阅读说明：本技术 树脂组合物、预浸料、覆金属箔层叠板、树脂片及印刷电路板 (Resin combination, prepreg, clad with metal foil plywood, resin sheet and printed circuit board ) 是由 古贺将太 中住宜洋 高野健太郎 于 2018-04-09 设计创作，主要内容包括：一种树脂组合物,其含有通式(1)所示的环氧树脂(A)及氰酸酯化合物(B)。<Image he="203" wi="700" file="DDA0002226675070000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(A kind of resin combination contains epoxy resin (A) shown in general formula (1) and cyanate esters (B).)

1. a kind of resin combination, containing epoxy resin (A) shown in the following general formula (1) and cyanate esters (B),

In formula, R each independently represents the alkyl or hydrogen atom of carbon number 1~3.

2. resin combination according to claim 1, wherein content of the epoxy resin (A) in resin combination It is 1~90 mass parts relative to 100 mass parts of resin solid content.

3. resin combination according to claim 1 or 2, wherein also containing selected from by addition to the epoxy resin (A) Epoxy resin, maleimide compound, phenolic resin, oxetane resin, benzoxazine compound and have can gather One or more of the group of the compound composition of the unsaturated group of conjunction.

4. resin combination described in any one of claim 1 to 3, wherein cyanate esters (B) are selected from by benzene Phenol phenolic varnish type cyanate esters, naphthols aralkyl-type cyanate esters composition, biphenyl aralkyl-type cyanate esters, Asia Naphthalene ether type cyanate esters, xylene resin type cyanate esters and adamantane framework type cyanate esters and contain One or more of the group being made of the cyanate esters of allyl or acrylic.

5. resin combination according to claim 4, wherein cyanate esters (B) include naphthols aralkyl-type cyanic acid Ester compounds.

6. resin combination according to any one of claims 1 to 5, wherein also contain packing material (C).

7. resin combination according to claim 6, wherein content of the packing material (C) in resin combination It is 50~1600 mass parts relative to 100 mass parts of resin solid content.

8. a kind of prepreg includes substrate and infiltration or is coated on the according to any one of claims 1 to 7 of the substrate Resin combination.

9. a kind of clad with metal foil plywood includes stacking at least 1 or more prepreg according to any one of claims 8 and configuration In the metal foil of the one or two sides of the prepreg.

10. a kind of resin sheet, it includes resin combinations according to any one of claims 1 to 7.

11. a kind of printed circuit board includes insulating layer and is formed in the conductor layer on the surface of the insulating layer, the insulating layer Include resin combination according to any one of claims 1 to 7.

Technical field

The present invention relates to resin combination, prepreg, the clad with metal foil plywood for having used the resin combination, prepreg And resin sheet and use their printed circuit board.

Background technique

In recent years, in electronic equipment, communication equipment, personal computer etc. widely used semiconductor it is highly integrated fine Change increasingly accelerates.Therewith, each characteristic that semiconductor package body plywood used in printed circuit board requires becomes increasingly Strictly.As required characteristic, for example, can enumerate low water absorbable, moisture absorption heat resistance, anti-flammability, low relative dielectric constant, The characteristics such as low-dielectric loss angle tangent, low thermal coefficient of expansion, heat resistance, chemical resistance, high plating peel strength.But So far, these requirements characteristic may not be satisfied.

All the time, the printed circuit board resin excellent as heat resistance, electrical characteristics, it is known to cyanate esters, The resin combination that epoxy resin, bismaleimide compound etc. is applied in combination in cyanate esters in recent years is wide It is general to be used for H.D printed wiring materials such as semiconductor plastic packaging body use etc..In addition, due to multilayer board Miniaturization, densification, a large amount of heat storages are in electronic component, it is desirable that the thermal diffusivity of printed circuit board.In turn, multi-sheet printed Warpage expansion can be led to the problem of in circuit board, therefore low thermal expansion is required to the resin combination of the material as insulating layer Property, high bending modulus.

For example, proposing the characteristics such as adaptation, low water absorbable, moisture absorption heat resistance, insulating reliability in patent document 1 and 2 The excellent resin combination comprising cyanate esters and epoxy resin.

The epoxy resin with specific structure is disclosed in patent document 3, is disclosed to match in the epoxy resin and be mixed up For curing agent phenol resol resins and defined curing catalysts and when winner prepreg, the packet of obtained prepreg Include each excellent including heat resistance and thermal conductivity.In the document, as in the above-mentioned epoxy resin with specific structure Mesosome discloses following formula (4) compound represented.

(in formula, Z each independently represents hydrogen atom, halogen atom, the alkyl of carbon atom number 1~8 or carbon atom number 1~8 Alkoxy.)

Summary of the invention

Problems to be solved by the invention

Such as to propose the characteristics such as adaptation, low water absorbable, moisture absorption heat resistance, insulating reliability in patent document 1 and 2 excellent The different resin combination comprising cyanate esters and epoxy resin, but about thermal conductivity, low thermal linear expansion coefficient and The improvement of bending modulus is also insufficient, therefore it is required that the further improvement of these characteristics.In patent document 3, shown in formula (4) Compound is recorded as intermediate, does not evaluate performance in embodiment.In addition, without research balance in the document Improve thermal conductivity, low thermal linear expansion coefficient and bending modulus well.

Therefore, the object of the present invention is to provide achievable thermal conductivity, low heat expansion and the excellent prints of bending modulus The resin combination of printed circuit board etc. provides the prepreg for having used the resin combination, resin sheet (for example, single layer or stacking Piece), the clad with metal foil plywood and the printed circuit board that have used prepreg etc..

The solution to the problem

The inventors of the present invention have made intensive studies the above problem, as a result, it has been found that, by using containing shown in general formula (1) The resin combination of epoxy resin (A) and cyanate esters (B) can obtain having high thermal conductivity, bending modulus, low-heat swollen The solidfied material of swollen property, to realize the present invention.That is, the present invention is as follows.

[1]

A kind of resin combination contains epoxy resin (A) shown in the following general formula (1) and cyanate esters (B).

(in formula, R each independently represents the alkyl or hydrogen atom of carbon number 1~3.)

[2]

The resin combination according to [1], wherein content of the aforementioned epoxy resins (A) in resin combination is opposite In 100 mass parts of resin solid content be 1~90 mass parts.

[3]

According to resin combination described in [1] or [2], wherein also containing selected from the ring in addition to aforementioned epoxy resins (A) Oxygen resin, maleimide compound, phenolic resin, oxetane resin, benzoxazine compound and with can polymerize One or more of the group of the compound composition of unsaturated group.

[4]

The resin combination according to any one of [1]~[3], wherein cyanate esters (B) are selected from by phenol Phenolic varnish type cyanate esters, naphthols aralkyl-type cyanate esters composition, biphenyl aralkyl-type cyanate esters, sub- naphthalene Base ether type cyanate esters, xylene resin type cyanate esters and adamantane framework type cyanate esters and contain One or more of the group of the cyanate esters of allyl or acrylic composition.

