JP2015189165A - laminate and metal-clad laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which causes no degradation such as discoloration due to the oxidation of a surface of the laminate and occurrence of cracks even if placed under a high temperature of approximately 200°C over a long period of time, and to provide a metal-clad laminate.SOLUTION: There are provided: a laminate which comprises a crosslinkable resin composition layer obtained by mass polymerization of a polymerizable composition (1) comprising a cycloolefin monomer, a metathesis polymerization catalyst and a crosslinking assistant and an antioxidation layer obtained from a polymerizable composition (2) containing a polyphenyl ether resin or a phenol resin having at least one radical-polymerizable group, where at least one of the outermost layers of the laminate is the antioxidation layer; and a metal-clad laminate formed by further laminating a metal foil on the outside of the antioxidation layer.

Description

  The present invention relates to a laminate and a metal-clad laminate that are excellent in interlayer adhesion without causing thermal degradation of the surface even when placed at a high temperature for a long time.

  With recent downsizing and thinning of electronic parts and electronic devices, circuit boards and the like used therefor are required to be thin. Therefore, it is necessary to form a higher-density circuit wiring pattern on the circuit board.

Conventionally, in order to form a high-density circuit wiring pattern, a multilayer circuit board is used and the thickness of each layer constituting the circuit board is reduced. From the viewpoint of maintaining the mechanical strength of the circuit board even when the circuit board is thinned, a material such as glass fiber is used as a material for forming the interlayer insulating layer of the multilayer circuit board. A method using a prepreg containing a substrate has been studied.
However, when such a prepreg is placed at a high temperature for a long time, the surface layer may be discolored and thermally deteriorated.

In order to solve this problem, Patent Document 1 discloses a laminate in which an epoxy resin layer having a thickness of 2 μm is laminated on the surface of the prepreg as an antioxidant resin layer in order to protect the prepreg. Patent Document 2 describes that a crosslinked product excellent in heat resistance and the like can be obtained by using a polymerizable composition containing a cycloolefin monomer, a phenoxy group-containing oligomer, and a metathesis polymerization catalyst.
However, in the examples in these documents, only an evaluation test at a relatively low temperature (125 ° C. to 150 ° C.) is performed, and a test when placed at a high temperature (about 200 ° C.) is performed. Absent.

JP 2009-277893 A JP 2010-168488 A

  The present invention has been made in view of the above-described prior art, and even when it is placed at a high temperature (about 200 ° C.) for a long time, the surface of the laminate is oxidized and discolored, and cracks are generated. An object of the present invention is to provide a laminate that is not deteriorated and has excellent interlayer adhesion.

  The inventor has intensively studied to solve the above problems. As a result, it has a crosslinkable resin composition layer obtained by bulk polymerization of a polymerizable composition (1) containing a cycloolefin monomer, a metathesis polymerization catalyst, and a crosslinking aid, and at least one radically polymerizable group. A laminate having an antioxidant layer obtained from the polymerizable composition (2) containing a polyphenylene ether resin or a phenol resin, wherein at least one of the outermost layers of the laminate is the antioxidant layer, The present invention has found that even when it is placed at a high temperature (about 200 ° C.) for a long time, the surface of the laminate is not deteriorated due to oxidation and discoloration, and is excellent in interlayer adhesion. It came to complete.

Thus, according to the present invention, the following laminates [1] to [5] and the copper clad laminate [6] are provided.
[1] A crosslinkable resin composition layer obtained by bulk polymerization of a polymerizable composition (1) containing a cycloolefin monomer, a metathesis polymerization catalyst, and a crosslinking aid, and having at least one radical polymerizable group A laminate having an antioxidant layer obtained from a polymerizable composition (2) containing a polyphenylene ether resin or a phenol resin, wherein at least one of the outermost layers of the laminate is the antioxidant layer.

[2] The laminate according to [1], wherein the polymerizable composition (2) contains a polyphenylene ether resin having two radical polymerizable groups.
[3] The laminate according to [2], wherein the polyphenylene ether resin having the two radical polymerizable groups has a number average molecular weight of 500 to 5,000.
[4] The laminate according to any one of [1] to [3], wherein the crosslinking aid is a polyfunctional compound containing 2 to 4 radically polymerizable groups.

[5] The laminate according to any one of [1] to [4], wherein the polymerizable composition (2) further contains a hydrogenated styrenic thermoplastic elastomer.
[6] A metal-clad laminate obtained by further laminating a metal foil on the outer side of the antioxidant layer comprising the polymerizable composition (2) as the outermost layer in the laminate according to [1] to [5].

According to the present invention, even when the laminate is placed at a high temperature for a long time, the laminate is oxidized and discolored, and there is no deterioration such as generation of cracks, and the laminate has excellent interlayer adhesion. And a metal-clad laminate.
The laminate and metal-clad laminate of the present invention can be suitably used for printed wiring boards and the like.

Hereinafter, the present invention will be described in detail by dividing it into 1) a laminate and 2) a metal-clad laminate.
1) Laminate The laminate of the present invention comprises a crosslinkable resin composition layer obtained by bulk polymerization of a polymerizable composition (1) containing a cycloolefin monomer, a metathesis polymerization catalyst, and a crosslinking aid, and at least A laminate having an antioxidant layer obtained from a polymerizable composition (2) containing a polyphenylene ether resin or a phenol resin having one radical polymerizable group, wherein at least one of the outermost layers of the laminate is the above-mentioned It is an antioxidant layer.

(1) Crosslinkable resin composition layer The crosslinkable resin composition layer of the laminate of the present invention is obtained by bulk polymerization of a polymerizable composition (1) containing a cycloolefin monomer, a metathesis polymerization catalyst, and a crosslinking aid. It is obtained.

(I) Cycloolefin monomer The cycloolefin monomer is a compound having an alicyclic structure composed of carbon atoms and having at least one polymerizable carbon-carbon double bond in the alicyclic structure.

  In the present specification, the “polymerizable carbon-carbon double bond” refers to a carbon-carbon double bond capable of ring-opening polymerization. There are various types of ring-opening polymerization such as ionic polymerization, radical polymerization, and metathesis polymerization. In the present invention, metathesis polymerization is preferable.

Examples of the alicyclic structure possessed by the cycloolefin monomer include monocyclic, polycyclic, condensed polycyclic, bridged ring, and combination polycyclic thereof. Although there is no limitation in particular in carbon number which comprises each alicyclic structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces. Among these, a polycyclic structure is preferable from the viewpoint of highly balancing the dielectric properties and heat resistance of the obtained laminate.
As the cycloolefin monomer having a polycyclic structure, a norbornene-based monomer is particularly preferable. Here, the “norbornene monomer” refers to a cycloolefin monomer having a norbornene ring structure in the molecule. For example, norbornenes, dicyclopentadiene, tetracyclododecenes and the like can be mentioned.

The cycloolefin monomer may have a substituent at any position. Examples of the substituent include hydrocarbon groups having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkylidene group, and an aryl group; polar groups such as a carboxyl group and an acid anhydride group;
A cycloolefin monomer can be used individually by 1 type or in combination of 2 or more types.

  Among these, in the present invention, as the cycloolefin monomer, the cycloolefin monomer (a) having an alicyclic structure in the molecule and having a crosslinkable carbon-carbon unsaturated bond in the alicyclic structure. And having in the molecule at least one group selected from an alkenyl group having 2 to 6 carbon atoms, an alkylidene group having 1 to 6 carbon atoms, and a vinylidene group, and an alicyclic structure, And a cycloolefin monomer (b) having a carbon-carbon double bond (excluding the cycloolefin monomer (a)) or a cycloolefin monomer (b).

