement base materials such as glass cloth, make it be dried, Lamellar laminated material thus can also be made to become prepreg.Should illustrate also have and claimed by the lamellar laminated material with supporter Situation for adhesive film.

Drying condition is not particularly limited, and is dried, so that the content that organic solvent is in resin composition layer is 10 Below quality %, it is preferably below 5 mass %.Different according to the organic solvent amount in varnish, the boiling point of organic solvent, but such as By being dried about 3～10 minutes at 50～150 DEG C by the varnish of the organic solvent containing 30～60 mass %, resin can be formed Composition layer.

The thickness of the lamellar laminated material (resin composition layer) of gained is not particularly limited, the most preferably 1～150 μm Scope, the scope of more preferably 2～100 μm, and then the scope of preferably 3～70 μm, the model of particularly preferably 5～50 μm Enclose.

For this lamellar laminated material, resin composition layer can be multilamellar, can have in the one side of resin composition layer There is supporter, another side can have protecting film.

[supporter]

As the supporter that can use in the present invention, plastic foil, metal forming can be enumerated.Specifically, as plastic foil, permissible Enumerate the polyester such as polyethylene terephthalate (hereinafter sometimes referred to simply as " PET "), PEN, Merlon, Polyethylene, polypropylene, acrylic acid series, cyclic polyolefin, tri acetyl cellulose, polyether sulfides, polyether-ketone, polyimides Deng.Wherein, preferably polyethylene terephthalate film, PEN film, particularly preferred low price, it is prone to obtain The polyethylene terephthalate film obtained.

Metal forming can enumerate Copper Foil, aluminium foil etc..

From the point of view of versatility, preferably plastic foil, when using plastic foil, in order to improve fissility, it is preferably used The face connected with the layer containing compositions has been carried out the supporter that the demoulding processes.The releasing agent used in processing as the demoulding, As long as the layer containing compositions can be peeled off from supporter, it is not particularly limited, such as silicon system releasing agent, alkyd can be enumerated Resin system releasing agent, vistanex, polyurethane resin, fluororesin etc..Should illustrate, as having carried out the support that the demoulding processes Body, it is possible to use the commercially available plastic foil with release layer, as preferred supporter, can enumerate and such as have with alkyd tree Fat system releasing agent is the PET film of release layer of main constituent, i.e. PET501010, SK-1, AL-5, AL-7 (リ Application テ ッ Network (strain) system) Deng.It addition, plastic foil can implement delustring process or sided corona treatment, it is also possible to form release layer in this place on reason face.The opposing party Face, metal forming can also be removed by etching solution, or can not also remove and this metal forming be utilized as conductor layer.

The thickness of supporter is not particularly limited, but the scope of preferably 0.5～150 μm, more preferably 20～50 μm Scope, and then the scope of preferably 25～45 μm.

The protecting film that can use in the present invention can be attached to the purposes such as the layer containing compositions for preventing dust etc. And arrange.As this protecting film, it is possible to use the plastic foil as supporter.Additionally protecting film enforcement delustring can be processed, The surfaces such as sided corona treatment process, it is also possible to implement the demoulding similar to the above and process.The thickness of protecting film is preferably 3～30 μm, More preferably 5～20 μm.

[employing the multilayer printed circuit board of lamellar laminated material]

Then, an example of the method using lamellar laminated material fabricated as described above to manufacture multilayer printed circuit board is carried out Explanation.

First, lamellar laminated material vacuum laminator is laminated (stacking) in the one or two sides of circuit substrate.As For the substrate of circuit substrate, can enumerate such as: glass epoxy substrate, metal basal board, polyester substrate, polyimide substrate, BT Resin substrate, thermohardening type polyphenylene oxide substrate etc..Should illustrate, circuit substrate refers to the one side at substrate as described above herein Or two sides is formed with the substrate of the conductor layer (circuit) through pattern processing.Additionally, form at conductor layer and insulating barrier alternative stacked Multilayer printed circuit board in, the outermost one or two sides of this multilayer printed circuit board be formed through pattern processing conductor Layer (circuit) person be also contained in circuit substrate described herein.Should illustrate, Darkening process, copper erosion can be passed through in conductor layer surface Carve to wait and implement roughening process in advance.