[5]

The resin combination according to [4], wherein cyanate esters (B) are esterified comprising naphthols aralkyl-type cyanic acid Close object.

[6]

The resin combination according to any one of [1]~[5], wherein also contain packing material (C).

[7]

The resin combination according to [6], wherein content of the aforementioned packing material (C) in resin combination is opposite In 100 mass parts of resin solid content be 50~1600 mass parts.

[8]

A kind of prepreg includes tree described in substrate and any one of infiltration or [1]~[7] for being coated on the substrate Oil/fat composition.

[9]

A kind of clad with metal foil plywood includes prepreg described in stacking at least 1 or more [8] and is configured at this The metal foil of the one or two sides of prepreg.

[10]

A kind of resin sheet, it includes the resin combinations described in any one of [1]~[7].

[11]

A kind of printed circuit board includes insulating layer and is formed in the conductor layer on the surface of the insulating layer, aforementioned dielectric Layer includes resin combination described in any one of [1]~[7].

The effect of invention

It can be realized thermal conductivity, low heat expansion and the excellent printed circuit of bending modulus according to the present invention it is possible to provide The resin combination of plate etc. can provide the prepreg for having used the resin combination, resin sheet (for example, single layer or stacking Piece), the clad with metal foil plywood and the printed circuit board that have used prepreg etc..

Specific embodiment

Hereinafter, embodiments of the present invention will be described.It should be noted that the following embodiments and the accompanying drawings is for illustrating Illustration of the invention, the present invention are not limited to the embodiment.

[resin combination]

The resin combination of present embodiment contains epoxy resin (A) and cyanate esters shown in the following general formula (1) (B).Resin combination by making present embodiment contains epoxy resin (A) and cyanate esters (B), so as to realize Thermal conductivity, bending modulus and excellent prepreg, resin sheet, the clad with metal foil plywood of low heat expansion etc., can be realized high property The printed circuit board of energy, industrial practicability are high.

(epoxy resin (A))

(in formula, R each independently represents the alkyl (for example, methyl, ethyl and propyl) or hydrogen atom of carbon number 1~3.)

The manufacturing method of epoxy resin (A) shown in general formula (1) is not particularly limited, such as can be by will be corresponding double Phenol glycidyl obtains.In addition, commercially available substance also can be used in epoxy resin (A) shown in general formula (1), such as can " YSLV-80DE " of Nippon Steel & Sumitomo Metal Corporation is suitably used.Contain epoxy resin shown in general formula (1) (A) resin cured matter has the effect for improving thermal conductivity, low heat expansion and bending modulus.

Content of the epoxy resin (A) in resin combination shown in general formula (1) can be suitable for according to desired characteristic Setting, is not particularly limited, when the resin solid content in resin combination is set as 100 mass parts, preferably 1~90 mass Part.In the case that content is the range of 1~90 mass parts, the resin combination of excellent heat resistance can be obtained.From same viewpoint It sets out, content is more preferably 5~80 mass parts, further preferably 10~70 mass parts.Herein, " the tree in resin combination Rouge solid component " unless otherwise specified, just refer to it is in resin combination, other than solvent and packing material (C) Ingredient, 100 mass parts of resin solid content refer to the ingredient other than solvent and packing material (C) in resin combination Add up to 100 mass parts.

(cyanate esters (B))

Cyanate esters used in present embodiment (B) are as long as having to replace for intramolecular has at least one cyanato The resin of the aromatic moiety of (cyanic acid ester group, Cyanate group), is just not particularly limited.

As cyanate esters (B), for example, general formula (2) compound represented can be enumerated.

(in formula, Ar₁The naphthylene for each independently representing the phenylene optionally with substituent group, optionally there is substituent group Or optionally with the biphenylene of substituent group.Ra is each independently selected from hydrogen atom, optionally with the carbon number 1~6 of substituent group Alkyl, the aryl of the optionally carbon number 6~12 with substituent group, the alkoxy of the optionally carbon number 1~4 with substituent group, carbon number 1~ 6 alkyl optionally has the aralkyl of substituent group or the alkyl and carbon of carbon number 1~6 made of being bonded with the aryl of carbon number 6~12 Optionally with any one of the alkylaryl of substituent group made of the aryl bonding of number 6~12.P is indicated and Ar₁The cyanogen of bonding The quantity of acyl group is 1~3 integer.Q is indicated and Ar₁The quantity of the Ra of bonding, Ar₁When to be 4-p when phenylene, being naphthylene It is 8-p when being 6-p, being biphenylene.T indicates averaged repeating numbers, is 0~50 integer, can be the mixed of t different compounds Close object.X is each independently selected from divalent organic group (hydrogen atom can be substituted by hetero atom), the nitrogen number 1 of singly-bound, carbon number 1~50 ~10 divalent organic group (- N-R-N- etc.), carbonyl (- CO-), carboxyl (- C (=O) O-), carbonylic dioxo compound base (- OC (= O) O-), sulfonyl (- SO₂) or divalent sulphur atom or any one of the oxygen atom of divalent.)

Alkyl in the Ra of general formula (2) can have any one of chain structure and cyclic structure (naphthenic base etc.).

In addition, the hydrogen atom in aryl in alkyl and Ra in general formula (2) can be by the halogen atoms such as fluorine, chlorine, methoxy The alkoxies such as base, phenoxy group, cyano etc. replace.

As the concrete example of aforesaid alkyl, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tertiary fourth can be enumerated Base, n-pentyl, 1- ethyl propyl, 2,2- dimethyl propyl, cyclopenta, hexyl, cyclohexyl, trifluoromethyl etc..

As the concrete example of aforesaid aryl, phenyl, xylyl, mesitylene base, naphthalene, phenoxy group benzene can be enumerated Base, ethylphenyl, o-, m- or p- fluorophenyl, dichlorophenyl, dicyano phenyl, trifluorophenyl, methoxyphenyl, it is o-, M- or p- tolyl etc..And then it is used as alkoxy, methoxyl group, ethyoxyl, propoxyl group, isopropoxy, positive fourth oxygen can be enumerated Base, isobutoxy, tert-butoxy etc..

As the concrete example of the divalent organic group in the X of general formula (2), can enumerate methylene, ethylidene, trimethylene, Cyclopentylene, cyclohexylidene, trimethylcyclohexylene, biphenyl methylene, dimethylmethylene-phenylene-dimethylated methylene Base, fluorenes diyl (fluorenediyl), phthalide diyl (Off タ リ De ジ イ Le base) etc..Hydrogen atom in the divalent organic group can To be replaced by the alkoxies such as the halogen atoms such as fluorine, chlorine, methoxyl group, phenoxy group, cyano etc..