When the cycloolefin monomer (a) and the cycloolefin monomer (b) are mixed and used, the content ratio of the cycloolefin monomer (a) in the monomer mixture is 5 to 5 in all monomers constituting the monomer mixture. It is preferably 99.9% by mass, more preferably 20 to 95% by mass, still more preferably 40 to 90% by mass, and particularly preferably 50 to 80% by mass. The content ratio of the cycloolefin monomer (b) in the monomer mixture is preferably 0.1 to 95% by mass and more preferably 5 to 80% by mass in the total monomer constituting the monomer mixture. Preferably, it is 10-60 mass%, More preferably, it is 20-50 mass%.
If the content of the cycloolefin monomer (a) is too small, the peel strength of the resulting laminate may be reduced. On the other hand, if the content is too high, the heat resistance of the resulting laminate may be reduced.

  In the cycloolefin monomer (a), the “crosslinkable carbon-carbon unsaturated bond” refers to a carbon-carbon unsaturated bond that does not participate in ring-opening polymerization and can participate in a crosslinking reaction. The crosslinking reaction is a reaction that forms a bridge structure, and there are various forms such as a condensation reaction, an addition reaction, a radical reaction, and a metathesis reaction. In the present invention, usually, a radical crosslinking reaction or a metathesis crosslinking reaction. In particular, it refers to a radical crosslinking reaction. Crosslinkable carbon-carbon unsaturated bonds include carbon-carbon unsaturated bonds other than aromatic carbon-carbon unsaturated bonds, that is, aliphatic carbon-carbon double bonds or aliphatic carbon-carbon triple bonds. In the present invention, it usually means an aliphatic carbon-carbon double bond.

  As such a cycloolefin monomer (a), a monocyclic cycloolefin monomer having a crosslinkable carbon-carbon unsaturated bond in the alicyclic structure, and a crosslinkable carbon-carbon unsaturated bond in the alicyclic structure. Examples include norbornene-based monomers, and norbornene-based monomers having a crosslinkable carbon-carbon unsaturated bond in the alicyclic structure are preferable.

Specific examples of the cycloolefin monomer (a) include dicyclopentadiene, methyl-dicyclopentadiene, dimethyldicyclopentadiene, ethyldicyclopentadiene, 2,5-norbornadiene, 5-methyl-2,5-norbornadiene, 5- Examples thereof include compounds having two carbon-carbon unsaturated bonds in the alicyclic structure such as phenyl-2,5-norbornadiene and 5,6-dimethyl-2,5-norbornadiene. These can be used alone or in combination of two or more. Among these, dicyclopentadiene is preferable from the viewpoint that the effects of the present invention become more remarkable.
A cycloolefin monomer (a) can be used individually by 1 type or in combination of 2 or more types.

  The cycloolefin monomer (b) has, in the molecule, at least one group selected from a (meth) acryloyloxy group, an alkenyl group having 2 to 6 carbon atoms, an alkylidene group having 1 to 6 carbon atoms, and a vinylidene group, An alicyclic olefin monomer having an alicyclic structure and having a carbon-carbon double bond in the alicyclic structure. However, the cycloolefin monomer (a) is excluded.

As said C2-C6 alkenyl group, a vinyl group, 1-propenyl group, an allyl group, a butenyl group etc. are mentioned, A vinyl group and 1-propenyl group are preferable.
Examples of the alkylidene group having 1 to 6 carbon atoms include a methylidene group, an ethylidene group, a propylidene group, and a butylidene group.
As for the alicyclic structure which a cycloolefin monomer (b) has, the thing similar to the alicyclic structure which the said cycloolefin monomer (a) has is mentioned.

Specific examples of the cycloolefin monomer (b) include tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-3-carboxylic acid (acryloyloxy) methyl ester, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-3-carboxylic acid (methacryloyloxy) methyl ester, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-3-carboxylic acid 2- (acryloyloxy) ethyl ester, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-3-carboxylic acid 2- (methacryloyloxy) ethyl ester, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-3-carboxylic acid 2- (acryloyloxy) isopropyl ester, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-3-carboxylic acid 2- (methacryloyloxy) isopropyl ester, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-3-methyl-3-carboxylic acid (acryloyloxy) methyl ester, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-4-methyl-3-carboxylic acid (methacryloyloxy) methyl ester,
9-methylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-10-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-10-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-10-isopropyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-10-butyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-10-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-10-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-10-isopropyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-10-butyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-n-propylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-propylidene-10-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-propylidene-10-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-propylidene-10-isopropyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-propylidene-10-butyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-Isopropylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-isopropylidene-10-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-isopropylidene-10-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-isopropylidene-10-isopropyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-isopropylidene-10-butyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-Vinyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene;
9-isopropenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-allyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene;
9- (1-propenyl) tetracyclo [6.2.1.1 ^3,6 . ^{Tetracyclododecenes} such as 0 ^2,7 ] dodec-4-ene;
5-norbornen-2-yl acrylate, 5-norbornen-2-yl methacrylate, 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, 5,6-diethylidene-2-norbornene, n-propylidene- 2-norbornene, 5-isopropylidene-2-norbornene, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5- (1-propenyl) -2-norbornene, 5-allyl-2-norbornene; And norbornenes; and the like.

A cycloolefin monomer (b) can be used individually by 1 type or in combination of 2 or more types.
Among these, as a cycloolefin monomer (b), it has a (meth) acryloyloxy group and a C1-C6 alkylidene group in a molecule | numerator from the point that the effect of this invention becomes more remarkable. A thing with a (meth) acryloyloxy group in a molecule | numerator and a thing with a C1-C6 alkylidene group is more preferable.

  In addition to the cycloolefin monomer (a) and the cycloolefin monomer (b), the polymerizable composition (1) may contain other cycloolefin monomer (c).

  Examples of other cycloolefin monomers (c) include norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-propyl-2-norbornene, 5,6-dimethyl-2-norbornene, and 1-methyl. 2-norbornene, 7-methyl-2-norbornene, 5,5,6-trimethyl-2-norbornene, 5-phenyl-2-norbornene, tetracyclododecene, 1,4,5,8-dimethano-1, 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro Naphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8- Jime -1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8, 8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3- Dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahi Lonaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloro- 2-norbornene, 5,5-dichloro-2-norbornene, 5-fluoro-2-norbornene, 5,5,6-trifluoro-6-trifluoromethyl-2-norbornene, 5-chloromethyl-2-norbornene, Examples include 5-methoxy-2-norbornene, 5,6-dicarboxyl-2-norbornene anhydrate, 5-dimethylamino-2-norbornene, and 5-cyano-2-norbornene. These can be used alone or in combination of two or more.

  In the case of using the cycloolefin monomer (c), the content ratio of the cycloolefin monomer (c) is usually 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less in all monomers. .

(Ii) Metathesis polymerization catalyst The polymerizable composition (1) contains a metathesis polymerization catalyst for metathesis ring-opening (co) polymerization of the above-described cycloolefin monomer.
As the metathesis polymerization catalyst to be used, a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds with a transition metal atom as a central atom is usually mentioned. As transition metal atoms, atoms of Group 5, Group 6, and Group 8 (long period periodic table, the same applies hereinafter) are used. Although the atoms of each group are not particularly limited, examples of the Group 5 atom include tantalum, examples of the Group 6 atom include molybdenum and tungsten, and examples of the Group 8 atom include: Examples include ruthenium and osmium. Among these, a group 8 ruthenium or osmium complex is preferably used as a metathesis polymerization catalyst, and a ruthenium carbene complex is particularly preferable. The ruthenium carbene complex is excellent in catalytic activity during bulk polymerization, so it is excellent in the productivity of the crosslinkable resin composition layer, and the resulting crosslinkable resin composition layer has less odor derived from unreacted monomers and is easy to work with. Excellent. The ruthenium carbene complex is relatively stable to oxygen and moisture in the air and is not easily deactivated, so that it can be used for production in the atmosphere.

  Examples of the ruthenium carbene complex include those represented by the following general formula (i) or (ii).

In the general formulas (i) and (ii), R ¹¹ and R ¹² may each independently contain a hydrogen atom, a halogen atom, or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. A good C1-C20 hydrocarbon group is represented.