In above-mentioned lamination, when lamellar laminated material has protecting film, after this protecting film is removed, as required by lamellar Laminated material and circuit substrate preheating, lamellar laminated material is pressurizeed and heated is laminated to circuit substrate.For this The lamellar laminated material of invention, applicable use utilizes the method that vacuum layer platen press is under reduced pressure laminated on circuit substrate.Lamination Condition be not particularly limited, the most preferably air pressure 20mmHg (26.7hPa) reduce pressure about 10～120 seconds below, then Crimping temperature (laminating temperature) be preferably set to 70～140 DEG C, crimping pressure (lamination pressure) be preferably set to 0.1～1.5MPa, more Preferably 0.5～1.2MPa, crimping time (lamination times) is laminated under conditions of being preferably set to 5～180 seconds.It addition, lamination Method can be batch (-type), it is also possible to be the use of the continuous way of roller.Vacuum lamination can use commercially available vacuum laminator Carry out.As commercially available vacuum laminator, such as ニ チ go モ ト Application (strain) vacuum attaching machine processed, (strain) name can be enumerated Mechanism makees made vacuum pressure type laminating machine, (strain) Hitachi イ Application ダ ス ト リ イ ズ roll-type dry type coating machine, Hitachi エ ア イ シ (strain) vacuum laminator processed etc..

It is then cooled to after near room temperature (25 DEG C), then peel off, by resin combination heat cure when peeling off supporter And form solidfied material, thus can form insulating barrier on circuit substrate.The condition of heat cure can be according in resin combination The kind of resinous principle, content etc. suitably select, such as, make solidification temperature be 100～220 DEG C, preferably 160 DEG C～210 DEG C, consolidate The change time is to heat for 20 minutes～180 minutes, preferably 30～120 minutes, thus carries out heat cure.Alternatively, it is also possible to point It is 2 stages to carry out heat cure.After forming insulating barrier, in the case of not peeling off supporter, the most also Can peel off.

Alternatively, it is also possible to use vacuum pressed machine that lamellar laminated material is laminated in the one or both sides of circuit substrate.? The lamination process carrying out heating and pressurize under decompression can use common vacuum hotpressing machine to carry out.Such as can be by from supporter The metallic plate pressurizations such as heated SUS plate are carried out by side.As pressurized conditions, preferably at 70～250 DEG C, preferably 100～230 At a temperature of DEG C, make vacuum be usually under the decompression of below 0.01MPa, preferred below 0.001MPa, moulding pressure be 0.5～ The scope of 4MPa, pressing time are to carry out under conditions of 30～150 minutes.Heating and pressurization also can be carried out within a stage, But from the point of view of controlling the oozing out of resin, condition is preferably divided into more than two stages to be carried out.Such as, the first stage Pressurization preferably temperature be 70～150 DEG C, moulding pressure be 0.1～1.5MPa scope under conditions of carry out, second-order The pressurization of section preferably temperature be 150～200 DEG C, pressure be 0.5～4MPa scope under conditions of carry out.Each stage time Between preferably carry out 20～120 minutes.By so resin composition layer being carried out heat cure, can be formed on circuit substrate Insulating barrier.As commercially available vacuum hotpressing machine, such as MNPC-V-750-5-200 ((strain) name mechanism is made made), VH1-can be enumerated 1603 (Beichuan essence machine (strain) systems) etc..

Then, the insulating barrier being formed on circuit substrate is carried out perforate processing, through hole (via hole), open-work can be formed (through hole).Perforate processing such as can pass through the known method such as drill bit, laser instrument, plasma, according further to needing These Combination of Methods are carried out, but the perforate processing of the employing laser instrument such as carbon dioxide gas laser, YAG laser is Most conventional methods.When not peeling off supporter before perforate processing, peel off at this moment.

Then, surface of insulating layer is carried out above-mentioned roughening and processes, and then utilize dry type plating or the wet type plating can be Conductor layer is formed on insulating barrier.As dry type plating, it is possible to use be deposited with, sputter, the known method such as ion plating.As wet Formula plating, can enumerate the method that non-electrolytic plating and electrolysis plating combination are formed conductor layer；Being formed with conductor layer is phase The resist pattern of an inverse pattern, merely with the method etc. of electroless plating conformal one-tenth conductor layer.The method formed as pattern afterwards, Can use and such as well known to a person skilled in the art and subtract each other (subtractive) method, semi-additive process etc., by repeatedly going up State a series of operation, be laminated with while multistage can be formed the multilayer printed circuit board of stack layer.In the present invention, due to for low Roughness, high stripping, therefore can be suitable as the stack layer of multilayer printed circuit board.

