JP2013075985A - Crosslinking complex, crosslinked complex, and method for production of the crosslinked complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crosslinking complex useful for production of a laminate excellent in peel strength with less warping, a crosslinked complex with high flexural modulus obtained by using the crosslinking complex and to provide a method for production of the crosslinked complex.SOLUTION: The crosslinking complex contains a cycloolefinic polymer, a crosslinking agent, a trifunctional compound having three crosslinking functional groups, and a crosslinking fibrous reinforcement. The cycloolefinic polymer contains a repeating unit A derived from a cycloolefinic monomer having a (meth)acryloyl group, and a repeating unit B derived from a cycloolefinic monomer having no (meth)acryloyl group in a range of a weight ratio [(repeating unit A):(repeating unit B)] of 1:99 to 30:70.

Description

  The present invention relates to a crosslinkable composite having excellent peel strength and useful for producing a laminate having a small warp, a crosslinkable composite having a high flexural modulus obtained by using this crosslinkable composite, and this crosslinkable composite The present invention relates to a method for manufacturing a body.

In recent years, with the advent of advanced information technology, information transmission has begun to increase in speed and frequency, and microwave communication and millimeter wave communication have become a reality, and the dielectric loss tangent is small to reduce transmission loss at high frequencies to the limit. There is a need for materials.
As a resin material having a small dielectric loss tangent, a cycloolefin polymer obtained by polymerizing a cycloolefin monomer has attracted attention.

For example, Patent Document 1 describes a cycloolefin polymer composite including a cycloolefin polymer and a glass fiber reinforcing material containing 55% by weight or more of SiO ₂ . Further, in Patent Document 1, the composite is excellent in low thermal expansion, electrical insulation, moldability, adhesion, mechanical strength, heat resistance, and the like, and is useful as an insulating material used for an electric circuit board. It is also described.

International Publication No. 2008/117799 Pamphlet

As described above, cycloolefin polymer composites having excellent performance have been obtained so far. However, conventional cycloolefin polymer composites have a cycloolefin polymer impregnation property to a fibrous reinforcing material, cyclohexane polymer composites, In some cases, the strength between the olefin polymer and the fibrous reinforcing material is not sufficient, and the substrate obtained using such a composite may be warped by heating during reflow.
As a method for obtaining a substrate that is difficult to warp, it is conceivable to increase the flexural modulus of the cycloolefin polymer composite. However, it is difficult for a substrate having a layer made of such a cycloolefin polymer composite to improve the adhesion between the layer made of the composite and the metal foil, and the peel strength may be lowered. .
The present invention has been made in view of such prior art, and is a crosslinkable composite useful for the production of a laminate having excellent peel strength and low warpage, and bending elasticity obtained using this crosslinkable composite. It is an object of the present invention to provide a crosslinked composite having a high rate and a method for producing the crosslinked composite.

  In order to solve the above problems, the present inventors have intensively studied a crosslinkable composite containing a cycloolefin polymer and a fibrous reinforcing material. As a result, by using a crosslinkable composite containing a cycloolefin polymer having a specific repeating unit, a crosslinker, a trifunctional compound having three crosslinkable functional groups, and a crosslinkable fibrous reinforcing material, As a result, the present invention has been completed.

Thus, according to the first aspect of the present invention, the following crosslinkable composites (1) to (6) are provided.
(1) A crosslinkable composite containing a cycloolefin polymer, a crosslinking agent, a trifunctional compound having three crosslinkable functional groups, and a crosslinkable fibrous reinforcing material, wherein the cycloolefin polymer is (meth) A repeating unit derived from a cycloolefin monomer having an acryloyl group (repeating unit A) and a repeating unit derived from a cycloolefin monomer not having a (meth) acryloyl group (repeating unit B) are in a weight ratio (repeating unit A: repeating unit). The crosslinkable composite which B) contains in the range of 1: 99-30: 70.
(2) The cycloolefin polymer comprises a cycloolefin monomer having a (meth) acryloyl group and a cycloolefin monomer having no (meth) acryloyl group in a weight ratio (cycloolefin monomer having a (meth) acryloyl group: ( The crosslinkable composite according to (1), which is obtained by polymerizing a cycloolefin monomer having no (meth) acryloyl group in a range of 1:99 to 30:70.
(3) a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, and a trifunctional compound having three crosslinkable functional groups, wherein the cycloolefin monomer has a (meth) acryloyl group and (meth) A cycloolefin monomer having no acryloyl group and a weight ratio (cycloolefin monomer having a (meth) acryloyl group: cycloolefin monomer having no (meth) acryloyl group) in a range of 1:99 to 30:70 The crosslinkable composite according to (1) or (2), which is obtained by impregnating the polymerizable composition contained in a crosslinkable fibrous reinforcing material and then bulk polymerizing the impregnated polymerizable composition. .
(4) The crosslinkable functional group in the trifunctional compound having three crosslinkable functional groups is a group having an aliphatic carbon-carbon double bond, according to any one of (1) to (3). Crosslinkable complex.
(5) In any one of (1) to (4), the crosslinkable fibrous reinforcing material is obtained by surface-treating the fibrous reinforcing material with a surface treatment agent having a crosslinkable functional group. The crosslinkable composite described.
(6) The crosslinkable composite according to any one of (1) to (5), wherein the crosslinkable fibrous reinforcing material is a fibrous reinforcing material having an aliphatic carbon-carbon double bond on the surface thereof. .

According to a second aspect of the present invention, there is provided a crosslinked complex of the following (7).
(7) A crosslinked complex obtained by crosslinking the crosslinkable complex according to any one of (1) to (6).
According to a third aspect of the present invention, there is provided a method for producing a crosslinked composite according to the following (8).
(8) A cycloolefin monomer, a polymerization catalyst, a crosslinking agent, and a trifunctional compound having three crosslinkable functional groups, wherein the cycloolefin monomer has a (meth) acryloyl group and (meth) A cycloolefin monomer having no acryloyl group and a weight ratio (cycloolefin monomer having a (meth) acryloyl group: cycloolefin monomer having no (meth) acryloyl group) in a range of 1:99 to 30:70 A step of impregnating the crosslinkable fibrous reinforcing material with the polymerizable composition contained therein,
Next, a step of bulk polymerizing the impregnated polymerizable composition to obtain a crosslinkable composite,
A step of crosslinking the obtained crosslinkable composite,
The manufacturing method of the crosslinked composite_body | complex as described in (7) which has these.

According to the first aspect of the present invention, it is possible to obtain a crosslinkable composite which is excellent in peel strength and useful for the production of a laminate having a small warpage.
According to the second aspect of the present invention, a crosslinked composite having a large flexural modulus can be obtained.
According to the third aspect of the present invention, a method for easily producing the crosslinked composite can be obtained.

  The crosslinkable composite of the present invention is a crosslinkable composite containing a cycloolefin polymer, a crosslinking agent, a trifunctional compound having three crosslinkable functional groups, and a crosslinkable fibrous reinforcing material, and the cycloolefin The weight ratio of the repeating unit derived from a cycloolefin monomer having a (meth) acryloyl group (repeating unit A) and the repeating unit derived from a cycloolefin monomer not having a (meth) acryloyl group (repeating unit B) The repeating unit A: the repeating unit B) is contained in the range of 1:99 to 30:70. In general, the (meth) acryloyl group may be referred to as a (meth) acryl group.