X ¹¹ and X ¹² each independently represent an arbitrary anionic ligand. An anionic ligand is a ligand having a negative charge when pulled away from a central metal atom, such as a halogen atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxyl group, an aryloxy group, A carboxyl group etc. can be mentioned. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

L ¹ and L ² each independently represent a hetero atom-containing carbene compound or a neutral electron donating compound other than the hetero atom-containing carbene compound. A heteroatom means an atom of Groups 15 and 16 of the Periodic Table, and specific examples include N, O, P, S, As, and Se atoms. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, and S atoms are preferable, and N atom is particularly preferable.

  The neutral electron donating compound may be any ligand as long as it has a neutral charge when pulled away from the central metal. Specific examples thereof include phosphines, ethers and pyridines, phosphines are preferable, and trialkylphosphine is more preferable.

In the general formulas (i) and (ii), R ¹¹ and R ¹² may be bonded to each other to form a ring, and further R ¹¹ , R ¹² , X ¹¹ , X ¹² , L ¹ and L ² may be bonded together in any combination to form a multidentate chelating ligand.

In the present invention, from the viewpoint of increasing the production efficiency of the crosslinkable resin composition layer and the like, the hetero atom-containing carbene compound is preferably a compound having a heterocyclic structure. As a hetero atom which comprises a heterocyclic structure, an O atom, an N atom, etc. are mentioned, for example, Preferably it is an N atom. Moreover, as a heterocyclic structure, an imidazoline structure and an imidazolidine structure are preferable.
Examples of the compound having a heterocyclic structure include compounds represented by the following general formula (iii) or general formula (iv).

In the formula, R ^{13 to} R ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms that may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Represents a hydrogen group. R ^{13 to} R ¹⁶ may be bonded to each other in any combination to form a ring.
Specific examples of the compound having a heterocyclic structure include 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3-diidene. (1-phenylethyl) -4-imidazoline-2-ylidene, benzylidene (1,3-dimesitylimidazolidin-2-ylidene), 1,3-dimesitylimidazolidin-2-ylidene, 1,3- Examples include dicyclohexylimidazolidine-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene, and the like.

The ruthenium carbene complex having such a compound having a heterocyclic structure as a ligand is represented by the above general formula (i) or (ii), and is composed of a compound having a heterocyclic structure as L ¹ or L ^2. Examples thereof include a ruthenium carbene complex having a ligand.

  Specific examples of the ruthenium carbene complex having a ligand composed of a compound having a heterocyclic structure include benzylidene (1,3-dimesityrylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3 -Dimesitylimidazolidin-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) Tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydro Imidazole-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole -5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityloimidazolidine-2-ylidene) Examples thereof include a ruthenium carbene complex in which a compound having a heterocyclic structure as a ligand such as pyridine ruthenium dichloride and a neutral electron donating compound other than the compound are bonded.

  These metathesis polymerization catalysts are used alone or in combination of two or more. The use amount of the metathesis polymerization catalyst is usually 1: 2,000 to 1: 2,000,000, preferably 1: 5,000 to 1: in a molar ratio of (metal atoms in the catalyst: total monomers). The range is 1,000,000, more preferably 1: 10,000 to 1: 500,000.

  If desired, the metathesis polymerization catalyst can be used by dissolving or suspending in a small amount of an inert solvent. Examples of such solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin, and mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, Alicyclic hydrocarbons such as diethylcyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; and alicyclic rings such as indene and tetrahydronaphthalene Hydrocarbons having an aromatic ring; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; oxygen-containing hydrocarbons such as diethyl ether and tetrahydrofuran; Among these, it is preferable to use aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and hydrocarbons having an alicyclic ring and an aromatic ring.

(Iii) Crosslinking aid The crosslinking aid is added to promote the crosslinking reaction. For example, polyfunctional compounds having two or more isopropenyl groups such as p-diisopropenylbenzene, m-diisopropenylbenzene, and o-diisopropenylbenzene; ethylene dimethacrylate, 1,3-butylene dimethacrylate, 1,4-butylene dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 2,2′-bis (4 -Methacryloxydiethoxyphenyl) propane, trimethylolpropane trimethacrylate, and pentaerythritol trimethacrylate Functional compounds; and the like. Among these, from the viewpoint of easily expressing the effects of the present invention, a polyfunctional compound having two or more methacryl groups is preferable, and a polyfunctional compound having three methacryl groups such as trimethylolpropane trimethacrylate and pentaerythritol trimethacrylate. Compounds are more preferred.

  The crosslinking assistants can be used alone or in combination of two or more. As content of the crosslinking adjuvant in the polymeric composition of this invention, it is 0.1-100 weight part normally with respect to 100 weight part of cycloolefin monomers, Preferably it is 0.5-50 weight part, More preferably 1 to 30 parts by weight.

(Iii) Crosslinking agent In addition, a crosslinking agent is added to the polymerizable composition (1) for the purpose of inducing a crosslinking reaction in a crosslinkable resin molded product obtained by bulk polymerization of the polymerizable composition (1). It is preferable to contain.
The resulting crosslinkable resin molded article can be a postcrosslinkable thermoplastic resin. Here, “after-crosslinking is possible” means that the resin can be heated to advance a crosslinking reaction to form a crosslinked resin.

  As the crosslinking agent, a radical generator is preferably used. Examples of the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators, with organic peroxides being preferred.

  Examples of the organic peroxide include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (t- Butylperoxy-m-isopropyl) benzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5-di ( dialkyl peroxides such as t-butylperoxy) hexane; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,2-di (t-butylperoxy) butane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -2-methylcycl Peroxyketals such as rhohexane and 1,1-di (t-butylperoxy) cyclohexane; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropylcarbonate, di (isopropylperoxy) Peroxycarbonates such as dicarbonate; alkylsilyl peroxides such as t-butyltrimethylsilyl peroxide; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, 3,6,9-triethyl-3, And cyclic peroxides such as 6,9-trimethyl-1,4,7-triperoxonane and 3,6-diethyl-3,6-dimethyl-1,2,4,5-tetroxane. Among these, dialkyl peroxides, peroxyketals, and cyclic peroxides are preferable in that there are few obstacles to the polymerization reaction.

  Examples of the diazo compound include 4,4'-bisazidobenzal (4-methyl) cyclohexanone, 2,6-bis (4'-azidobenzal) cyclohexanone, and the like.

  Nonpolar radical generators include 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1,1,2-triphenylethane, 1,1,1- And triphenyl-2-phenylethane.

  When a radical generator is used as the crosslinking agent, the 1 minute half-life temperature of the radical generator is appropriately selected depending on the crosslinking conditions, but is usually 100 to 300 ° C, preferably 150 to 250 ° C, more preferably. It is the range of 160-230 degreeC. The 1-minute half-life temperature of the radical generator may be referred to, for example, a catalog or homepage of each radical generator manufacturer (for example, NOF Corporation).

  A crosslinking agent can be used individually or in combination of 2 types or more, respectively. As content of the crosslinking agent in the polymeric composition used for this invention, it is 0.01-10 weight part normally with respect to 100 weight part of all the monomers, Preferably it is 0.1-10 weight part, More Preferably it is the range of 0.5-5 weight part.

(V) Other additives The polymerizable composition (1) is a chain transfer agent, a filler, a flame retardant, a polymerization regulator, a polymerization reaction retarder, an oxidation agent, if desired, in addition to the above components. An inhibitor or other compounding agent may further be contained.
Any of these components can be used alone or in combination of two or more. The addition amount may be appropriately selected within a range that does not impair the effects of the present invention.

  When a chain transfer agent is added, the followability at the time of heating and melting on the surface of the resulting crosslinkable resin composition layer can be further improved. Therefore, in a laminate obtained by laminating a crosslinkable resin composition layer obtained by using the polymerizable composition (1) formed by blending a chain transfer agent, heating, melting, and crosslinking, interlayer adhesion is obtained. And the peel strength is further improved. The chain transfer agent may further have one or more crosslinkable carbon-carbon unsaturated bonds. Such a crosslinkable carbon-carbon unsaturated bond is preferably present as a vinyl group or a vinylidene group.