Here, the dielectric dissipation factor (ASTM of the solidfied material formed by the compositions of the present invention of insulating barrier is become D2520) utilizing Resonant-cavity Method, measure under conditions of measuring frequency 5.8GHz, measuring temperature 23 DEG C, this dielectric dissipation factor is Less than 0.006, preferably less than 0.0055, more preferably 0.005 the following is suitable.Thus, consume power loss to tail off.

Flat with 25～150 DEG C of the coefficient of linear thermal expansion (JIS K7197) of the solidfied material formed by the compositions of the present invention Equal coefficient of linear thermal expansion measures, preferably less than 40ppm/ DEG C, more preferably less than 38ppm/ DEG C, more preferably 36ppm/ Below DEG C.Lower limit is not particularly limited, generally more than 4ppm/ DEG C.Thus, it is possible to prevent insulating barrier and conductor layer (distribution) Deformation, obtain reliability much higher layer printed substrate.

The glass transition temperature (JIS K7121) of the solidfied material formed by the compositions of the present invention utilizes tensile load method Being measured under conditions of load 200mN, programming rate 2 DEG C/min, suitably this glass transition temperature is 170 DEG C Above, preferably more than 175 DEG C, more preferably more than 180 DEG C, more than 190 DEG C, more than 200 DEG C.Thus, available thermostability is high Substrate.

[semiconductor device]

The multilayer printed circuit board manufactured as described above by use, can manufacture semiconductor device.Can be by the present invention The conduction position of the multilayer printed circuit board used is installed semiconductor chip and is manufactured semiconductor device." conduction position " refers to " in multilayer printed circuit board conduction the signal of telecommunication position ", this position can be surface can also be the position being embedded.This Outward, as long as turning on, can be a part for conductor layer, it is also possible to be the current-carrying part of adapter etc. beyond it." partly lead Body chip " as long as component with quasiconductor as material, it is not particularly limited.

As long as the installation method of semiconductor chip when manufacturing the semiconductor device of the present invention makes semiconductor chip effectively send out Wave function, be not particularly limited, specifically can enumerate: lead-in wire engage installation method, flip-chip installation method, utilize built-in non- The installation method of buckle layer (バ Le プ な PVC Le De ア ッ プ, BBUL), utilize the installation of anisotropic conductive film (ACF) Method, utilize the installation method etc. of non-conductive film (NCF).

Embodiment

＜ assay method, evaluation methodology ＞

The making ＞ of ＜ solidfied material

Utilize chill coating machine, the resin varnish of gained in embodiment and comparative example is uniformly coated on and has carried out demoulding process PET film (リ Application テ ッ Network (strain) system, " PET501010 ", thickness 50 μm) on so that the thickness of dried resin composition layer It is 40 μm, is dried 5 minutes at 80～100 DEG C (average 90 DEG C).Then, under nitrogen atmosphere, at the heat that 200 DEG C carry out 90 minutes Reason, peels off from supporter, thus obtains solidfied material film (thickness 40 μm).

Mensuration ＞ of ＜ dielectric dissipation factor

By solidfied material film obtained above (thickness 40 μm) cut growth 80mm, wide 2mm, formed and evaluate sample.For this evaluation Sample, uses Agilent Technologies (Agilent Technologies) company limited HP8362B device, utilizes Resonant-cavity Method (JIS C2565) measures dielectric dissipation factor under conditions of measuring frequency 5.8GHz, measuring temperature 23 DEG C.For 2 tests Sheet is measured, and calculates meansigma methods.

Mensuration ＞ of ＜ coefficient of linear thermal expansion

Solidfied material film obtained above (thickness 40 μm) is cut into width about 5mm, the test film of length about 15mm, uses heat engine Tool analytical equipment Thermo Plus TMA8310 ((strain) リ ガ Network system), utilizes tensile load method (JIS K7197) to carry out heat engine Tool is analyzed.After test film is assemblied in said apparatus, utilizes load 1g, programming rate 5 DEG C/min, be warming up to 250 from 30 DEG C DEG C condition determination METHOD FOR CONTINUOUS DETERMINATION 2 times.Calculate in the mensuration of the 2nd time from the average coefficient of linear thermal expansion of 25 DEG C to 150 DEG C (ppm/℃)。

Coefficient of linear thermal expansion is that the situation of less than 40ppm/ DEG C is designated as zero, the situation more than 40ppm/ DEG C is designated as ×.