[Cycloolefin polymer]
The cycloolefin polymer used in the present invention has, in the molecule, a repeating unit derived from a cycloolefin monomer having a (meth) acryloyl group (repeating unit A) and a repeating unit derived from a cycloolefin monomer not having a (meth) acryloyl group ( Repeating unit B) at least, and the weight ratio of these repeating units (repeating unit A: repeating unit B) is contained in the range of 1:99 to 30:70, preferably 5:95 to 30:70. To do.

A cycloolefin having a repeating unit derived from a cycloolefin monomer having a (meth) acryloyl group (in this specification, “(meth) acryloyl group” represents “acryloyl group” or “methacryloyl group”). The polymer is likely to participate in the crosslinking reaction. As a result, a cross-linked composite having excellent heat resistance is obtained, and a laminate having a layer made of the cross-linked composite has low warpage at high temperatures and high peel strength. In addition, by having a repeating unit derived from a cycloolefin monomer having no (meth) acryloyl group, the moldability (fluidity) at the time of heating and melting of the crosslinkable composite is improved, so that a laminate having high peel strength is obtained. be able to. When the weight ratio of the repeating unit A and the repeating unit B is not within the above range, these effects cannot be obtained, and particularly the peel strength of the laminate is lowered.
In addition, the cycloolefin polymer used for this invention may contain the repeating unit derived from arbitrary monomers, as long as expression of the effect of this invention is not inhibited.

  The cycloolefin monomer used for the production of the cycloolefin polymer is a compound having an alicyclic structure formed of carbon atoms and having one polymerizable carbon-carbon double bond in the alicyclic structure. Examples of the alicyclic structure of the cycloolefin monomer include monocycles, polycycles, condensed polycycles, bridged rings, and combination polycycles 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. In the present specification, “polymerizable carbon-carbon double bond” refers to a carbon-carbon double bond capable of chain polymerization (ring-opening polymerization). There are various types of ring-opening polymerization such as ionic polymerization, radical polymerization, and metathesis polymerization. Typically, this refers to metathesis ring-opening polymerization.

  The cycloolefin monomer having a (meth) acryloyl group may have a substituent in addition to the (meth) acryloyl group. Examples of the substituent include a hydrocarbon group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkylidene group, and an aryl group, and a polar group such as a carboxyl group and an acid anhydride group. However, from the viewpoint of making the obtained laminate a low dielectric loss tangent, the cycloolefin monomer having a (meth) acryloyl group preferably has no polar group.

  Examples of the cycloolefin monomer having a (meth) acryloyl group include a monocyclic cycloolefin monomer having a (meth) acryloyl group, a norbornene monomer having a (meth) acryloyl group, and a norbornene system having a (meth) acryloyl group. Monomers are preferred. In the present specification, the “norbornene monomer” refers to a cycloolefin monomer having a norbornene ring structure in the molecule. Examples include norbornenes, dicyclopentadiene, and tetracyclododecene.

  As a norbornene-type monomer which has a (meth) acryloyl group, the compound represented by the following formula | equation (I) is mentioned, for example.

In formula (I), R ^{1 to} R ⁴ each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, and at least ^{one of} R ^{1 to} R ⁴ is a (meth) acryloyl group. It is an organic group having n represents 0, 1 or 2.

Examples of the organic group having 1 to 30 carbon atoms represented by R ^{1 to} R ⁴ include the substituents exemplified above, such as a hydrocarbon group having 1 to 30 carbon atoms and a polar group. R ¹ or R ² may combine with R ³ or R ⁴ to form a ring.
Examples of the organic group having 1 to 30 carbon atoms having a (meth) acryloyl group include groups represented by the following formulae.

  In the above formula, the carbon atom represented by * represents the carbon atom constituting the alicyclic structure of the cycloolefin monomer. m represents an integer of 1 to 10. Among these, a group having a methacryloyl group is preferable because of excellent reactivity.

In the formula (I), n is 0, 1 or 2, preferably 0 or 1.
Examples of the monomer in which n is 0 include 5-norbornen-2-yl methacrylate, 5-norbornen-2-yl acrylate, 5-norbornen-2-ylmethyl methacrylate, 5-norbornen-2-ylmethyl acrylate, and methacrylic acid. 5-norbornen-2-ylethyl, 5-norbornen-2-ylethyl acrylate, 5-norbornen-2-ylpropyl methacrylate, 5-norbornen-2-ylpropyl acrylate, 5-norbornen-2-ylbutyl methacrylate, 5-norbornen-2-yl butyl acrylate, 5-norbornen-2-yl hexyl methacrylate, 5-norbornen-2-yl hexyl acrylate, 5-norbornen-2-yl octyl methacrylate, 5-norbornen-2-yl octyl acrylate, Methacryl 5-norbornene-2-Irudeshiru, acrylic acid 5-norbornene-2-Irudeshiru like.
As the monomer in which n is 1, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-3-carboxylic acid 2- (methacryloyloxy) ethyl, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-8-ene-3-carboxylic acid 2- (acryloyloxy) ethyl and the like.

Examples of the cycloolefin monomer having no (meth) acryloyl group include a monocyclic cycloolefin monomer and a polycyclic cycloolefin monomer. From the viewpoint of highly balancing the dielectric properties and heat resistance of the resulting crosslinked composite, polycyclic cycloolefin monomers are preferred. As the polycyclic cycloolefin monomer, a norbornene-based monomer is particularly preferable.
A cycloolefin monomer having no (meth) acryloyl group may have a substituent. Examples of the substituent include those described above in the cycloolefin monomer having a (meth) acryloyl group.

The cycloolefin monomer having no (meth) acryloyl group may have no crosslinkable carbon-carbon unsaturated bond, or may have one or more crosslinkable carbon-carbon unsaturated bonds. Good. As used herein, “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, but typically 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, i.e., aliphatic carbon-carbon double bonds or triple bonds, typically Refers to an aliphatic carbon-carbon double bond. In the cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds, the position of the unsaturated bond is not particularly limited, and in addition to the alicyclic structure formed by carbon atoms, other than the alicyclic structure It may be present at any position of, for example, at the end or inside of the side chain. For example, the aliphatic carbon-carbon double bond includes a vinyl group (CH ₂ ═CH—), a vinylidene group (CH ₂ ═C <), a vinylene group (—CH═CH—), or a 1-propenylidene group (> C = CH—CH ₃ ), and preferably exhibits a radical crosslinking reactivity. Therefore, it preferably exists as a vinyl group, vinylidene group or 1-propenylidene group, and exists as a vinylidene group or 1-propenylidene group. More preferably.