  Specific examples of the chain transfer agent include hydrocarbon compounds having no hetero atom such as 1-hexene, 2-hexene, styrene, vinylcyclohexane, divinylbenzene; allylamine, glycidyl acrylate, allyl glycidyl ether, ethyl vinyl ether, methyl vinyl. Ketone, 2- (diethylamino) ethyl acrylate, 4-vinylaniline, vinyl methacrylate, allyl methacrylate, styryl methacrylate, allyl acrylate, undecenyl methacrylate, styryl acrylate, ethylene glycol diacrylate, allyltrivinylsilane, tetraallylsilane Hydrocarbon compounds having a heteroatom such as; These can be used alone or in combination of two or more. Among these, a hydrocarbon compound having no hetero atom is preferable, and styrene and divinylbenzene are more preferable from the viewpoint that the obtained laminate can be excellent in peel strength and crack resistance.

  As a compounding quantity of a chain transfer agent, Preferably it is 0.2-10 mol with respect to 1 mol of cycloolefin monomers, More preferably, it is 0.5-6 mol. When the blending ratio of the chain transfer agent is too small, the laminate property of the resulting crosslinkable resin composition layer tends to be lowered. On the other hand, when it is too much, the peel strength of the obtained laminate tends to be lowered.

  The filler is not particularly limited as long as it is generally used industrially, and both inorganic fillers and organic fillers can be used, but inorganic fillers are preferred. By mix | blending a filler with the polymeric composition (1) of this invention, the improvement of the mechanical strength and heat resistance of the laminated body obtained becomes possible.

As inorganic fillers, metal hydroxide fillers such as magnesium hydroxide, calcium hydroxide, aluminum hydroxide; silica balloon, alumina, iron oxide, tin oxide, beryllium oxide, barium ferrite, strontium ferrite, magnesium oxide, Metal oxide fillers such as titanium dioxide, zinc oxide and silicon dioxide (silica); Metal chloride fillers such as sodium chloride and calcium chloride; Metal sulfate fillers such as sodium sulfate and sodium hydrogen sulfate; Nitric acid Metal nitrate fillers such as sodium and calcium nitrate; Metal phosphate fillers such as sodium hydrogen phosphate and sodium dihydrogen phosphate; Metal titanates such as calcium titanate, strontium titanate and barium titanate Filler; sodium carbonate, calcium carbonate, magnesium carbonate Metal carbonate fillers such as sodium hydrogen carbonate; Carbide fillers such as boron carbide and silicon carbide; Nitride fillers such as boron nitride, aluminum nitride and silicon nitride; Aluminum, nickel, magnesium, copper, zinc Metal particle fillers such as iron, gold, silver, lead, tungsten; silicate fillers such as talc, clay, montmorillonite, calcium silicate, glass, glass balloon mica, kaolin, fly ash; glass powder; And carbon particles such as carbon black, graphite, activated carbon, and carbon balloon.
Examples of the organic filler include compound particles such as wood flour, starch, organic pigments, polystyrene, nylon, polyolefins such as polyethylene and polypropylene, vinyl chloride, and waste plastics.
The blending amount of the filler is usually 1 to 1000 parts by weight, preferably 10 to 500 parts by weight with respect to 100 parts by weight of all monomers.

As the flame retardant, any industrially used flame retardant can be used without any particular limitation. For example, tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, chlorinated polystyrene, chlorinated polyethylene, highly chlorinated polypropylene, chlorosulfonated polyethylene, hexabromobenzene, decabromodiphenyl oxide Bis (tribromophenoxy) ethane, 1,2-bis (pentabromophenyl) ethane, tetrabromobisphenol S, tetradecabromodiphenoxybenzene, 2,2-bis (4-hydroxy-3,5-dibromophenylpropane) ), Halogenated flame retardants such as pentabromotoluene; metal hydroxide flame retardants such as magnesium hydroxide and aluminum hydroxide; phosphorus-containing flame retardants; nitrogen-containing flame retardants; non-halogens such as antimony compounds such as antimony trioxide Emissions-based flame retardant; and the like.
The blending amount of the flame retardant is usually in the range of 1 to 1000 parts by weight, preferably 10 to 500 parts by weight with respect to 100 parts by weight of the total monomers.

  The polymerization regulator is blended for the purpose of controlling the polymerization activity or improving the polymerization reaction rate. Examples of the polymerization regulator include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium. , Tetraalkoxytin, tetraalkoxyzirconium and the like. These polymerization regulators can be used alone or in combination of two or more. In the case of using a polymerization regulator, the blending amount of the polymerization regulator is a molar ratio (metal atom in the metathesis polymerization catalyst: polymerization regulator), preferably 1: 0.05 to 1: 100, more preferably 1: It is in the range of 0.2 to 1:20, more preferably 1: 0.5 to 1:10.

  The polymerization reaction retarder is used for the purpose of suppressing an increase in the viscosity of the polymerizable composition (1) used in the present invention and more uniformly impregnating the reinforcing fiber of the composition. Polymerization reaction retarders include phosphine compounds such as triphenylphosphine, tributylphosphine, trimethylphosphine, triethylphosphine, dicyclohexylphosphine, vinyldiphenylphosphine, allyldiphenylphosphine, triallylphosphine, styryldiphenylphosphine; Lewis bases such as aniline and pyridine And the like.

  Examples of antioxidants include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. By blending these antioxidants, a crosslinking reaction It is preferable because the heat resistance of the obtained laminate can be improved to a high degree without hindering. Among these, a phenolic antioxidant and an amine antioxidant are preferable, and a phenolic antioxidant is more preferable.

  As other compounding agents, colorants, light stabilizers, foaming agents and the like can be used. As the colorant, a dye or a pigment is used. There are various kinds of dyes, and known ones may be appropriately selected and used.

  The polymerizable composition (1) can be obtained by mixing the above components. As a mixing method, according to a conventional method, for example, a liquid (catalyst liquid) in which a metathesis polymerization catalyst is dissolved or dispersed in an appropriate solvent is prepared. Separately, a cycloolefin monomer, a crosslinking aid, and other compounding agents as required. The liquid (monomer liquid) which mix | blended this is prepared, The said catalyst liquid is added to this monomer liquid, and the method of stirring is mentioned.

<Crosslinkable resin composition layer>
The crosslinkable resin composition layer is obtained by bulk polymerization of the polymerizable composition (1). Specifically, it can be obtained by coating or impregnating the polymerizable composition (1) on a support, and then bulk polymerizing the polymerizable composition (I).

Examples of the support used include a metal foil, a resin support film, a fibrous support, a metal drum, a steel belt, and a fluororesin belt.
As metal foil, metal foil which consists of metal materials, such as iron, stainless steel, copper, aluminum, nickel, chromium, gold, and silver, is mentioned.

Examples of the resin support film include polyethylene terephthalate film, polypropylene film, polyethylene film, polycarbonate film, polyethylene naphthalate film, polyarylate film, nylon film, polytetrafluoroethylene film, and polyimide film.
Although the thickness of these metal foil and resin support film is not particularly limited, it is usually 1 to 150 μm, preferably 2 to 100 μm, more preferably 3 to 75 μm from the viewpoint of workability and the like.

The fibrous support is not particularly limited, and a known organic or inorganic fibrous support can be used. Examples of the fibrous support include glass fiber, carbon fiber, aramid fiber, polyethylene terephthalate fiber, vinylon fiber, polyester fiber, amide fiber, metal fiber, and ceramic fiber. These can be used individually by 1 type or in combination of 2 or more types.
Examples of the shape of the fibrous support include a mat, a cloth, and a nonwoven fabric.

The method for applying the polymerizable composition (1) to the support is not particularly limited. For example, a known coating method such as a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a die coating method, a slit coating method, or ultrasonic spraying can be used. A film can be obtained.
The coating apparatus is not particularly limited as long as it can coat the polymerizable composition (1) on the support, and a known apparatus can be used. Specific examples include coating apparatuses described in JP-A-1-198639, JP-A-8-134235, and JP-A-8-174549.