Mensuration ＞ of ＜ glass transition temperature

Solidfied material film is cut into width about 5mm, the test film of length about 15mm, uses Measurement of Dynamic Viscoelasticity device (EXSTAR6000 (SII Na ノ テ Network ノ ロ ジ (strain)), carries out thermo-mechanical analysis by tensile load method.Test film is assembled After on said apparatus, load 200mN, programming rate 2 DEG C/min condition determination under METHOD FOR CONTINUOUS DETERMINATION 2 times.Surveyed by the 2nd time The point of the slope variation of fixed change in size signal calculates glass transition temperature (DEG C).

Mensuration ＞ of the pull-off strength (peel strength) of ＜ plated conductor layer

(making of adhesive film)

Utilize chill coating machine that the resin varnish obtained in embodiment and comparative example is uniformly coated to JX day ore deposit day stone On Metal mining (strain) Copper Foil processed (JXUT-III, thickness 2um, with carrier copper foil, Ra=250nm), so that dried tree The thickness of oil/fat composition layer is 40 μm, is dried 5 minutes at 80～100 DEG C (average 90 DEG C).

(base treatment of internal layer circuit substrate)

Defining glass cloth base material epoxy resin two sides copper foil covered lamination (thickness 18 μm of Copper Foil, the substrate of internal layer circuit Thickness 0.3mm, SUNX (strain) R5715ES processed) two sides carry out 1 μm etching, to copper table by メ ッ Network (strain) CZ8100 processed Face is roughened.

(lamination of adhesive film)

Use intermittent vacuum pressure level press MVLP-500 (name machine (strain) trade name processed) that above-mentioned adhesive film is laminated to internal layer The two sides of circuit substrate.Lamination is by being carried out as follows: reducing pressure 30 seconds and making air pressure is below 13hPa, then with 100 DEG C, pressure 0.74MPa crimps 30 seconds.

(solidification of resin combination)

For the adhesive film being laminated, with 200 DEG C, the condition of cure of 60 minutes resin composition formed insulating barrier, Then carrier copper foil is peeled off from adhesive film.

(copper plating treatment)

In order to form circuit at surface of insulating layer, carry out copper sulfate plating, form conductor layer with the thickness of 25 μm.

(mensuration of the pull-off strength (peel strength) of plated conductor layer)

The conductor layer of circuit substrate cuts width 10mm, the otch of length 100mm, by this one end strip off, by fixture (strain formula Commercial firm テ ィ エ ス イ, オ ト U system type testing machine AC-50CSL) clamp, measure at room temperature with 50mm/ minute Speed vertically peels the load (kgf/cm) during 35mm.

Be designated as when dhering strength is less than 0.30kgf/cm ×, dhering strength is that 0.30kgf/cm is less than 0.40kgf/ Being designated as △ during cm, dhering strength is to be designated as zero during more than 0.40kgf/cm.

(the plating pull-off strength (mensuration of peel strength) after resistance to environmental test (HAST)

For the circuit substrate carrying out copper plating treatment, use height accelerated life test device PM422 (this chemical conversion of nanmu (strain) System), 130 DEG C, implement the acceleration environment test of 100 hours under conditions of 85%RH after, the conductor layer of this circuit substrate is cut Open the otch of width 10mm, length 100mm, by this one end strip off, with fixture (Co., Ltd. テ ィ エ ス イ, オ ト U system type testing machine AC-50CSL) clamp, measure when vertically peeling 35mm with the speed of 50mm/ minute at room temperature Load (kgf/cm).

Be designated as when dhering strength is less than 0.30kgf/cm ×, dhering strength is that 0.30kgf/cm is less than 0.40kgf/ Being designated as △ during cm, dhering strength is to be designated as zero during more than 0.40kgf/cm.

In an embodiment, " part " expression " mass parts " of expression amount.

(embodiment 1)

By toluene solution (Rhizoma Sparganii gas chemistry (strain) system " OPE-2St (number-average molecular weight of phenylethene modified polyphenylene oxide resin 1200) " nonvolatile component 64.4wt%) 125 parts, polymerization initiator (Kayaku Akzo (strain) makes " Trigonox 311 ") 1 part, Phosphonate compound (sheet mountain chemistry (strain) system " V-1 " dimethylvinylphosphonate, molecular weight 130.09g/mol) 5 parts, spherical (mean diameter 0.5 μm, (strain) Admatechs system " SOC4 " (processing through aminophenylsilane) 130 parts exist silicon dioxide MEK15 part mixes, utilizes high speed rotating mixer to be uniformly dispersed, make resin varnish.