  Cycloolefin monomers having no crosslinkable carbon-carbon unsaturated bond include cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexane. Monocyclic cycloolefin monomers such as hexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, and cycloheptene; norbornene, 1-methyl-2-norbornene, 5- Methyl-2-norbornene, 7-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-propyl-2-norbornene, 5-phenyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5, 5,6-trimethyl Bicyclic cycloolefin monomers such as 2-norbornene; 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene (TCD), 2-methyl-1, 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4 4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-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- , 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-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano -1,2,3,4,4a, 5,8,8a-tetracyclic dodecene-structured tetracyclic cycloolefin monomers such as 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, 5-methoxy-2-norbornene, 5,6- And norbornene monomers such as dicarboxyl-2-norbornene anhydrate, 5-dimethylamino-2-norbornene, and 5-cyano-2-norbornene; Among these, since a crosslinked resin molded article having a high glass transition temperature and flexural elasticity and excellent crack resistance can be obtained, a tetracyclododecene structure having no crosslinkable carbon-carbon unsaturated bond is obtained. Cyclic cycloolefin monomers are preferred.

Cycloolefin monomers having one or more crosslinkable carbon-carbon unsaturated bonds include 3-vinylcyclohexene, 4-vinylcyclohexene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexene. Monocyclic cycloolefin monomers such as xadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, and 1,3-cyclooctadiene; 5-methylidene-2-norbornene, 5-ethylidene- Such as 2-norbornene, 5-n-propylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 5,6-diethylidene-2-norbornene, etc. Bicyclic cycloolefin monomers; tricyclic cycloolefins such as dicyclopentadiene Fin monomer; 9-methylidene-tetracyclo [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-propenyltetracyclo [6.2.1.1 ^3,6 . ^0,7 ] dodeca-4-ene and other tetracyclic cycloolefin monomers having a tetracyclododecene structure; and 2,5-norbornadiene and other norbornene monomers; and the like. Among these, since a crosslinked resin molded article having high glass transition temperature and flexural elasticity and excellent crack resistance can be obtained, it has one or more crosslinkable carbon-carbon unsaturated bonds, and has a tetracyclododecene structure. Preferred are tetracyclic cycloolefin monomers.

The cycloolefin polymer comprises a cycloolefin monomer having a (meth) acryloyl group and a cycloolefin monomer not having a (meth) acryloyl group in a weight ratio (cycloolefin monomer having a (meth) acryloyl group: (meth) acryloyl group). Can be obtained by polymerizing in the range of 1:99 to 30:70, preferably 5:95 to 30:70. When outside the above range, the peel strength of the laminate tends to decrease.
A cycloolefin monomer having a (meth) acryloyl group can be used alone or in combination of two or more, and a cycloolefin monomer having no (meth) acryloyl group can be used alone or in combination. Two or more kinds can be used in combination.
In addition, as long as expression of the effect of this invention is not inhibited, you may superpose | polymerize using the arbitrary monomers copolymerizable with said cycloolefin monomer.

  In the polymerization reaction of cycloolefin monomer, a polymerization catalyst is usually used. The polymerization catalyst is not particularly limited as long as it can polymerize the cycloolefin monomer, but when producing the crosslinkable composite of the present invention, it is preferable to use bulk polymerization, usually metathesis polymerization. A catalyst is used.

  Examples of the metathesis polymerization catalyst include a complex formed by bonding a plurality of ions, atoms, polyatomic ions, compounds, etc. with a transition metal atom as a central atom, which is capable of metathesis ring-opening polymerization of the cycloolefin monomer. It is done. As transition metal atoms, atoms of Group 5, Group 6, and Group 8 (according to the 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 them, the group 8 ruthenium or osmium is preferable as the transition metal atom. That is, as the metathesis polymerization catalyst, a complex having ruthenium or osmium as a central atom is preferable, and a complex having ruthenium as a central atom is more preferable. As the complex having ruthenium as a central atom, a ruthenium carbene complex in which a carbene compound is coordinated to ruthenium is preferable. Here, the “carbene compound” is a general term for compounds having a methylene free group, and refers to a compound having an uncharged divalent carbon atom (carbene carbon) as represented by (> C :). Since the ruthenium carbene complex is excellent in catalytic activity during bulk polymerization, the polymerization product has little odor derived from unreacted monomers, and a high-quality polymerization product with high productivity can be obtained. In addition, it is relatively stable to oxygen and moisture in the air and is not easily deactivated, so that it can be used even in the atmosphere.

  Specific examples of the ruthenium carbene complex include complexes represented by the following formula (II) or formula (III).

In formulas (II) and (III), R ⁵ and R ⁶ each independently contain a hydrogen atom; a halogen atom; or a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom or silicon atom. It represents a good cyclic or chain hydrocarbon group having 1 to 20 carbon atoms. X ¹ and X ² each independently represent an arbitrary anionic ligand. 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. R ⁵ and R ⁶ may be bonded to each other to form an aliphatic ring or an aromatic ring that may contain a hetero atom. Furthermore, R ⁵ , R ⁶ , X ¹ , X ² , L ¹ and L ² may be bonded together in any combination to form a multidentate chelating ligand.

  A heteroatom means an atom of groups 15 and 16 of the periodic table, and specifically, a nitrogen atom (N), an oxygen atom (O), a phosphorus atom (P), a sulfur atom (S), an arsenic atom (As), a selenium atom (Se), etc. can be mentioned. Among these, N, O, P, and S are preferable from the viewpoint of obtaining a stable carbene compound, and N is particularly preferable.

  As the ruthenium carbene complex, since the mechanical strength and impact resistance of the resulting crosslinked composite can be highly balanced, at least one carbene compound having a heterocyclic structure as a hetero atom-containing carbene compound is used as a ligand. Are preferably included. As the heterocyclic structure, an imidazoline ring structure or an imidazolidine ring structure is preferable.

  Examples of the carbene compound having a heterocyclic structure include compounds represented by the following formula (IV) or formula (V).

In formulas (IV) and (V), R ^{7 to} R ¹⁰ each independently include 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. Represents a good cyclic or chain hydrocarbon group having 1 to 20 carbon atoms. R ^{7 to} R ¹⁰ may be bonded to each other in any combination to form a ring.

  Examples of the compound represented by the formula (IV) or formula (V) include 1,3-dimesitylimidazolidin-2-ylidene, 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1 , 3-dicyclohexylimidazolidine-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-di (1-phenyl) Ethyl) -4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene, and the like.

  In addition to the compound represented by the formula (IV) or formula (V), 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole- 5-ylidene, 1,3-dicyclohexylhexahydropyrimidin-2-ylidene, N, N, N ′, N′-tetraisopropylformamidinylidene, 1,3,4-triphenyl-4,5-dihydro-1H Heteroatom-containing carbene compounds such as -1,2,4-triazole-5-ylidene and 3- (2,6-diisopropylphenyl) -2,3-dihydrothiazol-2-ylidene can also be used.

In the formulas (II) and (III), the anionic (anionic) ligands X ¹ and X ² are ligands having a negative charge when separated from the central atom. For example, halogen atoms such as fluorine atom (F), chlorine atom (Cl), bromine atom (Br), and iodine atom (I), diketonate group, substituted cyclopentadienyl group, alkoxy group, aryloxy group, and carboxyl Examples include groups. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

  The neutral electron-donating compound may be any ligand as long as it has a neutral charge when it is separated from the central atom. Specific examples thereof include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, and thiocyanates. Among these, phosphines, ethers and pyridines are preferable, and trialkylphosphine is more preferable.