As the divalent organic group of the nitrogen number 1~10 in the X of general formula (2), can enumerate imino group (imino group), It is polyimide-based etc..

In addition, structure shown in the following general formula (3) or the following general formula (4) can be enumerated as the X in general formula (2).

(in formula, Ar₂Selected from any one of phenylene, naphthylene and biphenylene.Rb, Rc, Rf, Rg are each independently Selected from hydrogen atom, the alkyl of carbon number 1~6, the aryl of carbon number 6~12, trifluoromethyl and replace the aryl for having at least one phenolic hydroxyl group Any one of.Rd, Re are each independently selected from hydrogen atom, the alkyl of carbon number 1~6, the aryl of carbon number 6~12, carbon number 1~4 Alkoxy and any one of hydroxyl.U indicates 0~5 integer, but can be the mixture of u different compounds.)

(in formula, Ar₃Selected from any one of phenylene, naphthylene or biphenylene.Ri, Rj are each independently selected from hydrogen Atom, the alkyl of carbon number 1~6, the aryl of carbon number 6~12, benzyl, the alkoxy of carbon number 1~4, hydroxyl, trifluoromethyl and substitution There is any one of the aryl of at least one cyanato.V indicates 0~5 integer, but can be the mixing of v different compounds Object.)

In turn, as the X in general formula (2), divalent group shown in following formula can be enumerated.

(in formula, z indicates 4~7 integer.Rk each independently represents the alkyl of hydrogen atom or carbon number 1~6.)

Ar as general formula (3)₂And the Ar of general formula (4)₃Concrete example, can enumerate Isosorbide-5-Nitrae-phenylene, 1,3- phenylene, 4,4 '-biphenylenes, 2,4 '-biphenylenes, 2,2 '-biphenylenes, 2,3 '-biphenylenes, 3,3 '-biphenylenes, 3,4 '-Asias Xenyl, 2,6- naphthylene, 1,5- naphthylene, 1,6- naphthylene, 1,8- naphthylene, 1,3- naphthylene, 1,4- naphthylene etc..

Rb~Rg of general formula (3) and alkyl in Ri, Rj of general formula (4) and aryl with recorded in general formula (2) it is same.