(embodiment 2)

Except to make the toluene solution of phenylethene modified polyphenylene oxide resin be 117 parts, in addition to phosphonate compound is 10 parts, other with Embodiment 1 similarly makes resin varnish.

(embodiment 3)

Except to make the toluene solution of phenylethene modified polyphenylene oxide resin be 86 parts, in addition to phosphonate compound is 30 parts, other with Embodiment 1 similarly makes resin varnish.

(embodiment 4)

By toluene solution (Rhizoma Sparganii gas chemistry (strain) system " OPE-2St (number-average molecular weight of phenylethene modified polyphenylene oxide resin 1200) " nonvolatile component 64.4wt%) 102 parts, polymerization initiator (Kayaku Akzo (strain) makes " Trigonox 311 ") 1 part, Phosphonate compound (sheet mountain chemistry (strain) system " V-2 " diethyl vinylphosphonate, molecular weight 164.14g/mol) 20 parts, ball (mean diameter 0.5 μm, (strain) Admatechs system " SOC4 " (processing through aminophenylsilane) 130 parts exist shape silicon dioxide MEK15 part mixes, utilizes high speed rotating mixer to be uniformly dispersed, make resin varnish.

(embodiment 5)

By toluene solution (Rhizoma Sparganii gas chemistry (strain) system " OPE-2St (number-average molecular weight of phenylethene modified polyphenylene oxide resin 1200) " nonvolatile component 64.4wt%) 102 parts, polymerization initiator (Kayaku Akzo (strain) makes " Trigonox 311 ") 1 part, Phosphonate compound (sheet mountain chemistry (strain) system " V-3 " diphenylacetylene phosphonate ester, molecular weight 260.22g/mol) 20 parts, ball (mean diameter 0.5 μm, (strain) Admatechs system " SOC4 " (processing through aminophenylsilane) 130 parts exist shape silicon dioxide MEK15 part mixes, utilizes high speed rotating mixer to be uniformly dispersed, make resin varnish.

(embodiment 6)

By toluene solution (Rhizoma Sparganii gas chemistry (strain) system " OPE-2St (number-average molecular weight of phenylethene modified polyphenylene oxide resin 1200) " nonvolatile component 64.4wt%) 102 parts, di-cresols diallyl ether resin (Mitsubishi Chemical's (strain) system " YL7776 (number-average molecular weight 331) ") 5 parts, the esterification of polymerization initiator (Kayaku Akzo (strain) makes " Trigonox 311 ") 1 part, phosphonic acids Compound (sheet mountain chemistry (strain) system " V-1 " dimethylvinylphosphonate, molecular weight 130.09g/mol) 15 parts, spherical titanium dioxide (mean diameter 0.5 μm, (strain) Admatechs system " SOC4 " (processing through aminophenylsilane) 130 parts are in MEK15 part for silicon Mixing, utilizes high speed rotating mixer to be uniformly dispersed, and makes resin varnish.

(embodiment 7)

By toluene solution (Rhizoma Sparganii gas chemistry (strain) system " OPE-2St (number-average molecular weight of phenylethene modified polyphenylene oxide resin 1200) " nonvolatile component 64.4wt%) 102 parts, dihydroxymethyl-tristane diacrylate (common prosperity society chemistry (strain) system, " DCP-A ") 5 parts, polymerization initiator (Kayaku Akzo (strain) makes " Trigonox 311 ") 1 part, phosphonate compound (sheet mountain Chemistry (strain) system " V-1 " dimethylvinylphosphonate, molecular weight 130.09g/mol) 15 parts, preparing spherical SiO 2 (average particle Footpath 0.5 μm, (strain) Admatechs system " SOC4 " (processing through aminophenylsilane) 130 parts mix in MEK15 part, utilize High speed rotating mixer is uniformly dispersed, and makes resin varnish.

(embodiment 8)

By toluene solution (Rhizoma Sparganii gas chemistry (strain) system " OPE-2St (number-average molecular weight of phenylethene modified polyphenylene oxide resin 1200) " nonvolatile component 64.4wt%) 102 parts, dihydroxymethyl-tristane dimethylacrylate (common prosperity society chemistry (strain) System, DCP-M ") 5 parts, polymerization initiator (Kayaku Akzo (strain) makes " Trigonox 311 ") 1 part, phosphonate compound (sheet Mountain chemistry (strain) system " V-1 " dimethylvinylphosphonate, molecular weight 130.09g/mol) 15 parts, preparing spherical SiO 2 (average Particle diameter 0.5 μm, (strain) Admatechs system " SOC4 " (processing through aminophenylsilane) 130 parts mix in MEK15 part, profit It is uniformly dispersed with high speed rotating mixer, makes resin varnish.