  Examples of the ruthenium carbene complex represented by the formula (II) include benzylidene (1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-4,5 -Dibromo-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4-imidazoline-2-ylidene) (3-phenyl-1H-indene-1-ylidene) (tricyclohexyl) Phosphine) ruthenium dichloride, (1,3-dimesitylimidazolidine-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octa Hydrobenzui Dazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3- Dimesityl-2,3-dihydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H- 1,2,4-triazol-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylid (1,3-Dimesitylimidazolidin-2-ylidene) pyridine ruthenium dichloride, (1,3-Dimesitylimidazolidin-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, 1,3-Dimesityl-4-imidazoline-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) [ (Phenylthio) methylene] (tricyclohexylphosphine) ruthenium dichloride and (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) (2-pyrrolidone-1-ylmethylene) (tricyclohexylphosphine) ruthenium Dichloride Which is a ruthenium carbene complex in which a heteroatom-containing carbene compound and a neutral electron-donating compound are each bonded;

  A ruthenium carbene complex in which two neutral electron donating compounds such as benzylidenebis (tricyclohexylphosphine) ruthenium dichloride and (3-methyl-2-buten-1-ylidene) bis (tricyclopentylphosphine) ruthenium dichloride are bonded;

  Two heteroatom-containing carbene compounds such as benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride and benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride bonded together Ruthenium carbene complex; and the like.

  Examples of the ruthenium carbene complex represented by the formula (III) include (1,3-dimesitymylimidazolidine-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene) (1 , 3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride, and the like.

  Among these ruthenium carbene complexes, those having one compound represented by the formula (II) and represented by the formula (V) as a ligand are most preferable.

  These ruthenium carbene complexes are described in Org. Lett. 1999, Vol. 1, page 953, and Tetrahedron. Lett. 1999, Vol. 40, page 2247, and the like.

The metathesis polymerization catalyst can be used alone or in combination of two or more.
The amount of the metathesis polymerization catalyst used is a molar ratio (metal atom in the metathesis polymerization catalyst: cycloolefin monomer) and is usually from 1: 2,000 to 1: 2,000,000, preferably from 1: 5,000 to 1. : 1,000,000, more preferably in the range of 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. 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, diethyl Cycloaliphatic hydrocarbons such as cyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic rings such as indene and tetrahydronaphthalene And 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 a chain aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, and a hydrocarbon having an alicyclic ring and an aromatic ring.

[Crosslinking agent]
The crosslinking agent used in the present invention is a compound that can induce a crosslinking reaction of the cycloolefin polymer. Therefore, the composite according to the first aspect of the present invention is a composite that can be post-crosslinked. Here, “after-crosslinking is possible” means that the crosslinking reaction can proceed by heating the complex. In this specification, this complex is referred to as a “crosslinkable complex”, and the crosslinking reaction. The composite finished with is called a “crosslinked composite”. Since the crosslinkable composite has a certain viscosity even when heated and melted, its shape is maintained. On the other hand, when an arbitrary member is brought into contact, the surface of the crosslinkable composite finally crosslinks and cures while exhibiting followability to the shape of the member. Therefore, by using a crosslinkable composite, it is possible to obtain a laminate having a layer composed of a crosslinkable composite having a high flexural modulus and excellent interlayer adhesion.

  Although it does not specifically limit as a crosslinking agent, Usually, a radical generator is used suitably. Examples of the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators, and organic peroxides and nonpolar radical generators are preferable.

  Examples of organic peroxides 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 (t- Dialkyl peroxides such as 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-methylcyclohexa Peroxyketals such as 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 a crosslinking agent, the half-life temperature for 1 minute is appropriately selected depending on the conditions for curing (crosslinking of the crosslinkable complex), but is usually 100 to 300 ° C, preferably 150 to 250 ° C. More preferably, it is the range of 160-230 degreeC. Here, the half-life temperature for 1 minute is a temperature at which half of the radical generator decomposes in 1 minute. For example, it is 186 ° C. for di-t-butyl peroxide and 194 ° C. for 2,5-dimethyl-2,5-bis (t-butylperoxy) -3-hexyne.

A crosslinking agent can be used individually by 1 type or in combination of 2 or more types.
Content of a crosslinking agent is 0.01-10 weight part normally with respect to 100 weight part of cycloolefin polymers, Preferably it is 0.1-10 weight part, More preferably, it is 0.5-5 weight part.

[Trifunctional compound having three crosslinkable functional groups]
The trifunctional compound having three crosslinkable functional groups used in the present invention (hereinafter, “trifunctional compound having three crosslinkable functional groups” may be abbreviated as “trifunctional compound”) is a crosslinking aid. It is a compound that is used as an agent and does not participate in a ring-opening polymerization reaction, but is a compound that can participate in a crosslinking reaction induced by a crosslinking agent and constitute a part of a crosslinked structure. By using a trifunctional compound, a crosslinked composite having a high crosslinking density and excellent heat resistance can be obtained.
Examples of the crosslinkable functional group of the trifunctional compound include a group having a crosslinkable carbon-carbon unsaturated bond, and a group having an aliphatic carbon-carbon double bond is preferable. Especially, since it is excellent in crosslinking reactivity, a vinylidene group or a group having a vinylidene structure is preferable, an isopropenyl group or a methacryloyl group is more preferable, and a methacryloyl group is more preferable.
The trifunctional compound is preferably a trifunctional compound having three vinylidene groups or groups having a vinylidene structure, and more preferably a trifunctional compound having three methacryloyl groups. Specific examples include trimethylolpropane trimethacrylate and pentaerythritol trimethacrylate.

A trifunctional compound can be used individually by 1 type or in combination of 2 or more types.
The content of the trifunctional compound is usually 10 to 25 parts by weight, preferably 15 to 25 parts by weight with respect to 100 parts by weight of the cycloolefin polymer.
When the content of the trifunctional compound is in the above range, a crosslinked composite having excellent heat resistance and dielectric loss tangent can be obtained.

[Crosslinkable fibrous reinforcement]
The crosslinkable fibrous reinforcing material used in the present invention is a fibrous reinforcing material that has a crosslinkable functional group on its surface and can participate in a crosslinking reaction. As the crosslinkable functional group, a hydrophobic group is usually selected. By using such a crosslinkable fibrous reinforcing material, the cycloolefin polymer and the crosslinkable fibrous reinforcing material can be crosslinked, and a crosslinked composite having a large flexural modulus can be obtained. Moreover, the impregnation property of a cycloolefin polymer improves compared with the case where a normal fibrous reinforcement is used.
Examples of the crosslinkable functional group in the crosslinkable fibrous reinforcement include the same as those described above as the crosslinkable functional group of the trifunctional compound. A preferable crosslinkable fibrous reinforcing material includes a fibrous reinforcing material having an aliphatic carbon-carbon double bond on the surface thereof.
The crosslinkable fibrous reinforcing material can be obtained, for example, by treating an untreated fibrous reinforcing material with a surface treatment agent having a crosslinkable functional group.