  Moreover, when using a fibrous support as the support, a predetermined amount of the polymerizable composition (1) is applied to the fibrous support by the above-described method, and a protective film is stacked thereon as necessary. Further, if necessary, a method of impregnation by pressing with a roller or the like from the upper side, casting (coating) the polymerizable composition (1) on a sheet-like support, and stacking a fibrous support thereon, The method etc. which apply | coat polymeric composition (1) on it, and then press an application surface are mentioned.

  Examples of the protective film include the resin film exemplified as the sheet-like support. These surfaces may be subjected to a peeling treatment.

The amount of the polymerizable composition (1) used when it is applied or impregnated on the support is not particularly limited and can be appropriately set according to the thickness of the target layer.
The temperature when applying or impregnating the polymerizable composition (1) is usually 0 to 80 ° C. If the temperature at the time of application or impregnation is too high, a polymerization reaction starts at the time of application or impregnation, so that it is difficult to uniformly apply or impregnate the polymerizable composition (1).

  After the fibrous support is impregnated with the polymerizable composition (1), it is dried as desired, and then bulk polymerized. Bulk polymerization is usually performed by heating the polymerizable composition (1) to a predetermined temperature. The heating method of the polymerizable composition (1) is not particularly limited, and is a method of heating on a heating plate, a method of heating (hot pressing) while applying pressure using a press, and a method of pressing with a heated roller. And a method of heating in a heating furnace.

  The temperature for bulk polymerization of the polymerizable composition (1) is usually 30 to 250 ° C., preferably 50 to 200 ° C., more preferably 90 to 150 ° C., and 1 of the crosslinking agent, usually a radical generator. The half-life temperature is 1 minute or less, preferably 10 ° C. or less, more preferably 20 ° C. or less. The polymerization time may be appropriately selected, but is usually 1 second to 20 minutes, preferably 10 seconds to 5 minutes. By heating the polymerizable composition (1) under such conditions, a crosslinkable resin composition layer with few unreacted monomers can be obtained.

  The polymer constituting the crosslinkable resin composition layer obtained by bulk polymerization of the polymerizable composition (1) as described above has substantially no crosslink structure and is soluble in, for example, toluene. . The molecular weight of the polymer is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (eluent: tetrahydrofuran), and is usually 1,000 to 1,000,000, preferably 5,000 to It is in the range of 500,000, more preferably 10,000 to 100,000.

  Although the polymer which comprises the crosslinkable resin composition layer obtained is a resin composition which can be post-crosslinked, a part of the constituent resin may be crosslinked.

  The polymer constituting the crosslinkable resin composition layer is obtained by completing bulk polymerization, and there is no fear that the polymerization reaction further proceeds during storage.

  The thickness of the resulting crosslinkable resin composition layer is usually 10 to 1000 μm, preferably 10 to 300 μm, and more preferably 30 to 150 μm.

(2) Antioxidant layer The antioxidant layer of the laminate of the present invention has a polymerizability containing a polyphenylene ether resin having at least one radical polymerizable group or a phenol resin having at least one radical polymerizable group. It is a layer obtained from the composition (2).

The radical polymerizable group is not particularly limited as long as it has radical polymerizability, but is preferably an ethylenically unsaturated double bond group, more preferably a group containing a terminal ethylenically unsaturated bond. preferable. Examples of the group containing a terminal ethylenically unsaturated bond include a vinyl group containing a styryl group, an acryloyl group, and a methacryloyl group.
Further, the substitution position of the radical polymerizable group is not particularly limited, and may be one end or both ends of the polymer main chain, and the side chain (any position in the repeating unit of the polymer). It may be.

(I) Polyphenylene ether resin having at least one radical polymerizable group The polyphenylene ether resin is an oligomer or polymer having a repeating unit having a structure represented by the following formula.

  The polyphenylene ether resin used in the present invention (hereinafter sometimes referred to as “polyphenylene ether resin (2)”) is obtained by substituting at least one radical polymerizable group for such a polyphenylene ether resin. is there.

  The polyphenylene ether resin (2) used in the present invention is not particularly limited as long as it is a polyphenylene ether resin having a repeating unit having the structure represented by the above formula and has at least one radical polymerizable group. Examples thereof include compounds represented by the following formula (1) or (2).

The compound represented by the formula (1) represents a random copolymer of a phenol derivative, and l and m are degrees of polymerization and represent an integer of 1 or more. R ^{a to} R ^h each independently represent a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms.
Examples of the hydrocarbon group having 1 to 9 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, and n-hexyl. Alkyl groups having 1 to 9 carbon atoms such as a group, n-heptyl group, 1-methylpentyl group and 1-ethylpentyl group; C 1-9 cyclocarbons such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group. An alkyl group; an alkenyl group having 2 to 9 carbon atoms such as a vinyl group, an allyl group, an isopropenyl group, and a butenyl group; an alkynyl group having 2 to 9 carbon atoms such as a propynyl group and a butynyl group; 9 aromatic groups; or a group having 1 to 9 carbon atoms to which these groups are bonded; and the like.
However, at least one, preferably two, of R ^{a to} R ^h are hydrocarbon groups containing an unsaturated hydrocarbon group having 2 to 9 carbon atoms.

The compound represented by the formula (2) has a structure in which a phenol derivative is polymerized to a 4,4′-biphenoyl derivative and 4-vinylbenzyl groups are bonded to both ends.
In formula (2), n and p are polymerization degrees and represent an integer of 1 or more.
R ^u and R ^v each independently represents a divalent organic group having 1 or more carbon atoms.
Examples of the divalent organic group having 1 or more carbon atoms include, for example, an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, and an alkynylene having 2 to 20 carbon atoms. Groups, divalent hydrocarbon groups having an aromatic ring having 6 to 20 carbon atoms; and the like.

Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a trimethylene group, and a hexamethylene group.
Examples of the cycloalkylene group having 3 to 20 carbon atoms include a cyclopropylene group and a cyclohexylene group.
Examples of the alkenylene group having 2 to 20 carbon atoms include vinylene group and isopropenylene group.
A propynylene group etc. are mentioned as a C2-C20 alkynylene group.
Examples of the divalent hydrocarbon group having an aromatic ring having 6 to 20 carbon atoms include a phenylene group and a 2,6-naphthylene group.

  These groups may have a substituent at any position. Examples of the substituent include halogen atoms such as fluorine atom and chlorine atom; cyano group; hydroxyl group; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, n-butoxy group; vinyl group, allyl group, etc. An alkenyl group having 2 to 6 carbon atoms; a halogenated alkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group; a substituted amino group such as a dimethylamino group; and a carbon number 1 such as a methoxy group, an ethoxy group, and an isopropoxy group An alkoxy group having 1 to 6 carbon atoms substituted with an alkoxy group having 1 to 6 carbon atoms such as a methoxymethoxy group or a methoxyethoxy group; a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group A cycloalkyl group having 3 to 8 carbon atoms such as nitro group; an aryl group such as phenyl group, 4-chlorophenyl group and naphthyl group;

R ^{i to} R ^t each independently represents a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms, which is the same as R ^{a to} R ^h .

The number average molecular weight in terms of styrene in the gel permeation chromatography measurement (GPC) of the polyphenylene ether resin (2) is usually preferably from 500 to 5000, and more preferably from 1000 to 3000.
The polyphenylene ether resin (2) can be produced by a conventionally known method (for example, JP-A No. 2010-111758).
Moreover, a commercial item can also be used as it is as polyphenylene ether resin (2).