As the concrete example of cyanato substituted aromatic compound shown in general formula (2), cyanato benzene, 1- cyanogen can be enumerated Acyl group -2- methylbenzene, 1- cyanato -3- methylbenzene or 1- cyanato -4- methylbenzene, 1- cyanato -2- methoxybenzene, 1- cyanogen Acyl group -3- methoxybenzene or 1- cyanato -4- methoxybenzene, 1- cyanato -2,3- dimethyl benzene, 1- cyanato -2,4- diformazan Base benzene, 1- cyanato -2,5- dimethyl benzene, 1- cyanato -2,6- dimethyl benzene, 1- cyanato -3,4- dimethyl benzene or 1- cyanogen Acyl group -3,5- dimethyl benzene, cyanato ethylo benzene, cyanato butyl benzene, cyanato octyl benzene, cyanato nonyl benzene, 2- (4- cyanogen Aminosulfonylphenyl) -2- phenyl-propane (4- α-cumyl phenol cyanate), 1- cyanato -4- cyclohexyl benzene, 1- cyanato -4- second Alkenyl benzene, 1- cyanato -2- chlorobenzene or 1- cyanato -3- chlorobenzene, 1- cyanato -2,6- dichloro-benzenes, 1- cyanato -2- methyl - 3- chlorobenzene, cyanato nitrobenzene, 1- cyanato -4- nitro -2- ethylo benzene, 1- cyanato -2- methoxyl group -4- allyl benzene (fourth The cyanate of eugenol), methyl (4- cyanatophenyl) sulfide, 1- cyanato -3- trifluoromethylbenzene, 4- cyanato biphenyl, 1- cyanato -2- acetylbenzene or 1- cyanato -4- acetylbenzene, 4- cyanato- benzaldehyde, 4- cyanato methyl benzoate, 4- Cyanato phenol benzoate, 1- cyanato -4- acetyl amino phenyl, 4- cyanato benzophenone, 1- cyanato -2,6- di-t-butyl Benzene, 1,2- -bis-cyanato benzene, 1,3- -bis-cyanato benzene, 1,4- -bis-cyanato benzene, bis- cyanato -2- tert-butyl benzene of 1,4-, 1,4- Two cyanato -2,4- dimethyl benzenes, bis- cyanato -2,3,4- dimethyl benzene of 1,4-, bis- cyanato -2,4,6- trimethyl of 1,3- Benzene, bis- cyanato -5- methylbenzene of 1,3-, 1- cyanato naphthalene or 2- cyanato naphthalene, 1- cyanato 4- methoxynaphthalene, 2- cyanato - 6- methyl naphthalene, 2- cyanato -7- methoxynaphthalene, 2,2 '-two cyanatos -1,1 '-dinaphthalene, 1,3-, 1,4-, 1,5-, 1,6-, 1, The cyanato biphenyl of 7-, 2,3-, 2,6- or 2,7- dicyan acyl-naphthaline, 2,2 '-or 4,4 '-two, 4,4 '-two cyanato octafluorobiphenyls, 2,4 '-or 4,4 '-two cyanato diphenyl methanes, bis- (4- cyanato -3,5- 3,5-dimethylphenyl) methane, bis- (the 4- cyanato-s of 1,1- Base phenyl) ethane, bis- (4- cyanatophenyl) propane of 1,1-, bis- (4- cyanatophenyl) propane of 2,2-, bis- (the 4- cyanato-s of 2,2- Base -3- aminomethyl phenyl) propane, bis- (2- cyanato -5- xenyl) propane of 2,2-, bis- (4- cyanatophenyl) hexafluoros third of 2,2- Bis- (4- cyanato -3,5- 3,5-dimethylphenyl) propane of alkane, 2,2-, bis- (4- cyanatophenyl) butane of 1,1-, bis- (the 4- cyanato-s of 1,1- Base phenyl) iso-butane, bis- (4- cyanatophenyl) pentanes of 1,1-, bis- (4- the cyanatophenyl) -3- methybutanes of 1,1-, 1,1- be bis- Bis- (4- the cyanatophenyl) -2,2- dimethylpropanes of (4- cyanatophenyl) -2- methybutane, 1,1-, bis- (the 4- cyanatos of 2,2- Phenyl) butane, bis- (4- cyanatophenyl) pentanes of 2,2-, bis- (4- cyanatophenyl) hexanes of 2,2-, bis- (the 4- cyanato benzene of 2,2- Base) -3- methybutane, bis- (4- the cyanatophenyl) -4- methylpentanes of 2,2-, bis- (4- the cyanatophenyl) -3,3- diformazans of 2,2- Bis- (4- cyanatophenyl) hexanes of base butane, 3,3-, bis- (4- cyanatophenyl) heptane of 3,3-, 3,3- bis- (4- cyanatophenyls) Bis- (4- the cyanatophenyl) -2- methylpentanes of octane, 3,3-, bis- (4- the cyanatophenyl) -2- methyl hexanes of 3,3-, 3,3- are bis- Bis- (4- the cyanatophenyl) -3- methyl heptanes of (4- cyanatophenyl) -2,2- dimethyl pentane, 4,4-, bis- (the 4- cyanatos of 3,3- Phenyl) -2- methyl heptane, bis- (4- the cyanatophenyl) -2,2- dimethylhexanes of 3,3-, bis- (the 4- cyanatophenyls) -2 of 3,3-, Bis- (4- the cyanatophenyl) -2,2,4- trimethylpentanes of 4- dimethylhexane, 3,3-, bis- (the 4- cyanatophenyls) -1,1 of 2,2-, It is 1,3,3,3- hexafluoropropane, bis- (4- cyanatophenyl) phenylmethanes, bis- (4- the cyanatophenyl) -1- diphenylphosphino ethanes of 1,1-, double Bis- (4- cyanatophenyl) pentamethylene of (4- cyanatophenyl) biphenyl methane, 1,1-, bis- (4- cyanatophenyl) hexamethylenes of 1,1-, Bis- (4- cyanato -3- isopropyl phenyl) propane of 2,2-, 1,1- bis- (3- cyclohexyl -4- cyanatophenyl) hexamethylenes, bis- (4- cyanogen Aminosulfonylphenyl) diphenyl methane, bis- (4- cyanatophenyl) -2,2- dichloroethylene, bis- [2- (4- the cyanatophenyl) -2- of 1,3- Propyl] benzene, bis- [2- (4- the cyanatophenyl) -2- propyl] benzene of 1,4-, bis- (4- the cyanatophenyl) -3,3,5- front three basic rings of 1,1- Hexane, 4- [bis- (4- cyanatophenyl) methyl] biphenyl, bis- cyanato benzophenone of 4,4-, 1,3- bis- (4- cyanatophenyls)- 2- propylene -1- ketone, bis- (4- cyanatophenyl) ethers, bis- (4- cyanatophenyl) sulfide, bis- (4- cyanatophenyl) sulfones, 4- cyanogen Acyl group benzoic acid -4- cyanatophenyl ester (4- cyanatophenyl -4- cyanato benzoic ether), double-(4- cyanatophenyl) carbon Bis- (4- cyanatophenyl) adamantane of acid esters, 1,3-, bis- (4- the cyanatophenyl) -5,7- dimethyladamantanes of 1,3-, 3,3- are bis- (4- cyanatophenyl) isobenzofuran -1 (3H) -one (cyanate of phenolphthalein), 3,3- bis- (4- cyanato -3- aminomethyl phenyls) are different Benzofuran -1 (3H) -one (cyanate of o-cresolphthalein), 9,9 '-bis- (4- cyanatophenyl) fluorenes, bis- (the 4- cyanatos-of 9,9- 3- aminomethyl phenyl) fluorenes, bis- (2- cyanato -5- xenyl) fluorenes of 9,9-, three (4- cyanatophenyl) methane, (the 4- cyanogen of 1,1,1- tri- Aminosulfonylphenyl) ethane, 1,1,3- tri- (4- cyanatophenyl) propane, α, α, α '-three (4- cyanatophenyl) -1- ethyl -4- is different Propylbenzene, 1,1,2,2- tetra- (4- cyanatophenyl) ethane, four (4- cyanatophenyl) methane, (N- methyl -4- cyanogen of 2,4,6- tri- Anilid base) -1,3,5- triazine, bis- (N- methyl -4- cyanato anilino-) -6- (methylphenylamine the base) -1,3,5- of 2,4- Triazine, bis- (N-4- cyanato -2- aminomethyl phenyls) -4,4 '-oxos double phthalimides, bis- (N-3- cyanato -4- methyl Phenyl) it is the double phthalimide of -4,4 '-oxos, the double phthalimides of bis- (N-4- cyanatophenyls) -4,4 '-oxygen, double (N-4- cyanato -2- aminomethyl phenyl) double phthalimides of -4,4 '-(hexafluoroisopropylidenyls), three (3,5- dimethyl -4- Cyanato benzyl) isocyanuric acid ester, bis- (4- cyanatophenyl) the benzyl first lactams (phthalimidine) of 2- phenyl -3,3-, 2- Bis- (4- cyanato -3- the methylbenzenes of bis- (4- cyanatophenyl) the benzyl first lactams of (4- aminomethyl phenyl) -3,3-, 2- phenyl -3,3- Base) benzyl first lactams, bis- (4- cyanatophenyl) indole-2-ketones of 1- methyl -3,3-, bis- (the 4- cyanato benzene of 2- phenyl -3,3- Base) indole-2-ketone, so that phenol resol resins, cresol novolac resin (is passed through public affairs by method similar to the above The method known makes phenol, alkyl substituted phenol or the formaldehyde compounds such as halogen-substituted phenol and formalin, paraformaldehyde in acid Reacted and winner in property solution), trisphenol novolac resin (make hydroxy benzaldehyde and phenol in the presence of acidic catalysts Reaction and winner), fluorenes novolac resin (make fluorenone compound and bis- (hydroxyaryl) fluorenes class the depositing in acidic catalyst of 9,9- It is lower reaction and winner), phenol aralkyl resin, cresols aralkyl resin, naphthols aralkyl resin, biphenyl aralkyl resin (by well known method, make Ar₄-(CH₂Y)₂Shown such double halogenated methyl chemical combination objects and phenolic compounds are in acidic catalyst Or winner, make Ar without reacting under catalyst₅-(CH₂OR)₂Shown such bis- (alkoxy methyl) compounds, Ar₆- (CH₂OH)₂Shown such bis- (hydroxymethyl) compounds reacted in the presence of acidic catalysts with phenolic compounds and winner, Or make aromatic aldehyde compound, aralkyl compound, phenolic compounds polycondensation and winner), the modified xylene formaldehyde resin of phenol it is (logical Cross well known method, react xylene formaldehyde resin and winner in the presence of acidic catalysts with phenolic compounds), modified naphthalene Formaldehyde resin (by well known method, makes naphthaldehyde resin and hydroxyl substituted aromatic compound in the presence of acidic catalyst Lower reaction and winner), the modified dicyclopentadiene novolacs of phenol, the phenolic resin with poly- naphthylene ether structure (pass through well known side Method forms dehydrating condensation in the presence of basic catalyst of the polyhydroxy naphthalene compound in 1 molecule with 2 or more phenolic hydroxyl groups Person) etc. phenolic cyanate resins esterification and winner etc., but be not particularly limited.These cyanate esters can be used a kind or mixed It closes and uses two or more.As aforementioned Ar₄、Ar₅And Ar₆Concrete example, can enumerate Isosorbide-5-Nitrae-phenylene, 1,3- phenylene, 4,4 '- Biphenylene, 2,4 '-biphenylenes, 2,2 '-biphenylenes, 2,3 '-biphenylenes, 3,3 '-biphenylenes, 3,4 '-sub- biphenyl Base, 2,6- naphthylene, 1,5- naphthylene, 1,6- naphthylene, 1,8- naphthylene, 1,3- naphthylene, 1,4- naphthylene etc..