  As a surface treating agent which has a crosslinkable functional group, the compound represented by Formula (VI) is mentioned, for example.

In the formula (VI), M represents a silicon atom or a titanium atom, R ¹¹ represents a group having a crosslinkable and hydrophobic aliphatic carbon-carbon double bond, and X ³ represents a hydrolyzable group or R ¹² represents a hydroxyl group, and R ¹² represents an alkyl group which may have a substituent. m and n each independently represent an integer of 1 to 3, and m + n represents an integer of 2 to 4.

The group having a crosslinkable and hydrophobic aliphatic carbon-carbon double bond represented by R ¹¹ is preferably an organic group having 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and a vinyl group Or a group having a vinyl structure or a vinylidene structure is preferable. Specifically, vinyl group, allyl group, isopropenyl group, 3-butenyl group, vinylphenyl group (p-styryl group), (meth) acryloxyethyl group, (meth) acryloxypropyl group, and (meth) An acryloxybutyl group etc. are mentioned.
The hydrolyzable group represented by X ³ is preferably an alkoxyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Specific examples include a methoxy group and an ethoxy group.
The alkyl group represented by R ¹² is preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Examples of the substituent include a glycidyl group and an amino group.

  In the formula (VI), M is preferably a silicon atom. Examples of the compound in which M is a silicon atom include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-butenyltrimethoxysilane, 3-butenyltriethoxysilane, and vinylphenyltrimethoxysilane. (P-styryltrimethoxysilane), vinylphenyltriethoxysilane (p-styryltriethoxysilane), β-methacryloxyethyltrimethoxysilane, β-methacryloxyethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, δ-methacryloxybutyltrimethoxysilane, δ-methacryloxybutyltriethoxysilane, β-acryloxyethyltrimethoxysilane, β-acryloxyethyltri Examples include ethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, δ-acryloxybutyltrimethoxysilane, and δ-acryloxybutyltriethoxysilane.

  As the fibrous reinforcing material treated with the surface treatment agent, inorganic and / or organic fibers can be used. For example, PET (polyethylene terephthalate) fibers, aramid fibers, ultra-high molecular polyethylene fibers, polyamide (nylon) Fibers, and organic fibers such as liquid crystal polyester fibers; inorganic fibers such as glass fibers, carbon fibers, alumina fibers, tungsten fibers, molybdenum fibers, butene fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, and silica fibers; Etc. Among these, organic fibers and glass fibers are preferable, and aramid fibers, liquid crystal polyester fibers, and glass fibers are particularly preferable. As the glass fiber, fibers such as E glass, NE glass, S glass, D glass, and H glass can be suitably used.

  The surface treatment can be performed by bringing the surface treatment agent into contact with the surface of the fibrous reinforcing material. The contact method is not particularly limited. For example, a dry method in which a surface treatment agent is directly sprayed on the surface of the fibrous reinforcing material, or a solution obtained by dissolving the surface treatment agent in a solvent is applied to the surface of the fibrous reinforcing material. The wet method to contact is mentioned. A surface treating agent can be used individually by 1 type or in combination of 2 or more types.

The crosslinkable fibrous reinforcing material can be used alone or in combination of two or more. The form of the crosslinkable fibrous reinforcing material is not particularly limited, and examples thereof include mats, cloths, and nonwoven fabrics.
The content of the crosslinkable fibrous reinforcing material is usually 10 to 90 parts by weight, preferably 20 to 80 parts by weight, and more preferably 30 to 70 parts by weight with respect to 100 parts by weight of the cycloolefin polymer. By being in this range, the balance between the dielectric properties and mechanical strength of the resulting crosslinked composite is maintained, which is preferable.

(Crosslinkable complex)
The crosslinkable composite of the present invention contains, for example, a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, and a trifunctional compound having three crosslinkable functional groups, and the cycloolefin monomer has a (meth) acryloyl group. A cycloolefin monomer having a cycloolefin monomer having no (meth) acryloyl group and a cycloolefin monomer having a (meth) acryloyl group to a cycloolefin monomer having a (meth) acryloyl group: 1:99 It can be easily obtained by impregnating a polymerizable composition contained in a range of ˜30: 70 into a crosslinkable fibrous reinforcing material and then bulk polymerizing the impregnated polymerizable composition.

  In addition to the cycloolefin monomer, the polymerization catalyst, and the trifunctional compound having three crosslinkable functional groups, the polymerizable composition to be used may optionally include a reactive fluidizing agent, a chain transfer agent, a filler, and a flame retardant. , Polymerization regulators, polymerization reaction retarders, anti-aging agents, other compounding agents, and the like can be added.

The reactive fluidizing agent is a compound that can improve the plasticity of the crosslinkable composite and participate in the crosslinking reaction to constitute a part of the crosslinking. Examples of the reactive fluidizing agent include monofunctional or bifunctional compounds having a vinylidene group or a group having a vinylidene structure.
The reactive fluidizing agent can be used alone or in combination of two or more. The content of the reactive fluidizing agent is usually 1 to 20 parts by weight, preferably 5 to 20 parts by weight with respect to 100 parts by weight of the cycloolefin monomer.

A known chain transfer agent can be used as the chain transfer agent. By including a chain transfer agent, the followability at the time of heating and melting is improved, so that a laminate superior in peel strength can be obtained. The chain transfer agent may have a crosslinkable carbon-carbon unsaturated bond. Such a crosslinkable carbon-carbon unsaturated bond is preferably present as a vinyl group or vinylidene group.
Specific examples of such chain transfer agents include aliphatic olefins such as 1-hexene and 2-hexene; aromatic olefins such as styrene, divinylbenzene and stilbene; alicyclic olefins such as vinylcyclohexane; Vinyl ethers such as vinyl ether; vinyl ketones such as methyl vinyl ketone, 1,5-hexadien-3-one, 2-methyl-1,5-hexadien-3-one, and the like. Among these, a hydrocarbon compound having no hetero atom is preferable, and divinylbenzene is more preferable because a crosslinked composite or laminate having a small dielectric loss tangent can be obtained.
A chain transfer agent can be used individually by 1 type or in combination of 2 or more types. The content of the chain transfer agent is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the cycloolefin monomer.

A known filler can be used as the filler. Either an inorganic filler or an organic filler can be used, but usually an inorganic filler is preferably used. By containing the filler, a crosslinked composite and a laminate having excellent mechanical strength and heat resistance can be obtained.
A filler can be used individually by 1 type or in combination of 2 or more types. The content of the filler is usually 1 to 1,000 parts by weight, preferably 10 to 500 parts by weight, and more preferably 50 to 350 parts by weight with respect to 100 parts by weight of the cycloolefin monomer.

  As the flame retardant, a known halogen flame retardant or non-halogen flame retardant can be used. Halogen flame retardants include 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), pentabromotoluene and the like.