(Ii) Phenolic resin having at least one radical polymerizable group The phenolic resin is an oligomer or polymer obtained by condensing phenols and aldehydes.
The phenol resin used in the present invention (hereinafter sometimes referred to as “phenol resin (2)”) is obtained by substituting at least one radical polymerizable group for such a phenol resin fat.
The phenol resin is not particularly limited, but for example, the following formula (3)

(In the formula, R ^w represents a methyl group or an ethyl group, R ^x represents a hydrogen atom or an organic group having 1 to 10 carbon atoms which may have a substituent, and r is an integer of 2 to 5). Examples of the organic group having 1 to 10 carbon atoms include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group and alicyclic carbon group. (The hydrogen group and the aromatic hydrocarbon group may contain a nitrogen atom, an oxygen atom, or a sulfur atom, and may be linear or branched.)
A compound represented by formula (4):

(In the formula, s represents an integer of 0 to 20.)
In addition, a phenol aralkyl resin, a naphthol aralkyl resin, a biphenyl type phenol novolak resin, a biphenyl type naphthol novolak resin, a dicyclopentadiene-based phenol resin, and the like.

  The phenol resin (2) used in the present invention is an oligomer and polymer phenol resin obtained by condensing phenols and aldehydes, and particularly those having at least one radical polymerizable group substituted. Although not limited, a resin in which a substituent having a radical polymerizable group is substituted for a hydrogen atom of at least one phenolic hydroxyl group of the phenol resin is preferable.

  Examples of such a resin include a vinylbenzyl etherified phenol resin in which a 4-vinylbenzyl group is bonded to a phenolic hydroxyl group of a phenol resin. Specific examples thereof are shown in the following (5) and (6).

(In the formula, R ^w , R ^x , r, and s have the same meaning as described above.)
The compound represented by the formula (5) is a compound in which the phenol resin is represented by the formula (3), and a 4-vinylbenzyl group is bonded to all or a part of the phenolic hydroxyl group of the phenol resin. The compound represented by the formula (6) is a compound in which the phenol resin is represented by the formula (4), and all or a part of the phenolic hydroxyl group of the phenol resin contains 4-vinyl. A compound to which a benzyl group is bonded.

The vinyl benzyl etherified phenol resin can be obtained, for example, by reacting the phenol resin with vinyl benzyl halide in a polar neutral solvent using an alkali metal hydroxide as a dehydrohalogenating agent (for example, JP, 9-31006, A).
Moreover, as a phenol resin, what is marketed can be used suitably.

  Examples of the vinyl benzyl halide include p-vinyl benzyl chloride, m-vinyl benzyl chloride, a mixture of p-vinyl benzyl chloride and m-vinyl benzyl chloride, p-vinyl benzyl bromide, m-vinyl benzyl bromide, p-vinyl benzyl bromide. And a mixture of m-vinylbenzyl bromide and the like. Among these, it is preferable to use p-vinylbenzyl chloride and a mixture of p-vinylbenzyl chloride and m-vinylbenzyl chloride. When p-vinylbenzyl chloride is used, the symmetry is improved, and a vinylbenzyl compound having a high melting point and a high softening point can be obtained. Further, when a mixture of p-vinylbenzyl chloride and m-vinylbenzyl chloride is used, a vinylbenzyl compound having a low melting point and a low softening point is obtained, and the workability is improved.

  The mixing ratio of the phenol resin and the vinyl benzyl halide can be appropriately selected. For example, the molar ratio of the phenolic hydroxyl group of the phenol resin to the vinyl benzyl halide is a ratio of about 100: 40 to 100: 120. .

  Examples of polar neutral solvents include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and hexamethylphosphoramide; sulfur-containing systems such as dimethyl sulfoxide, tetramethylene sulfone and sulfolane. Solvent; nitrile solvents such as acetonitrile; ether solvents such as dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, 1,2-dimethoxyethane, 1,3-dimethoxypropane; ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetone, cyclohexanone Solvent; and mixtures thereof; and the like.

  Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide and a mixture thereof. The amount of the alkali metal hydroxide used is preferably about 1.1 to 2.0 times mol for 1 mol of phenolic hydroxyl group, for example.

In addition, in the presence of a phase transfer catalyst such as a quaternary ammonium compound, a quaternary phosphonium compound, or a tertiary sulfonium compound, the phenol resin and vinylbenzyl halide are removed from the alkali metal hydroxide in the water / organic solvent mixture. By reacting as a hydrogen halide agent, a vinylbenzyl etherified phenol resin can also be obtained.
The amount of these phase transfer catalysts to be used depends on the catalyst type, reaction temperature, etc., but is usually about 0.01 to 0.5 times mol for 1 mol of phenolic hydroxyl group.

The reaction temperature is usually 30 to 100 ° C., and the reaction time is usually 0.5 to 20 hours, although it depends on the reaction scale and the like.
Moreover, a commercial item can also be used as it is as a phenol resin (2).

In addition to the polyphenylene ether resin (2) or the phenol resin (2), the polymerizable composition (2) preferably contains a high molecular weight component and an inorganic filler.
The blending ratio of the resin component, the high molecular weight component, and the inorganic filler is preferably 70 to 90 parts by weight of the resin component, 10 to 30 parts by weight of the high molecular weight component, and 150 to 400 parts by weight of the inorganic filler.

As the high molecular weight component, it is preferable to use a styrene elastomer excellent in compatibility with the polyphenylene ether resin (2), and it is more preferable to use a hydrogenated styrene thermoplastic elastomer from the viewpoint of dielectric properties.
Examples of the hydrogenated styrene-based thermoplastic elastomer include hydrogenated styrene-butadiene copolymers having a styrene content of 10 to 70 wt% and a styrene equivalent number average molecular weight of 50,000 to 100,000. A commercially available product can be used as it is as the hydrogenated styrene-based thermoplastic elastomer.

As the inorganic filler, it is preferable to use a silicon oxide filler in order to improve the dielectric properties of the cured product of the polymerizable composition (2). Moreover, it is preferable to use a spherical filler from a viewpoint of highly filling the filler. Although there is no restriction | limiting in particular in the particle size of a spherical silicon oxide filler, it is preferable that it is 10 micrometers or less, and it is still more preferable that it is the range of 0.2-3 micrometers.
The spherical silicon oxide filler is preferably used after its surface is treated with a silane coupling agent from the viewpoint of improving dielectric properties, low moisture absorption, and solder heat resistance. The surface treatment of the spherical silicon oxide filler with a coupling agent may be performed by adding a filler that has been surface-treated in advance to the resin composition, or by adding a silane coupling agent to the resin composition and adjusting the resin composition You may carry it in.

The polymerizable composition (2) preferably further contains a polymerization initiator.
Although it does not restrict | limit especially as a polymerization initiator, It is preferable to apply a radical polymerization initiator. The starting temperature of the curing reaction can be adjusted according to the type of radical polymerization initiator.

Examples of the radical polymerization initiator include isobutyl peroxide, α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, 1, 1, 3 3-tetramethylbutylperoxyneodecanoate, diisopropylperoxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di-2-ethoxyethylperoxydicarbonate, di (2 -Ethylhexylperoxy) dicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydidecanate, di (3-methyl-3-methoxybutylperoxy) dicarbonate, t-butylperoxyneodecanoate, t-hexyl peroxypivale , T-butylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2, 5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, m-toluoyl peroxide, t-butylperoxyisobutyrate, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumylperoxa De, di -t- butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne -3, t-butyl trimethylsilyl peroxide.
Among these, those that are solid at room temperature are preferable because foaming can be suppressed.
These can be used individually by 1 type or in combination of 2 or more types.
The addition amount is adjusted in the range of 0.0005 to 20 parts by weight, with the total amount of the resin components being 100 parts by weight.

The polymerizable composition (2) preferably further contains a solvent.
As the solvent to be used, those having a boiling point of 140 ° C. or lower are preferable, and those having a boiling point of 110 ° C. or lower are preferable. Examples of such a solvent include xylene, toluene, cyclohexane, and mixed solvents thereof. Further, it may contain a solvent used for the coupling treatment of the inorganic filler, for example, a polar solvent such as methyl ethyl ketone and methanol.
The amount of solvent used is preferably such that, for example, the resin concentration in the solvent is 40 to 65% by weight.

Moreover, the polymerizable composition (2) may further contain other compounding agents and the like exemplified as those that can be contained in the polymerizable composition (1).
The polymerizable composition (2) can be obtained by mixing the respective components in the same manner as the polymerizable composition (1).
The melt viscosity of the polymerizable composition (2) is preferably 100 to 2000 mPa · s.