(embodiment 9)

By toluene solution (Rhizoma Sparganii gas chemistry (strain) system " OPE-2St (number-average molecular weight of phenylethene modified polyphenylene oxide resin 1200) " nonvolatile component 64.4wt%) 102 parts, acrylic oligomers (contest road chemical industry (strain) system, " サ イ Network ロ マ P Z230AA " nonvolatile component 53wt%) 6 parts, biphenyl aralkyl-type epoxy resin (Japan's chemical medicine (strain) system " NC3000L ", Epoxide equivalent about 288) 2 parts, polymerization initiator (Kayaku Akzo (strain) makes " Trigonox 311 ") 1 part, phosphonate compound (sheet mountain chemistry (strain) system " V-1 " dimethylvinylphosphonate, molecular weight 130.09g/mol) 15 parts, preparing spherical SiO 2 are (flat All particle diameter 0.5 μm, (strain) Admatechs systems " SOC4 " (processing through aminophenylsilane) 130 parts mix in MEK15 part, Utilize high speed rotating mixer to be uniformly dispersed, make resin varnish.

(embodiment 10)

By toluene solution (Rhizoma Sparganii gas chemistry (strain) system " OPE-2St (number-average molecular weight of phenylethene modified polyphenylene oxide resin 1200) " nonvolatile component 64.4wt%) 60 parts, acrylic oligomers containing carboxylic acid group (contest road chemical industry (strain) system, " サ イ Network ロ マ P Z251 " nonvolatile component 45wt%) 20 parts, acrylic oligomers (contest road containing carboxylic acid group Learn industry (strain) system, " サ イ Network ロ マ P Z254F " nonvolatile component 55wt%) 20 parts, fluorination bisphenol A type epoxy resin (three Pedicellus et Pericarpium Trapae chemistry (strain) system " YL7760 ", epoxide equivalent about 243) 12 parts, (Kayaku Akzo (strain) makes " Trigonox to polymerization initiator 311 ") 1 part, phosphonate compound (sheet mountain chemistry (strain) system " V-1 " dimethylvinylphosphonate, molecular weight 130.09g/ Mol) 15 parts, (mean diameter 0.5 μm, (strain) Admatechs system " SOC4 " are (at aminophenylsilane for preparing spherical SiO 2 Reason) 130 parts mix in MEK15 part, utilize high speed rotating mixer to be uniformly dispersed, make resin varnish.

(embodiment 11)

By toluene solution (Rhizoma Sparganii gas chemistry (strain) system " OPE-2St (number-average molecular weight of phenylethene modified polyphenylene oxide resin 1200) " nonvolatile component 64.4wt%) 102 parts, polymerization initiator (Kayaku Akzo (strain) makes " Trigonox 311 ") 1 part, Phosphonate compound (sheet mountain chemistry (strain) system " V-1 " dimethylvinylphosphonate, molecular weight 130.09g/mol) 20 parts, ball Shape silicon dioxide (mean diameter 0.5 μm, (strain) Admatechs system " SOC4 " (processing through aminophenylsilane) 172 parts, connection Benzene aralkyl-type epoxy resin (Japan's chemical medicine (strain) system " NC3000L ", epoxide equivalent about 288) 15 parts, active ester firming agent (DIC (strain) system " HPC8000L-65M ", the MEK solution of nonvolatile component 65 mass % of active group equivalent about 220) 20 parts, solid Change accelerator (4-dimethylaminopyridine (DMAP), the MEK solution of nonvolatile component 5 mass %) 3 parts to mix in MEK15 part, Utilize high speed rotating mixer to be uniformly dispersed, make resin varnish.