  In the present invention, if blended with the polymerizable composition, the flame retardancy of the resulting laminate can be improved, and since there is no fear of dioxin generation when the laminate is burned, a non-halogen flame retardant is preferably used. It is done. Non-halogen flame retardants are composed of flame retardant compounds that do not contain halogen atoms. As the non-halogen flame retardant, any industrially used one can be used without any particular limitation. For example, antimony compounds such as antimony trioxide; metal hydroxide flame retardants such as aluminum hydroxide and magnesium hydroxide; phosphinate flame retardants such as aluminum dimethylphosphinate and aluminum diethylphosphinate; magnesium oxide and aluminum oxide Metal oxide flame retardants; such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, and bisphenol A bis (dicresyl) phosphate Phosphorus-containing flame retardants other than phosphinates; nitrogen-containing flame retardants such as melamine derivatives, guanidines and isocyanurs; ammonium polyphosphate, melamine phosphate, polyphosphorus Melamine polyphosphate melam, guanidine phosphate, and flame retardants containing both phosphorus and nitrogen phosphazene, and the like; and the like. As the non-halogen flame retardant, an antimony compound, a metal hydroxide flame retardant, a phosphinate flame retardant, and a phosphorus-containing flame retardant other than phosphinate are preferable. As the phosphorus-containing flame retardant, tricresyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, and bisphenol A bis (dicresyl) phosphate are particularly preferable.

  A flame retardant can be used individually by 1 type or in combination of 2 or more types. Content of a flame retardant is 10-300 weight part normally with respect to 100 weight part of cycloolefin monomers, Preferably it is 20-200 weight part, More preferably, it is 30-150 weight part.

The polymerization regulator is a compound that can control the polymerization activity. Polymerization regulators include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium, tetra Examples thereof include alkoxy tin and tetraalkoxy zirconium.
A polymerization regulator can be used individually by 1 type or in combination of 2 or more types. The content 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: 0.2 to 1:20. More preferably, it is in the range of 1: 0.5 to 1:10.

A polymerization reaction retarder is a compound that can suppress an increase in the viscosity of the polymerizable 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 Etc. can be used.
A polymerization reaction retarder can be used individually by 1 type or in combination of 2 or more types. What is necessary is just to adjust suitably content of a polymerization reaction retarder as needed.

As the anti-aging agent, known anti-aging agents such as phenol-based anti-aging agents, amine-based anti-aging agents, phosphorus-based anti-aging agents, and sulfur-based anti-aging agents can be used. Among these, a phenolic antiaging agent and an amine antiaging agent are preferable, and a phenolic antiaging agent is more preferable. By containing an anti-aging agent, it is possible to obtain a crosslinked composite and a laminate having excellent heat resistance.
Antiaging agents can be used singly or in combination of two or more. The content of the anti-aging agent is preferably 0.0001 to 10 parts by weight, more preferably 0.001 to 5 parts by weight, and still more preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the cycloolefin monomer. is there.

  Examples of other compounding agents include colorants, light stabilizers, pigments, and foaming agents. These compounding agents can be used alone or in combination of two or more. The content is appropriately selected within a range that does not impair the effects of the present invention.

  The polymerizable composition can be obtained by mixing the above components. As a mixing method, a conventional method may be followed. For example, a liquid (catalyst liquid) in which a metathesis polymerization catalyst is dissolved or dispersed in an appropriate solvent is prepared, and another essential component such as a cycloolefin monomer and a crosslinking agent, If desired, a liquid containing other compounding agents can be prepared, and a catalyst solution can be added to the resulting liquid and stirred.

  Examples of the method for impregnating the polymerizable composition into the crosslinkable fibrous reinforcing material include, for example, a predetermined amount of the polymerizable composition, spray coating method, dip coating method, roll coating method, curtain coating method, die coating method, and Examples thereof include a method of applying to a crosslinkable fibrous reinforcing material by a known method such as a slit coating method, overlaying a protective film thereon if desired, and pressing with a roller or the like from above.

  After the polymerizable composition is impregnated into the crosslinkable fibrous reinforcing material, it can be dried as desired, and the impregnated product is heated to a predetermined temperature to polymerize the polymerizable composition to obtain a crosslinkable composite. . The heating temperature is usually in the range of 30 to 250 ° C., preferably 50 to 200 ° C., more preferably 90 to 150 ° C., and less than or equal to the one minute half-life temperature of the crosslinking agent, usually a radical generator, preferably The 1-minute half-life temperature is 10 ° C. or lower, more preferably the 1-minute half-life temperature is 20 ° C. or lower. 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 under such conditions, a crosslinkable complex with less unreacted monomer can be obtained.

  As a heating method, in the case of molding using a mold having a conventionally known split mold structure, a method using a heating means such as an electric heater or steam disposed in the mold, or a mold within an electric furnace The method of heating is mentioned.

Moreover, block polymerization can also be performed in the state which contacted the polymeric composition and the support body using the support body. In this case, a support may be used in place of the protective film, or the polymerizable composition may be applied to a crosslinkable fibrous reinforcing material previously laid on the support.
Examples of the support include films and plates made of resins such as polytetrafluoroethylene, polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, and nylon; iron, stainless steel, copper, aluminum, nickel, chromium And films and plates made of metal materials such as gold, silver, and the like. Among these, use of a metal foil or a resin film is preferable. The thickness of the metal foil or resin film 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 metal foil preferably has a smooth surface, and the surface roughness (Rz) is a value measured by an AFM (atomic force microscope), usually 10 μm or less, preferably 5 μm or less, more preferably Is 3 μm or less, more preferably 2 μm or less. If the surface roughness of the metal foil is in the above range, for example, in the obtained high-frequency circuit board, generation of noise, delay, transmission loss and the like in high-frequency transmission is suppressed, which is preferable. The surface of the metal foil is preferably treated with a known coupling agent or adhesive such as a silane coupling agent, a thiol coupling agent, and a titanate coupling agent. By using a support, a laminate having a layer composed of a crosslinked composite can be easily obtained. For example, when a copper foil is used as the support, a resin-coated copper foil (Resin Coated Copper (RCC)) is used. Can be easily obtained.

  When using a support, the heating method includes a method of heating the polymerizable composition applied to the support on a heating plate, a method of heating (hot pressing) while applying pressure using a press, and heating. And a method of pressing with a heated roller, a method of heating in a heating furnace, and the like. These methods are suitably used for obtaining a sheet-like or film-like crosslinkable composite. The thickness of the crosslinkable composite obtained is usually in the range of 0.001 to 10 mm, preferably 0.005 to 1 mm, more preferably 0.01 to 0.5 mm. If it exists in this range, the shaping property at the time of lamination | stacking and the mechanical strength, toughness, etc. of a laminated body will improve, and it is suitable.

  The polymer constituting the crosslinkable composite obtained 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.

  The crosslinkable composite of the present invention is a composite containing a post-crosslinkable resin, but a part of the constituent resin may be cross-linked. For example, when the polymerizable composition is bulk-polymerized in the mold, the temperature of a part of the mold may become too high because the polymerization reaction heat hardly diffuses in the central part of the mold. In the high temperature part, a cross-linking reaction occurs, and cross-linking may occur. However, if the surface part that easily dissipates heat is formed of a crosslinkable resin that can be postcrosslinked, the crosslinkable composite of the present invention can sufficiently exhibit a desired effect.