It is further more excellent from thermal conductivity, low heat expansion and bending modulus in these for cyanate esters (B) From the perspective of different, preferably phenol novolak type cyanate esters, naphthols aralkyl-type cyanate esters composition, biphenyl aralkyl Fundamental mode cyanate esters, naphthylene ether type cyanate esters, xylene resin type cyanate esters, adamantane framework type Cyanate esters and cyanate esters containing allyl or acrylic, more preferable naphthols aralkyl-type cyanate chemical combination Object.

As the cyanate esters containing allyl or acrylic, for example, cyanogen shown in following formula (1A) can be enumerated Ester compound.

(in formula (1A), n indicates the average value of number of repeat unit, indicates 1~50 number, R₁Indicate singly-bound, carbon number 1~50 Divalent organic group, nitrogen number 1~10 divalent organic group, carbonyl (- CO-), carboxyl (- C (=O) O-), carbonylic dioxo compound Base (- OC (=O) O-), sulfonyl (- SO₂), any one of the sulphur atom (- S-) of divalent and the oxygen atom (- O-) of divalent, R_x Indicate that allyl or acrylic, p each independently represent 1 or more integer, there are multiple R₁In the case where, multiple R₁It can phase Together, it can also be different.)

Formula (1A) compound represented can be for by the identical and R with the number of repeat unit n in formula (1A)₁Identical chemical combination The form that object is formed, or the form of the mixture of number of repeat unit n in formula (1A) different compounds, or R in formula (1A)₁The form of the mixture of different compounds.N in formula (1A) indicates the average value of number of repeat unit, is 1 ~50.

In formula (3), R₁Indicate the divalent organic group (example of singly-bound, the divalent organic group of carbon number 1~50, nitrogen number 1~10 Such as, formula: group shown in-N-R-N- (in formula, R indicates the alkyl of divalent), imino group, polyimide-based etc.), carbonyl (- CO-), Carboxyl (- C (=O) O-), carbonylic dioxo compound base (- OC (=O) O-), sulfonyl (- SO₂), the sulphur atom (- S-) and 2 of divalent Any one of oxygen atom (- O-) of valence, there are multiple R₁In the case where, multiple R₁It may be the same or different.In addition, R₁ The bonding position of aromatic rings is not particularly limited.In these, preferably carbon number 1~50 divalent organic group (hereinafter, Referred to as " specific divalent organic group ").

As specific divalent organic group, heteroatomic divalent alkyl can have for example, can enumerate.As above-mentioned Divalent alkyl, for example, alkylidene can be enumerated (for example, the Asia of the carbon numbers such as methylene, ethylidene, trimethylene, propylidene 1~10 Alkyl etc.), alkylidene radical (alkylidene) (for example, alkylidene radical of carbon numbers 1~10 such as ethidine, 2,2- propylidene base etc.), ring it is sub- Alkyl (for example, cyclopentylene, cyclohexylidene, trimethylcyclohexylene etc.), ring alkylidene radical are (for example, the cycloalkanes of carbon number 5~8 is pitched Base), the divalent organic group with aromatic rings is (for example, biphenyl methylene, fluorenes diyl, phthalide diyl, formula :-(CH₃)C(CH₃)- Ph-(CH₃)C(CH₃In)-(formula, Ph indicates phenylene.) shown in group etc.).Hydrogen atom in these divalent organic groups can be with It is substituted with a substituent, as substituent group, halogen atom (for example, fluorine atom and chlorine atom), alkoxy can be enumerated (for example, first Oxygroup and phenoxy group), cyano etc..

In formula (1A), R_xIndicate allyl or acrylic.P each independently represents 1 or more integer (preferably 1).

Content of the cyanate esters (B) in resin combination can be suitable for setting according to desired characteristic, not have It is particularly limited to, when the resin solid content in resin combination is set as 100 mass parts, preferably 1~90 mass parts.Content is 1 In the case where the range of~90 mass parts, it is easy to get low heat expansion, thermal conductivity and the superior resin combination of bending modulus Object.From the same viewpoint, content is more preferably 5~80 mass parts, further preferably 10~70 mass parts.

(packing material (C))

For the resin combination of present embodiment, from the further sight for improving formability, thermal conductivity, low thermal expansion characteristics Point sets out, and preferably also contains packing material (C).

It can be suitable for using well known packing material, type does not have as packing material used in present embodiment (C) It is particularly limited to, material usually used in this field can be suitably used.Specifically, natural titanium dioxide can be enumerated Silicon, fused silica, synthetic silica, amorphous silica, AEROSIL, hollow silica etc. be silica-based, Hard charcoal, titanium white, zinc oxide, magnesia, zirconium oxide, boron nitride, aggregation boron nitride, silicon nitride, aluminium nitride, barium sulfate, hydroxide Aluminium, heating aluminum hydroxide item for disposal (carrying out heat treatment to aluminium hydroxide reduces a part of the crystallization water and winner), Bo Mu The molybdenum compounds such as the metal hydrates such as stone, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate, zinc stannate, aluminium oxide, clay, height Ridge soil, talcum, calcined clay, roasting kaolin, fired talc, mica, E- glass, A- glass, NE- glass, C- glass, L- glass Glass, D- glass, S- glass, M- glass G20, staple glass fibre (include the glass such as E glass, T glass, D glass, S glass, Q glass Micropowder class.), hollow glass, the inorganic system such as globular glass packing material and styrene type, butadiene-type, acrylic type Equal rubber powders, the rubber powder of core-shell-type, silicone resin powder, silicone rubber powder, organosilicon composite powder etc. have The packing material etc. of machine system.These packing materials can be used alone or two or more is applied in combination.

For packing material (C), in these, selected from by silica, aluminium hydroxide, boehmite, magnesia and hydrogen-oxygen It is appropriate for changing one or more of the group of magnesium composition.By using these packing materials, there is the thermal expansion of resin combination special Property, the improved tendency of the characteristics such as dimensional stability, anti-flammability.

Content of the packing material (C) in resin combination can be suitable for setting according to desired characteristic, without special It limits, when the resin solid content in resin combination is set as 100 mass parts, preferably 50~1600 mass parts.Content is 50 In the case where the range of~1600 mass parts, the formability of resin combination becomes better, there is thermal conductivity, thermal expansion character etc. The tendency that characteristic further improves.From the same viewpoint, content is more preferably 60~1200 mass parts, is more preferably 70~1000 mass parts.