(embodiment 12)

By toluene solution (Rhizoma Sparganii gas chemistry (strain) system " OPE-2St (number-average molecular weight of phenylethene modified polyphenylene oxide resin 1200) " nonvolatile component 64.4wt%) 102 parts, polymerization initiator (Kayaku Akzo (strain) makes " Trigonox 311 ") 1 part, Phosphonate compound (sheet mountain chemistry (strain) system " V-1 " dimethylvinylphosphonate, molecular weight 130.09g/mol) 20 parts, ball Shape silicon dioxide (mean diameter 0.5 μm, (strain) Admatechs system " SOC4 " (processing through aminophenylsilane) 175 parts, naphthalene Type epoxy resin (DIC (strain) makes " EXA4032SS ") 15 parts, 15 parts of cyanic acid ester type firming agent (Lonza (strain) makes " PT30 "), solid Change accelerator (4-dimethylaminopyridine (DMAP), the MEK solution of nonvolatile component 5 mass %) 2 parts to mix in MEK15 part, Utilize high speed rotating mixer to be uniformly dispersed, make resin varnish.

(comparative example 1)

By toluene solution (Rhizoma Sparganii gas chemistry (strain) system " OPE-2St (number-average molecular weight of phenylethene modified polyphenylene oxide resin 1200) " nonvolatile component 64.4wt%) 133 parts, polymerization initiator (Kayaku Akzo (strain) makes " Trigonox 311 ") 1 part, (mean diameter 0.5 μm, (strain) Admatechs system " SOC4 " (processing through aminophenylsilane) 130 parts exist preparing spherical SiO 2 MEK15 part mixes, utilizes high speed rotating mixer to be uniformly dispersed, make resin varnish.

(comparative example 2)

Utilize high speed rotating mixer by toluene solution (Rhizoma Sparganii gas chemistry (strain) system of phenylethene modified polyphenylene oxide resin " OPE-2St (number-average molecular weight 1200) " nonvolatile component 64.4wt%) 117 parts, ring-type phosphorus compound (big chemistry (strain) system " SPS-100 ") 10 parts, polymerization initiator (Kayaku Akzo (strain) makes " Trigonox 311 ") 1 part, preparing spherical SiO 2 (flat All particle diameter 0.5 μm, (strain) Admatechs systems " SOC4 " (processing through aminophenylsilane) 130 parts are uniformly dispersed, and make tree Fat varnish.Should illustrate, the structural formula of SPS-100 is as shown below.

(comparative example 3)

By toluene solution (Rhizoma Sparganii gas chemistry (strain) system " OPE-2St (number-average molecular weight of phenylethene modified polyphenylene oxide resin 1200) " nonvolatile component 64.4wt%) 117 parts, phosphonate compound (sheet mountain chemistry (strain) system " V-5 " 9,10-dihydro-9-oxy Miscellaneous-10-phospho hetero phenanthrene-10-oxide, molecular weight 242.21g/mol)) nonvolatile component 50% MEK solution 20 parts, polymerization draw Send out agent (Kayaku Akzo (strain) makes " Trigonox 311 ") 1 part, preparing spherical SiO 2 (mean diameter 0.5 μm, (strain) Admatechs system " SOC4 " (processing through aminophenylsilane) 130 parts mixes in MEK15 part, utilizes high speed rotating to mix Machine is uniformly dispersed, and makes resin varnish.Should illustrate, " V-5 " 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Structural formula as shown below.

[table 1]

。

Claims (22)

1. compositions, it contains:

(1) there is the phosphonate compound of the ethylenic unsaturated bond of more than 1 in intramolecular；

(2) in intramolecular, there is the ethylenic unsaturated bond of more than 2 and the aromatic hydrocarbon of more than 1 or the freedom of ester ring type hydrocarbon Base polymerizable compound；And

(3) inorganic filling material,

Wherein, (1) composition and (2) composition are different compounds.

Compositions the most according to claim 1, wherein, (1) composition is represented by following formula (I),

In formula (I), R₄₁And R₄₂Being alkyl or aryl independently of one another, X is represented by following formula (X-1) or following formula (X-2),

In formula (X-1) and (X-2), R₃₅～R₄₀It is hydrogen, alkyl or aryl independently of one another.

Compositions the most according to claim 2, wherein, in formula (I), R₄₁And R₄₂Be independently of one another carbon number be 1 ～the alkyl or phenyl of 3.

4., according to the compositions described in Claims 2 or 3, wherein, in formula (I), X is represented by formula (X-1), in formula (X-1), R₃₅～R₃₇For hydrogen.

5. according to the compositions according to any one of Claims 1 to 4, wherein, the non-volatile of the compositions of (3) composition will be removed When becoming to be divided into 100 mass %, (1) composition is 3～45 mass %.