<Antioxidation layer>
The antioxidant layer is formed from the polymerizable composition (2). Specifically, it can be obtained by applying the polymerizable composition (2) to a support and then polymerizing it.

Examples of the support used include polyethylene terephthalate film, polypropylene film, polyethylene film, polycarbonate film, polyethylene naphthalate film, polyarylate film, nylon film, polytetrafluoroethylene film and the like.
As a method of apply | coating, the thing similar to the method of apply | coating the said polymeric composition (1) is mentioned.
Although the polymerization temperature depends on the resin used, etc., it is usually 30 to 250 ° C., preferably 50 to 150 ° C., and the polymerization time is usually 1 second to 20 minutes, preferably 10 seconds to 1 hour. .

After the reaction, the antioxidant layer can be obtained by peeling the support.
The thickness of the resulting antioxidant layer is not particularly limited, but is usually 0.5 to 500 μm, preferably 5 to 60 μm, and more preferably 10 to 50 μm.

(3) Laminate The laminate of the present invention has the crosslinkable resin composition layer and the antioxidant layer, and at least one of the outermost layers of the laminate is an antioxidant layer.
Each of the crosslinkable resin composition layer and the antioxidant layer may be a single layer or two or more layers.
As a structural example of the laminated body of this invention, crosslinkable resin composition layer / antioxidation layer, antioxidant layer / crosslinkable resin composition layer / antioxidation layer, etc. are mentioned.

The thickness of the laminate of the present invention is usually 20 to 2000 μm, preferably 50 to 500 μm.
The thickness of the antioxidant layer (total thickness in the case of two or more layers) is preferably 5% to 30% of the total thickness of the laminate.

  Although the manufacturing method of the laminated body of this invention is not restrict | limited in particular, Usually, the method of laminating | crosslinking a crosslinkable resin composition layer and an antioxidant layer in a predetermined order, and hot-pressing the whole is mentioned.

The temperature at the time of hot pressing is usually 100 to 300 ° C, preferably 150 to 280 ° C, more preferably 180 to 250 ° C.
The pressure at the time of hot pressing is usually 0.5 to 20 MPa, preferably 2 to 10 MPa. The hot pressing may be performed in a vacuum or a reduced pressure atmosphere. The hot pressing can be performed using a known press having a press frame mold for flat plate forming, a press molding machine such as a sheet mold compound (SMC) or a bulk mold compound (BMC).

  In the laminate of the present invention, since the antioxidant layer is formed on the outermost layer, even when the obtained laminate is placed under a high temperature (about 200 ° C.) for a long time, the surface deteriorates. Thus, cracks do not occur and the interlayer adhesion is excellent.

  The fact that the laminate of the present invention has such characteristics is, for example, a test in which the laminate is placed at a high temperature of 200 ° C. and observed for occurrence of cracks using an optical microscope every 100 hours. This can be confirmed. The laminate of the present invention does not cause cracks or the like due to the surface being deteriorated by heat even after being placed at a high temperature of 200 ° C. for 400 hours, and the crosslinkable resin composition layer and the antioxidant are prevented. There is no delamination at the interface of the layers.

2) Metal-clad laminate The metal-clad laminate of the present invention is obtained by further laminating a metal foil on the outer side of the antioxidant layer comprising the polymerizable composition (2) which is the outermost layer in the laminate of the present invention. It is characterized by becoming.
The metal-clad laminate of the present invention is (α) a method of laminating a metal foil on the outer side of the antioxidant layer located in the outermost layer of the laminate of the present invention, placing this between stainless steel plates, and hot pressing. And (β) when producing the laminate of the present invention, a method in which a crosslinkable resin composition layer and an antioxidant layer are laminated in a predetermined order, and a metal foil is laminated on the top and bottom of the method, Can be manufactured by.
The hot pressing can be performed by the same method as that for manufacturing the laminate.

  Since the metal foil laminate of the present invention uses the laminate of the present invention, the surface does not deteriorate even when placed at a high temperature for a long time, and has excellent interlayer adhesion. is there.

  The metal-clad laminate of the present invention having the above characteristics can be suitably used as a circuit board material for electric / electronic devices. More specifically, it is suitable for single-sided, double-sided or multilayered substrate materials, and core materials for package substrates.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples.

(Example 1)
(Step 1) Synthesis of 5-norbornen-2-yl methacrylate (bicyclo [2.2.1] hept-5-en-2-yl methacrylate) (hereinafter abbreviated as “MAcNB”)

  20 g (0.18 mol) of 5-norbornen-2-ol was dissolved in 100 g of a mixed solution of ethyl acetate: toluene = 1: 1 (mass ratio). Thereto was further added 22 g (0.22 mol) of triethylamine, and further slowly added 21 g (0.20 mol) of methacrylic acid chloride in an ice bath, and then the whole volume was reduced to 4 in an ice bath (10 ° C. or lower). Stir for hours. At this time, disappearance of the raw materials was confirmed by gas chromatography analysis.

After completion of the reaction, 48 g of 1N hydrochloric acid was gradually added while stirring the reaction mixture, and then 48 g of saturated brine was added and stirred for 30 minutes. Thereafter, liquid separation was performed, and an organic layer was separated. To the obtained organic layer, 90 g of a 10% aqueous sodium carbonate solution was added, and the whole volume was stirred at room temperature (25 ° C.) for 12 hours, followed by liquid separation. The organic layer was separated, washed twice with 60 g of 10% brine, dried over anhydrous sodium sulfate, and sodium sulfate was filtered off. The organic solvent was removed from the filtrate under reduced pressure, and the resulting residue was purified by silica gel column chromatography (developing solvent: n-hexane (volume ratio)) to give the target MAcNB as a colorless liquid. 0.4 g (0.11 mol) was obtained (yield 60%).
As a result of analyzing the final purified product by gas chromatography, it contained 0.3% by mass of methacrylic acid chloride as an impurity. However, the raw material 5-norbornen-2-ol was not detected, and the purity was 99.0%. Met.

(Step 2) Preparation of polymerizable composition (1-1) 0.6 part of benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and triphenylphosphine 12 parts was dissolved in 18.1 parts of indene to prepare a catalyst solution.

  Separately, as cycloolefin monomer, 9-ethylidenetetracyclo [6.2.1.13, 6.02,7] dodec-4-ene (ETD) 40 parts, dicyclopentadiene 60 parts, Production Example 1 A mixture containing 15 parts of MAcNB synthesized in the above and 0.28 part of 2,6-bis (1,1-dimethylethyl) -4-methylphenol as an antioxidant was placed in a glass container, and an inorganic filler was added here. 100 parts of silica (treated with silane coupling agent, average particle size 0.5 μm), 31 parts of trimethylolpropane trimethacrylate as a crosslinking aid, and 60 parts of aluminum dimethylphosphinate as a flame retardant are mixed uniformly. did.

Next, 2 parts of styrene as a chain transfer agent and 2 parts of di-t-butyl peroxide as a crosslinking agent were added thereto to obtain a monomer liquid.
The entire amount of the metathesis catalyst solution was added to the obtained monomer solution and stirred to obtain a polymerizable composition (1-1).

(Step 3) Production of Crosslinkable Resin Composition Layer 1 The polymerizable composition (1-1) is applied to both sides of a 43 μm thick fibrous support (IPC product number # 1078, fiber-opening treatment, manufactured by Nittobo Co., Ltd.). Then, a PET film having a thickness of 50 μm was bonded to both surfaces as a support film. This was heated at 120 ° C. for 3.5 minutes to conduct a polymerization reaction, and then the support film was peeled off to obtain a crosslinkable resin composition layer 1 having a thickness of 100 μm.