When being used herein as packing material (C), silane coupling agent, Ricinate is preferably applied in combination.As silane coupled Agent, can be suitably used silane coupling agent used in the surface treatment of usual inorganic matter, and type is not particularly limited.Tool For body, γ aminopropyltriethoxy silane, N- β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane can be enumerated Etc. amino silicone methane series, γ-glycidoxypropyltrime,hoxysilane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane Equal epoxy silanes system, γ-methacryloxypropyl trimethoxy silane, vinyl three ('beta '-methoxy ethyoxyl) silane etc. The cations such as vinyl silanes system, N- β-(N- vinylbenzylaminoethyl)-gamma-amino propyl trimethoxy silicane hydrochloride Property silane system, phenyl silane system etc..Silane coupling agent can be used alone or two or more is applied in combination.In addition, as wet Moisten dispersing agent, the Ricinate commonly used in coating can be suitably used, type is not particularly limited.It is preferable to use The Ricinate on copolymer basis, as its concrete example, can enumerate BYK Japan KK. Disperbyk-110, 111,161,180, BYK-W996, BYK-W9010, BYK-W903, BYK-W940 etc..Ricinate can be used alone Or two or more is applied in combination.

In turn, the resin combination of present embodiment can be in the range of not damaging desired characteristic containing selected from by removing Epoxy resin (hereinafter referred to as " other epoxy resin " other than epoxy resin (A).), maleimide compound, phenolic aldehyde tree In the group that rouge, oxetane resin, benzoxazine compound and the compound with the unsaturated group that can polymerize form 1 kind or more.By the way that these resins are applied in combination, so as to improve resin combination is solidified made of solidfied material it is fire-retardant The desired characteristics such as property, low-dielectric.

As other epoxy resin, as long as the epoxy resin in 1 molecule with 2 or more epoxy groups and not being general formula (1) compound represented can be suitable for that its type is not particularly limited using well known epoxy resin.Specifically, can arrange Enumerate bisphenol A type epoxy resin, bisphenol E-type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolac Type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, glycidyl ester type epoxy resin, aralkyl phenolic varnish type Epoxy resin, biphenyl aralkyl-type epoxy resin, naphthylene ether type epoxy, cresol novolak type epoxy resin, more officials It can phenol-type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, phenol virtue Alkane type epoxy resin, naphthols aralkyl-type epoxy resin, dicyclopentadiene-type epoxy resin, biphenyl type epoxy resin, alicyclic ring Formula epoxy resin, polyol type epoxy resin, phosphorous epoxy resin, glycidyl amine, ethylene oxidic ester, make butadiene etc. it is double Compound made of key epoxidation passes through hydroxyl organic siliconresin class and the compound of epoxychloropropane reacted etc.. Among these epoxy resin, biphenyl aralkyl-type epoxy resin, naphthylene ether type epoxy, multifunctional phenol-type epoxy resin, Naphthalene type epoxy resin is preferred in terms of anti-flammability, heat resistance.These epoxy resin, which can be used alone or combine, to be made Use two or more.

As maleimide compound, as long as to have the compound of 1 or more dimaleoyl imino in 1 molecule, Generally well-known maleimide compound can be used.For example, 4,4- diphenyl methane bismaleimide, benzene can be enumerated Bis- (4- (4- the maleimidephenoxy)-phenyl) third of methylmethane maleimide, meta-phenylene bismaleimide, 2,2- Alkane, 3,3- dimethyl -5,5- diethyl -4,4- diphenyl methane bismaleimide, 4- methyl-1,3- phenylene span carry out acyl Imines, 1,6- bismaleimide-(2,2,4- trimethyl) hexane, 4,4- diphenyl ether bismaleimide, 4,4- diphenyl Bis- (3- maleimidephenoxy) benzene of sulfone bismaleimide, 1,3-, 1,3- bis- (4- maleimidephenoxy) benzene, polyphenyl Methylmethane maleimide, phenolic varnish type maleimide, biphenyl aralkyl-type maleimide and these maleimides Prepolymer or maleimide compound and the prepolymer of amine compounds of compound etc., are not particularly limited.These Malaysia acyls Group with imine moiety can be used a kind or be mixed with two or more.Wherein, particularly preferred phenolic varnish type maleimide chemical combination Object, biphenyl aralkyl-type maleimide compound.

As phenolic resin, as long as, with the phenolic resin of 2 or more hydroxyls, usual public affairs to can be used in 1 molecule The phenolic resin known.For example, bisphenol A type phenolic resin, bisphenol E-type phenolic resin, bisphenol F type phenolic resin, double can be enumerated Phenol S type phenolic resin, phenol resol resins, bisphenol A novolac type phenolic resin, glycidyl ester type phenolic resin, Aralkyl novolak phenolics, biphenyl aralkyl-type phenol resin, cresol novolak type phenolic resin, multifunctional phenol Urea formaldehyde, naphthol resin, naphthol novolac varnish gum, multifunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified phenolic are clear Paint shaped phenolic resin, phenol aralkyl type phenolic resin, naphthols aralkyl-type phenol resin, dicyclopentadiene type phenol resin, Biphenyl type phenolic resin, ester ring type phenolic resin, polyol type phenolic resin, phosphorus containing phenolic resin, hydroxyl organic siliconresin Class etc., is not particularly limited.In these phenolic resin, biphenyl aralkyl-type phenol resin, contains naphthols aralkyl-type phenol resin Phosphorous-containing phenolic resin, hydroxyl organic siliconresin are preferred in terms of anti-flammability.These phenolic resin can be used alone or Two or more is applied in combination.

As oxetane resin, generally well-known oxetane resin can be used.For example, oxa- can be enumerated Cyclobutane, 2- methy oxetane, 2,2- dimethyl oxygen azetidine, 3- methy oxetane, 3,3- dimethyl oxa- The alkyl such as cyclobutane oxetanes, 3- methyl -3- methoxy oxetanes, 3,3- bis- (trifluoromethyl) perfluor oxa- Bis- (chloromethyl) oxetanes of cyclobutane, 2- chloromethyl oxetanes, 3,3-, biphenyl type oxetanes, OXT-101 (East Asia synthesizes trade name processed), OXT-121 (East Asia synthesizes trade name processed) etc., are not particularly limited.These oxetanes trees Rouge can be used a kind or two or more is applied in combination.

As benzoxazine compound, as long as to have the compound of 2 or more dihydrobenzo oxazines rings in 1 molecule, Commonly known benzoxazine compound can be used.For example, bisphenol A-type benzoxazine BA-BXZ (small westernization can be enumerated Trade name processed), bisphenol-f type benzoxazine BF-BXZ (small westernization length of schooling trade name), (the small west bisphenol S type benzoxazine BS-BXZ Chemistry trade name), P-d type benzoxazine (Shikoku Chem's trade name), F-a type benzoxazine (four countries Chemical conversion industry Co. Ltd. system trade name) etc., it is not particularly limited.1 kind or mixing can be used in these benzoxazine compounds Use two or more.