The crosslinkable composite obtained by the above method is preferably a polymer obtained by completing bulk polymerization. By completing the bulk polymerization, there is no possibility that the polymerization reaction further proceeds during storage. In addition, the crosslinkable composite of the present invention contains a crosslinking agent such as a radical generator, but unless it is heated to a temperature that causes a crosslinking reaction, the surface hardness does not change and storage stability is improved. Excellent.
The crosslinkable resin constituting the crosslinkable composite of the present invention has a glass transition point of usually 130 ° C. or lower, preferably 120 ° C. or lower. When the glass transition point of the crosslinkable resin is 130 ° C. or less, the moldability is excellent. Therefore, when the crosslinkable composite of the present invention is used as a prepreg, a laminate having excellent interlayer adhesion can be produced.

[Crosslinked composite]
The cross-linked composite of the present invention is obtained by cross-linking the cross-linkable composite. The crosslinking reaction can be performed by heating the crosslinkable complex to a predetermined temperature or higher. The heating temperature is usually equal to or higher than the temperature at which a crosslinking reaction is induced by the crosslinking agent. For example, when a radical generator is used as a crosslinking agent, it is usually at least 1 minute half-life temperature, preferably at least 5 ° C. above 1-minute half-life temperature, more preferably at least 10 ° C. above 1-minute half-life temperature. It is. Typically, it is in the range of 100 to 300 ° C, preferably 150 to 250 ° C. The heating time is in the range of 0.1 to 180 minutes, preferably 0.5 to 120 minutes, more preferably 1 to 60 minutes. Moreover, a crosslinked composite can also be produced using the polymerizable composition without stopping at the stage of the crosslinkable composite. That is, after impregnating the polymerizable composition into the crosslinkable fibrous reinforcing material, by maintaining it above the temperature at which the above-mentioned crosslinkable composite crosslinks (specifically, heating at the above temperature and time). By doing so, it is possible to proceed together with the bulk polymerization of the cycloolefin monomer and the crosslinking reaction in the cycloolefin polymer produced by the polymerization to produce the crosslinked composite of the present invention. Thus, when manufacturing a crosslinked composite, according to said method, if copper foil is used as a support body, a copper clad laminated board [Copper Clad Laminates (CCL)] can be obtained, for example.

  In the crosslinked composite of the present invention, the crosslinkable functional group on the surface of the crosslinkable fibrous reinforcing material is involved in the crosslinking reaction together with the (meth) acryloyl group in the cycloolefin polymer and the crosslinkable functional group in the trifunctional compound. For this reason, a cycloolefin polymer and a crosslinkable fibrous reinforcing material can be combined, and the crosslinked composite of the present invention has a large flexural modulus.

The crosslinked composite of the present invention can be used as a layer constituting a laminate. As a laminated body, said RCC and CCL are mentioned, for example. Moreover, in the manufacturing method using said support body, a laminated body can also be obtained by using the resin molding and composite_body | complex obtained separately as a support body. Moreover, a laminated body can also be obtained by laminating a plurality of the crosslinkable composites of the present invention, or further laminating a metal foil and crosslinking by hot pressing.
The crosslinkable composite before the cross-linking reaction exhibits high followability with respect to an arbitrary member when heated and melted. For this reason, by using the crosslinked composite of the present invention as a layer constituting the laminate, it is possible to obtain a laminate having small warpage and excellent peel strength.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. Parts and% in each example are based on weight unless otherwise specified.

The definition of each characteristic and the evaluation method are as follows.
(1) Warpage measurement (260 ° C)
After etching one side of the laminate to remove the copper foil, the laminate was heated from 30 ° C. to 260 ° C. according to JESD22B112 using a shadow moire device (Acrometrics, PS200), and laminated at 260 ° C. Body warpage was measured and evaluated according to the following criteria.
○: 350 μm or less ×: over 350 μm

(2) Warpage measurement (30 ° C)
After the copper foil is removed by etching one side of the laminate, the laminate heated to 260 ° C. is cooled to 30 ° C. according to JESD22B112 using a shadow moire device (manufactured by Achromometrics, PS200). The warpage of the laminate at ℃ was measured and evaluated according to the following criteria.
○: 200 μm or less ×: Over 200 μm

(3) Flexural modulus After the laminate was etched to remove the copper foil, the flexural modulus was measured at 30 ° C. in accordance with JIS K7074 and evaluated according to the following criteria.
○: 23 GPa or more ×: less than 23 GPa

(6) Peel strength The strength when peeling a copper foil (thickness 12 μm) from the laminate at 25 ° C. was measured based on JIS C6481, and evaluated according to the following criteria.
○: More than 0.5 kN / m ×: 0.5 kN / m or less

[Example 1]
Benzylidene (1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride 0.05 part and triphenylphosphine 0.01 part were dissolved in indene 1.51 part to obtain a catalyst solution. Was prepared. Apart from this, as cycloolefin monomer, ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] 90 parts dodec-4-ene (ETD) and 10 parts 5-norbornen-2-yl methacrylate (MAc-NB); di-tert-butyl peroxide (1 minute half-life temperature) 186 ° C.) 1.14 parts; 2.1 parts of styrene as a chain transfer agent; 20 parts of trimethylolpropane trimethacrylate as a crosslinking aid; a phenolic antioxidant (Irganox 1330, manufactured by BASF) as an antioxidant The mixture to which 0 part was added was placed in a glass container, and 100 parts of silica (manufactured by Admatechs, product name SO-E2, silane coupling agent-treated product average particle diameter 0.5 μm) as a filler, and difficult 20 parts of antimony oxide (PATOX-M, manufactured by Nippon Seiko Co., Ltd.) and ethane-1,2-bis (pentabromophenyl) (SAYTE) 8010, manufactured by Albemarle) was placed 40 parts were mixed uniformly.

Next, the obtained polymerizable composition was impregnated into a glass cloth (E glass, 1078) surface-treated with γ-methacryloxypropyltrimethoxysilane, and this was subjected to a polymerization reaction at 120 ° C. for 3.5 minutes. And a crosslinkable composite having a thickness of 0.06 mm was obtained. Further, the obtained seven crosslinkable composites were sandwiched between electrolytic copper foils (Type F0, treated with a silane coupling agent, thickness 0.012 mm, manufactured by Furukawa Electric Co., Ltd.), and the flat plate shape was maintained by a hot press machine. While being hot-pressed, a 0.4 mm-thick laminate in which the crosslinkable composite was laminated was obtained. The conditions for hot pressing were a temperature of 200 ° C., 15 minutes, and a pressure of 3 MPa.
Using the obtained laminated body, each measurement of a curvature, a bending elastic modulus, and a peel strength was performed by the said method. The results are shown in Table 1.

[Example 2]
Ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Example 1 except that the amounts of dodec-4-ene (ETD) and 5-norbornen-2-yl methacrylate (MAc-NB) used were changed to ETD 80 parts and MAc-NB 20 parts. A polymerizable composition was prepared in the same manner as described above, and a laminate was produced using the polymerizable composition and each measurement was performed. The results are shown in Table 1.