(Step 4) Preparation of polymerizable composition (2-1) In a planetary stirrer, 40 parts of a polyphenylene ether oligomer (product name “SA9000”, manufactured by SABIC) and spherical silica having an average particle size of 0.5 μm as a filler 50 parts of surface-treated spherical silica treated with γ-methacryloxypropyldimethoxysilane, 10 parts of a hydrogenated styrene-based thermoplastic elastomer (product name “Tuftec H1043” manufactured by Asahi Kasei Co., Ltd.), and toluene as a solvent Charge and stir until dissolved. Subsequently, 0.5 part of α, α′-di (t-butylperoxy) diisopropylbenzene was mixed as a polymerization initiator to obtain a polymerizable composition (2-1) having a solid content concentration of 65%.

(Step 5) Production of antioxidant layer 1 After the polymerizable composition (2-1) was applied on a polyimide film by a die coater, and then heated at 80 ° C. for 5 minutes to remove the solvent. The polyimide film was peeled off to obtain an antioxidant layer 1 having a thickness of 12 μm.

(Step 6)
The both sides of the 100 μm thick crosslinkable resin composition layer 1 are sandwiched between uncured 12 μm thick antioxidant layers 1, which are further sandwiched between 18 μm thick copper foils, and pressurized to 3 MPa by a vacuum press. The temperature was increased at a constant rate from (25 ° C.) and held at 180 ° C. for 60 minutes to obtain a copper clad laminate 1.

(Example 2)
Steps 1 to 4 were performed in the same manner as in Example 1.

(Step 5) Production of Antioxidation Layer 2 An oxidation prevention layer 2 having a thickness of 25 μm was obtained in the same manner as in Step 5 of Example 1, except that the coating amount by the die coater was changed in Step 5 of Example 1. It was.

(Step 6)
A copper-clad laminate 2 was obtained in the same manner as in Step 6 of Example 1, except that the antioxidant layer 1 having a thickness of 12 μm was changed to the antioxidant layer 2 having a thickness of 25 μm in Step 6 of Example 1. .

(Example 3)
Steps 1 to 3 were performed in the same manner as in Example 1.

(Step 4) Preparation of polymerizable composition (2-2) In the presence of a quaternary ammonium salt (tetra-n-butylammonium bromide) according to the method disclosed in JP-A-2007-119531, a phenol resin (product) Name “SK Resin HE-100C-30”, manufactured by Air Water) and vinylbenzyl chloride (product name “CMS-P”, manufactured by AGC Seimi Chemical Co., m / p isomer: 50/50 wt% mixture) Was reacted at 80 ° C. in a water / organic solvent mixture using an alkali metal hydroxide (sodium hydroxide) as a dehydrohalogenating agent to obtain a vinylbenzyl etherified phenol resin.
40 parts of vinyl benzyl etherified phenol resin, 50 parts of surface-treated spherical silica treated with γ-methacryloxypropyldimethoxysilane on spherical silica having an average particle size of 0.5 μm as a filler, hydrogenated styrene thermoplastic 10 parts of an elastomer (product name “Tuftec H1043”, manufactured by Asahi Kasei Co., Ltd.) and toluene as a solvent were added and stirred until dissolved. Subsequently, 0.5 parts of dicumyl peroxide was mixed as a polymerization initiator to obtain a polymerizable composition (2-2) having a solid content concentration of 65%.

(Step 5) Production of Antioxidation Layer 3 Step 5 of Example 1 except that the polymerizable composition (2-1) was changed to the polymerizable composition (2-2) in Step 5 of Example 1. Similarly, an antioxidant layer 3 having a thickness of 12 μm was obtained.

(Step 6)
A copper clad laminate 3 was obtained in the same manner as in Step 6 of Example 1 except that the antioxidant layer 1 was changed to the antioxidant layer 3 in Step 6 of Example 1.

Example 4
Steps 1 to 5 were performed in the same manner as in Example 1.

(Step 6)
In Step 6 of Example 1, the copper clad laminate 4 was obtained in the same manner as in Step 6 of Example 1, except that the number of the antioxidant layers 1 used for the antioxidant layer was changed from one to three. It was.

(Comparative Example 1)
Steps 1 to 5 were performed in the same manner as in Example 1.

(Step 6)
In Step 6 of Example 1, a copper-clad laminate 5 was obtained in the same manner as Step 6 of Example 1 except that the antioxidant layer 1 was not used.

(Comparative Example 2)
Steps 1 to 3 were performed in the same manner as in Example 1.

(Step 4) Preparation of Resin Composition (1) 42.5 parts of tetrabromobisphenol A type epoxy resin (manufactured by Japan Epoxy Resin, “Epicoat 5047”, epoxy equivalent 550), cresol novolak type epoxy resin (Dainippon Ink Chemical Co., Ltd.) “Epicron N-690”, epoxy equivalent 210) 7.5 parts, surface treated spherical silica treated with epoxy silane on spherical silica with an average particle size of 0.5 μm as a filler, curing agent As a curing accelerator, 0.1 part of 2-ethyl-4-methylimidazole was dissolved in N, N-dimethylformamide as a curing accelerator, and the resin composition (1 )

(Step 5) Production of Antioxidation Layer 4 Except that the polymerizable composition (2-1) was changed to the resin composition (1) in Step 5 of Example 1, it was the same as Step 5 of Example 1. Thus, an antioxidant layer 4 having a thickness of 12 μm was obtained.

(Step 6)
A copper clad laminate 6 was obtained in the same manner as in Step 6 of Example 1 except that the antioxidant layer 1 was changed to the antioxidant layer 4 in Step 6 of Example 1.

(Comparative Example 3)
In Example 4, a copper clad laminate 7 was obtained in the same manner as in Example 4 except that the antioxidant layer 4 was used instead of the antioxidant layer 1.

  About the copper clad laminated bodies 1-7 obtained in Examples 1-4 and Comparative Examples 1-3, the crack test and the adhesiveness test shown below were done.

(Crack test)
For the copper clad laminates 1 to 7, each of the copper foils removed by etching was cut into 5 cm squares to prepare samples, and 10 obtained samples were put into an oven at a temperature of 200 ° C. every 100 hours. One by one was taken and the time (h) until cracks were confirmed with an optical microscope was measured. The results are shown in Table 1 below.

(Adhesion test)
The cross section of the sample after aging was visually observed, and the presence or absence of peeling at the interface between the crosslinkable resin composition layer and the antioxidant layer was confirmed. The case where there was no peeling was evaluated as ○, and the case where there was peeling was evaluated as ×. The results are shown in Table 1 below.

From Table 1, it can be seen that the copper clad laminates 1 to 4 of Examples 1 to 4 do not generate cracks for a long time and have excellent adhesion.
On the other hand, cracks occurred early in the copper clad laminate 5 of Comparative Example 1 that did not use an antioxidant layer. Moreover, the copper clad laminated bodies 6 and 7 of Comparative Examples 2 and 3 using the antioxidant layer 4 manufactured by the resin composition (1) were inferior in adhesion.

Claims (6)

A crosslinkable resin composition layer obtained by bulk polymerization of a polymerizable composition (1) containing a cycloolefin monomer, a metathesis polymerization catalyst, and a crosslinking aid, and a polyphenylene ether having at least one radical polymerizable group A laminate having an antioxidant layer obtained from a polymerizable composition (2) containing a resin or a phenol resin,
At least one of the outermost layers of the laminate is the antioxidant layer.   The laminate according to claim 1, wherein the polymerizable composition (2) contains a polyphenylene ether resin having two radical polymerizable groups.   The laminate according to claim 2, wherein the number average molecular weight of the polyphenylene ether resin having two radical polymerizable groups is 500 to 5,000.   The laminate according to any one of claims 1 to 3, wherein the crosslinking aid is a polyfunctional compound containing 2 to 4 radically polymerizable groups.   The laminate according to any one of claims 1 to 4, wherein the polymerizable composition (2) further contains a hydrogenated styrenic thermoplastic elastomer.   The metal-clad laminate in which the metal foil is further laminated | stacked on the outer side of the antioxidant layer which consists of the polymeric composition (2) which is the outermost layer in the laminated body of Claims 1-5.