6. according to the compositions according to any one of Claims 1 to 5, wherein, the nonvolatile component of compositions is set to 100 matter During amount %, (1) composition adds up to 1～70 mass % with (2) composition.

7. according to the compositions according to any one of claim 1～6, wherein, the inorganic filling material of (3) composition is titanium dioxide Silicon.

8. according to the compositions according to any one of claim 1～7, wherein, by the inorganic filling material silane of (3) composition Coupling agent carries out surface process, described silane coupler have selected from acryloyl group, methylacryloyl, styryl, amino, The functional group of more than a kind in epoxy radicals, vinyl.

9. according to the compositions according to any one of claim 1～7, wherein, by the inorganic filling material amino of (3) composition Silane series coupling agent, vinyl silanes system coupling agent or styryl silane series coupling agent carry out surface process.

10., according to the compositions according to any one of claim 1～9, wherein, the nonvolatile component of compositions is set to 100 During quality %, (3) composition is 30～80 mass %.

11. according to the compositions according to any one of claim 1～10, and wherein, (2) composition is oneself shown in following formula (II) By base polymerizable compound,

In formula (II), R₁～R₆Being hydrogen or alkyl that carbon number is 1～4 independently of one another, A is containing aromatic hydrocarbon or fat The divalent group of ring type hydrocarbon.

12. compositions according to claim 11, wherein, in formula (II), A is by following formula (A-1), (A-2), (A-3) Or (A-4) represents,

In formula (A-1), (A-2), B is the divalent group containing aromatic hydrocarbon or ester ring type hydrocarbon, in formula (A-1), and E₁And E₂Respectively From being alkylidene or alkylidene epoxide independently,

In formula (A-3), D is following formula (D-1),

In formula (D-1), R₇～R₁₄Be independently of one another hydrogen, carbon number be the alkyl or phenyl of less than 6, a, b are at least one Person is not the integer of 0～the 100 of 0, and B is the divalent group containing aromatic hydrocarbon or ester ring type hydrocarbon,

In formula (A-4), B is the divalent group containing aromatic hydrocarbon or ester ring type hydrocarbon, E₄And E₅Be independently of one another alkylidene or Alkylidene epoxide.

13. compositionss according to claim 12, wherein, in formula (A-1), (A-2), (D-1) and (A-4), B is by following Any one of formula (B-1)～(B-6) represents,

In formula (B-1)～(B-5), R₁₅～R₃₄And R₄₃～R₅₀Be independently of one another hydrogen, carbon number be less than 6 alkyl or Phenyl, in formula (B-3), E is alkylidene or alkylidene epoxide.

14. according to the compositions according to any one of claim 1～10, and wherein, (2) composition is containing at least 2 formulas (V) institute Show construction unit and by free-radical polymerised compound obtained by construction unit atactic polymerization shown in formula (III)～(V),

In formula (III)～(V), X is hydrogen or carbon number is the alkyl of less than 6, in formula (IV), and R₅₁For alkyl or hydroxyl alkane Base, in formula (V), R₅₂For containing ethylenic unsaturated bond and aromatic hydrocarbon or the group of ester ring type hydrocarbon.

15. compositionss according to claim 14, wherein, formula (V) is represented by formula (VI),

。

The composition for insulating layer of 16. multilayer printed circuit boards, it is characterised in that containing institute any one of claim 1～15 The compositions stated.

17. lamellar laminated materials, it is characterised in that containing the compositions according to any one of claim 1～16.

18. solidfied materials, it is the compositions according to any one of claim 1～16 or the lamellar described in claim 17 to be folded Solidfied material obtained by layer material heat cure, wherein, the dielectric dissipation factor of this solidfied material is less than 0.005.

19. solidfied materials, it is the compositions according to any one of claim 1～16 or the lamellar described in claim 17 to be folded Solidfied material obtained by layer material heat cure, wherein, the coefficient of linear thermal expansion of this solidfied material is less than 40ppm/ DEG C.

20. solidfied materials, it is the compositions according to any one of claim 1～16 or the lamellar described in claim 17 to be folded Solidfied material obtained by layer material heat cure, wherein, the glass transition temperature of this solidfied material is more than 170 DEG C.

21. multilayer printed circuit boards, it is characterised in that containing by the compositions according to any one of claim 1～16 or power Profit requires insulating barrier obtained by the lamellar laminated material heat cure described in 17.

22. semiconductor devices, it is characterised in that containing the multilayer printed circuit board described in claim 21.