As the compound with the unsaturated group that can polymerize, commonly known compound can be used.For example, can arrange Enumerate the vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, divinyl biphenyls, (methyl) methyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, polypropylene glycol two (methyl) acrylate, three hydroxyl first Base propane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, (methyl) esters of acrylic acid of 1 yuan of alcohol such as dipentaerythritol six (methyl) acrylate or polyalcohol, bisphenol type epoxy (methyl) Epoxies (methyl) esters of acrylic acid, benzocyclobutane olefine resin, (double) such as acrylate, bisphenol F type epoxy (methyl) acrylate Maleimide resin etc., is not particularly limited.These compounds with unsaturated group can be used a kind or be used in mixed way Two or more.

In addition, the resin combination of present embodiment as needed can be containing for being suitable for the solidification for adjusting curing rate Promotor.As the curing accelerator, it is logical as curing accelerator that cyanate esters, epoxy resin etc. can be suitably used The substance being often used, type are not particularly limited.As its concrete example, zinc octoate, zinc naphthenate, aphthenic acids can be enumerated The organic metal such as cobalt, copper naphthenate, ferric acetyl acetonade, nickel octoate, manganese octoate salt, phenol, xylenol, cresols, resorcinol, The alcohols such as the phenolic compounds such as catechol, octyl phenol, nonyl phenol, n-butyl alcohol, 2-Ethylhexyl Alcohol, 2-methylimidazole, 2- ethyl- 4-methylimidazole, 2- phenylimidazole, 1- cyano ethyl -2- phenylimidazole, 1- cyano ethyl -2-ethyl-4-methylimidazole, 2- benzene The carboxylic acid of the imidazoles such as base -4,5- bishydroxymethyl imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazole and these imidazoles Or the derivatives such as addition product of its anhydride, dicyandiamide, benzyldimethylamine, 2,4,4- methyl-N, N- dimethyl benzyl amine, N, N- bis- Methylbenzyl amine, N, accelerine, N, N- dimethyl toluidine, N, N- dimethyl aminopyridine, 2-N- ethylo benzene amido Ethyl alcohol, tri-n-butyl amine, lutidines, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethyl The amines such as butanediamine, N- methyl piperidine, phosphine based compound, phosphine oxide based compound, phosphonium salt based compound, diphosphine based compound etc. Phosphorus compound, epoxy ifyzidazole adduct based compound, benzoyl peroxide, p-chlorobenzoyl peroxide, di-tert-butyl peroxide The azos such as peroxide or azobis isobutyronitrile such as object, diisopropyl peroxide carbonate, two -2- ethylhexyl of peroxidating carbonic acid Compound etc..Curing accelerator can be used alone or two or more is applied in combination.

It should be noted that the viscosity etc. of the curing degree of resin, resin combination can be considered in the dosage of curing accelerator It being suitable for adjustment, is not particularly limited, is 0.005 usually relative to 100 mass parts of resin solid content in resin combination ~10 mass parts.

In turn, other can be applied in combination in the range of not damaging desired characteristic in the resin combination of present embodiment It is the various high-molecular compounds such as heat-curing resin, thermoplastic resin and its oligomer, elastomer class, fire-retardant compound, each Kind additive etc..As long as these are usually used additive, it is not particularly limited.For example, as fire-retardant compound, it can Enumerate the bromine compounds such as 4,4 '-'-dibromobiphenyls, phosphate, melamine phosphate, phosphorous epoxy resin, melamine, benzo The nitrogen compounds such as guanamines, cycle compound containing oxazines, silicon-type compound etc..In addition, purple can be enumerated as various additives Ultraviolet absorbers, antioxidant, Photoepolymerizationinitiater initiater, fluorescent whitening agent, photosensitizer, dyestuff, pigment, thickener, flow adjustment Agent, lubricant, defoaming agent, dispersing agent, levelling agent, gloss agent, polymerization inhibitor etc..These can be used alone according to expectation or Two or more is applied in combination.

It should be noted that organic solvent can be used in the resin combination of present embodiment as needed.In this case, Resin combination of the invention can be used as at least part of above-mentioned various resin components, preferably all dissolve or be compatible to The form (solution or varnish) of solvent uses.As organic solvent, as long as at least the one of above-mentioned various resin components can be made Partially, preferably all dissolutions or compatible, then can be suitable for using well known organic solvent, type is not particularly limited.Specifically For, the ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), propylene glycol monomethyl ether, propylene glycol methyl ether acetate etc. can be enumerated Cellosolve series solvent, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methoxy propyl The amides isopolarity solvent such as the ester series solvents such as sour methyl esters, hydroxy-methyl isobutyl acid, dimethyl acetamide, dimethylformamide Non-polar solvents such as the aromatic hydrocarbons such as class, toluene, dimethylbenzene etc..These can be used alone or two or more is applied in combination.

The resin combination of present embodiment can be prepared by conventional method, as long as uniformly containing general formula to can be obtained (1) epoxy resin shown in (A) and cyanate esters (B), above-mentioned any other ingredient resin combination method, then its Method of adjustment is not particularly limited.For example, can be by epoxy resin (A) shown in general formula (1) and cyanate esters (B) successively It with being mixed in solvent, is sufficiently stirred, thus easily prepares the resin combination of present embodiment.

It should be noted that can be carried out in the preparation of resin combination for making each ingredient equably dissolve or disperse Well known processing (stirring, mixing, mixing process etc.).For example, packing material (C) it is evenly dispersed when, using being attached to The stirred tank of blender with appropriate stirring capacity is stirred decentralized processing, thus improves the dispersion to resin combination Property.Device or public affairs such as ball mill, ball mill for the purpose of mixing can be used in above-mentioned stirring, mixing, mixing process Turn device well known to mixing arrangement of rotation type etc. to be suitable for progress.

The resin combination of present embodiment can be used as the insulating layer of printed circuit board, semiconductor package body is made with material With.For example, can be by the way that resin combination of the invention will be made to be dissolved in the infiltration of solution made of solvent or be coated on substrate simultaneously It is dried prepreg is made.

Alternatively, it is also possible to be made by the way that the resin combination for making present embodiment is dissolved in the drying of solution made of solvent At resin sheet.Resin sheet can be used as lamination film or dry film solder resist uses.

In addition, the resin combination of present embodiment can be only to use the uncured state of solvent seasoning, it can also To be used as needed with the state of semi-solid preparation (B-staged).