Example 3
Ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-ene (ETD) and 5-norbornen-2-yl methacrylate (MAc-NB) were used in Example 1 except that the amount used was changed to 70 parts ETD and 30 parts MAc-NB. A polymerizable composition was prepared in the same manner as described above, and a laminate was produced using the polymerizable composition and each measurement was performed. The results are shown in Table 1.

Example 4
Ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (ETD) 90 parts is added to tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-ene (TCD) 80 parts, same as Example 1 except that 10 parts of 5-norbornen-2-yl methacrylate (MAc-NB) was changed to 20 parts. A polymerizable composition was prepared, a laminate was produced using the polymerizable composition, and each measurement was performed. The results are shown in Table 1.

Example 5
In the same manner as in Example 2 except that glass cloth surface-treated with vinyltrimethoxysilane was used instead of glass cloth surface-treated with γ-methacryloxypropyltrimethoxysilane (E glass, 1078). A polymerizable composition was prepared, a laminate was produced using the polymerizable composition, and each measurement was performed. The results are shown in Table 1.

Example 6
Example 2 except that glass cloth surface-treated with γ-acryloxypropyltrimethoxysilane was used instead of glass cloth surface-treated with γ-methacryloxypropyltrimethoxysilane (E glass, 1078). A polymerizable composition was prepared in the same manner as described above, and a laminate was produced using the polymerizable composition and each measurement was performed. The results are shown in Table 1.

Example 7
In the same manner as in Example 2, except that a glass cloth surface-treated with vinylphenyltrimethoxysilane was used instead of the glass cloth surface-treated with γ-methacryloxypropyltrimethoxysilane (E glass, 1078). Then, a polymerizable composition was prepared, and a laminate was produced using the polymerizable composition, and each measurement was performed. The results are shown in Table 1.

[Comparative Example 1]
Ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Example 1 except that the amount of dodec-4-ene (ETD) and 5-norbornen-2-yl methacrylate (MAc-NB) used was changed to 60 parts ETD and 40 parts MAc-NB. A polymerizable composition was prepared in the same manner as described above, and a laminate was produced using the polymerizable composition and each measurement was performed. The results are shown in Table 1.

[Comparative Example 2]
Ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-ene (ETD) and 5-norbornen-2-yl methacrylate (MAc-NB) were used in Example 1 except that the amount used was changed to 100 parts ETD and 0 parts MAc-NB. A polymerizable composition was prepared in the same manner as described above, and a laminate was produced using the polymerizable composition and each measurement was performed. The results are shown in Table 1.

[Comparative Example 3]
A polymerizable composition was prepared in the same manner as in Example 2 except that trimethylolpropane trimethacrylate as a crosslinking aid was not added, and a laminate was produced using the polymerizable composition, and each measurement was performed. . The results are shown in Table 1.

[Comparative Example 4]
Example 2 except that a glass cloth surface-treated with γ-aminopropyltrimethoxysilane was used instead of the glass cloth surface-treated with γ-methacryloxypropyltrimethoxysilane (E glass, 1078). Similarly, a polymerizable composition was prepared, and a laminate was produced using the polymerizable composition, and each measurement was performed. The results are shown in Table 1.

[Comparative Example 5]
A polymerizable composition was prepared in the same manner as in Example 2 except that untreated glass cloth was used instead of glass cloth (E glass, 1078) surface-treated with γ-methacryloxypropyltrimethoxysilane. Then, a laminate was manufactured using this, and each measurement was performed. The results are shown in Table 1.

From Table 1, it can be seen that in Examples 1 to 7, the warpage is small at both 260 ° C. and 30 ° C., the flexural modulus is large, and the peel strength is excellent.
On the other hand, in Comparative Example 1 in which the amount of 5-norbornen-2-yl methacrylate (MAc-NB) used is too large and in Comparative Example 2 where it is not used, warpage is observed and the peel strength is inferior.
Moreover, in the comparative example 3 which does not use the crosslinking adjuvant, it is inferior to all the performance.
In Comparative Example 4 using a fibrous reinforcing material surface-treated with γ-aminopropyltrimethoxysilane, in Comparative Example 5 in which the warp and the bending elastic modulus were inferior and the glass cloth was not surface-treated at all, the peel was further peeled off. The strength is inferior.

Claims (8)

A crosslinkable composite comprising a cycloolefin polymer, a crosslinker, a trifunctional compound having three crosslinkable functional groups, and a crosslinkable fibrous reinforcing material,
The cycloolefin polymer is a repeating unit derived from a cycloolefin monomer having a (meth) acryloyl group (repeating unit A) and a repeating unit derived from a cycloolefin monomer not having a (meth) acryloyl group (repeating unit B). A crosslinkable composite having a weight ratio (repeat unit A: repeat unit B) in the range of 1:99 to 30:70.   The cycloolefin polymer comprises a cycloolefin monomer having a (meth) acryloyl group and a cycloolefin monomer having no (meth) acryloyl group in a weight ratio (cycloolefin monomer having a (meth) acryloyl group: (meth) acryloyl). The crosslinkable composite according to claim 1, which is obtained by polymerizing a cycloolefin monomer having no group) in a range of 1:99 to 30:70.   A cycloolefin monomer, a polymerization catalyst, a crosslinking agent, and a trifunctional compound having three crosslinkable functional groups, the cycloolefin monomer having a (meth) acryloyl group and a (meth) acryloyl group Polymerization containing a cycloolefin monomer having no weight ratio (cycloolefin monomer having a (meth) acryloyl group: cycloolefin monomer having no (meth) acryloyl group) within a range of 1:99 to 30:70 The crosslinkable composite according to claim 1 or 2, which is obtained by impregnating a crosslinkable fibrous reinforcing material with a crosslinkable composition and then bulk polymerizing the impregnated polymerizable composition.   The crosslinkable complex according to any one of claims 1 to 3, wherein the crosslinkable functional group in the trifunctional compound having three crosslinkable functional groups is a group having an aliphatic carbon-carbon double bond.   The crosslinkable composite according to any one of claims 1 to 4, wherein the crosslinkable fibrous reinforcing material is obtained by surface-treating the fibrous reinforcing material with a surface treatment agent having a crosslinkable functional group. body.   The crosslinkable composite according to any one of claims 1 to 5, wherein the crosslinkable fibrous reinforcing material is a fibrous reinforcing material having an aliphatic carbon-carbon double bond on the surface thereof.   A cross-linked composite obtained by cross-linking the cross-linkable composite according to claim 1. A cycloolefin monomer, a polymerization catalyst, a crosslinking agent, and a trifunctional compound having three crosslinkable functional groups, the cycloolefin monomer having a (meth) acryloyl group and a (meth) acryloyl group Polymerization containing a cycloolefin monomer having no weight ratio (cycloolefin monomer having a (meth) acryloyl group: cycloolefin monomer having no (meth) acryloyl group) within a range of 1:99 to 30:70 Impregnating the crosslinkable fibrous reinforcing material with the adhesive composition,
Next, a step of bulk polymerizing the impregnated polymerizable composition to obtain a crosslinkable composite,
A step of crosslinking the obtained crosslinkable composite,
The manufacturing method of the crosslinked composite_body | complex of Claim 7 which has these.