Hereinafter, the prepreg to present embodiment is described in detail.The prepreg of present embodiment is by above-mentioned reality It applies the resin combination infiltration of mode or is coated on substrate and winner.As long as the manufacturing method of prepreg is by present embodiment Resin combination and substrate combination and the method for manufacturing prepreg, are just not particularly limited.Specifically, can be by by this reality It applies the resin combination infiltration of mode or is coated on the method for carrying out drying in 2~15 minutes or so after substrate at 120~220 DEG C Deng progress semi-solid preparation, the prepreg of present embodiment is thus manufactured.At this point, resin combination is to the adhesion amount of substrate, i.e. resin Amount of composition is (comprising packing material (C).) relative to the prepreg after semi-solid preparation total amount be preferably 20~99 mass % model It encloses.

The substrate used when as the prepreg for manufacturing present embodiment, can be used institute in various printed circuit board materials Well known substrate.For example, E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass can be enumerated Organic fibres such as inorfil, polyimides, polyamide, the polyester in addition to glass such as the glass fibres such as glass, globular glass, quartz The woven fabrics such as dimension, liquid crystal polyester, but it is not limited to these.Shape as substrate, it is known to which woven fabric, rove, is chopped at non-woven fabrics Felt, surface felt etc. can be any one.Substrate can be used alone or two or more is applied in combination.In addition, the thickness of substrate It is not particularly limited, when being plywood purposes, the preferred range of 0.01~0.2mm especially implements super fibrillation process, eyelet The woven fabric of plugging handling is suitable from the viewpoint of dimensional stability.In turn, epoxy silane processing, amino silane have been carried out The glass woven fabrics that are surface-treated with silane coupling agent etc. such as processing from the viewpoint of moisture absorption heat resistance be preferred.In addition, Liquid crystal polyester is preferred from electrical characteristics aspect.

In addition, the clad with metal foil plywood of present embodiment is by least 1 or more above-mentioned prepreg overlapping, in its single side Or made of configuration metal foil progress in two sides is cascading into shape.Specifically, one or more aforementioned prepreg can be overlapped, In Its one or two sides configures copper, the metal foils such as aluminium, carries out cascading into shape, thus makes.As long as metal foil used herein is Workable metal foil in printed circuit board material, there is no particular limitation, the copper foils such as preferred rolled copper foil, electrolytic copper foil.Separately Outside, the thickness of metal foil is not particularly limited, and preferably 2~70 μm, 3~35 μm more preferable.It, can be using logical as molding condition Normal printed circuit board plywood and multiple-plate method.It is, for example, possible to use multistage press, multi-stage vacuum press, Progressive forming machine, autoclave forming machine etc., with 180~350 DEG C of temperature, 100~300 minutes heating times, face pressure 20~ 100kg/cm²It carries out cascading into shape, thus manufactures clad with metal foil plywood of the invention.It will be above-mentioned pre- alternatively, it is also possible to pass through Leaching material is merged into that row is cascading into shape to be made multi-layer board with the wiring plate group of internal layer separately made.As multiple-plate manufacture Method, for example, 35 μm of copper foil can be configured on the two sides of 1 above-mentioned prepreg, carry out under the above conditions it is cascading into shape after, Internal layer circuit is formed, Darkening process is implemented to the circuit and forms inner layer circuit board, thereafter, by the inner layer circuit board and above-mentioned pre- Leaching material 11 be alternately arranged, and then outermost layer configure copper foil, preferably carry out under vacuum under the above conditions it is cascading into shape, Thus multi-layer board is made.

Moreover, the clad with metal foil plywood of present embodiment can be used appropriately as printed circuit board.Printed circuit Plate can manufacture by conventional method, and manufacturing method is not particularly limited.Hereinafter, showing the manufacturing method of printed circuit board An example.Firstly, preparing the clad with metal foil plywood such as above-mentioned copper-clad laminated board.Then, real to the surface of clad with metal foil plywood Etching process is applied, the formation of internal layer circuit is carried out, makes internal substrate.As needed to the internal layer circuit surface of the internal substrate The surface treatment for improving adhesive strength is carried out, the above-mentioned prepreg of number needed for being then overlapped on its internal layer circuit surface, into And the metal foil of outer circuit is laminated on the outside, carry out heating pressurization and it is integrally formed.In this way, manufacture internal layer circuit with Substrate is formed between the metal foil of outer circuit and the insulating layer that is formed by the solidfied material of hot curing resin composition The plywood of multilayer.Then, after the drilling processing for implementing through-hole, via hole to the plywood of the multilayer, the wall surface in the hole The metal lining overlay film for the metal foil of internal layer circuit and outer circuit to be connected is formed, and then to the gold of outer circuit Belong to foil and implement etching process to form outer circuit, thus manufactures printed circuit board.

Printed circuit board obtained in above-mentioned Production Example has insulating layer and is formed in the conductor on the surface of the insulating layer Layer, insulating layer are the composition of the resin combination comprising above-mentioned present embodiment.That is, prepreg (the base of above-mentioned present embodiment Material and infiltration or be coated on the substrate present embodiment resin combination), the stacking of the clad with metal foil of above-mentioned present embodiment The layer (layer formed by resin combination of the invention) of the resin combination of plate is by the resin combination comprising present embodiment Insulating layer constitute.

The resin sheet of present embodiment includes the resin combination of present embodiment.The resin sheet of present embodiment can lead to Crossing will make above-mentioned resin combination be dissolved in solution coating made of solvent in supporter and dry obtain.As being used herein as Supporter, be not particularly limited, for example, polyethylene film, polypropylene film, polycarbonate film, poly- to benzene can be enumerated Naphthalate film, ethylene tetrafluoroethylene copolymer film and release agent is coated on the surface of these films Conductor foils, glass plate, the SUS plate, FRP such as film substrate, copper foil, the aluminium foil of organic systems such as mould release film, Kapton Etc. the inorganic system of plates film.As coating method, for example, the following methods can be enumerated: using bar coater, die coating machine, scraping Knife, Bake applicator etc. will make above-mentioned resin combination be dissolved in solution coating made of solvent on supporter, thus make The laminates that supporter and resin sheet are integrally formed.Alternatively, it is also possible to by after the drying from laminates by supporter remove or It is etched single-layer sheet (resin sheet) is made.It should be noted that the resin combination of above-mentioned present embodiment can also will be made Object is dissolved in solution made of solvent and supplies in the mold of the die cavity with sheet and dry etc., so that it is configured to sheet, by This can also obtain single-layer sheet (resin sheet) under without using supporter.

It should be noted that in the production of the resin sheet (single layer or laminates) of present embodiment, doing when removing solvent Dry condition is not particularly limited, and if low temperature, then solvent is easy to remain in resin combination, if high temperature, then will do it tree The solidification of oil/fat composition, therefore 1~90 minute at a temperature of preferably 20 DEG C~200 DEG C.In addition, the resin sheet of present embodiment The thickness of the resin layer of (single layer or laminates) can pass through the concentration and coating of the solution of the resin combination of present embodiment Thickness adjusts, and is not particularly limited, if usually coating thickness thickens, solvent is easy residual when drying, therefore preferably 0.1~ 500μm。