JP5282586B2 - Polymerizable composition, crosslinked body and crosslinked resin composite - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition low in viscosity and excellent in moldability, adhesivity and crack resistance in a cold-heat impact test, and to provide a crosslinked form and a crosslinked resin composite obtained using the composition. <P>SOLUTION: The polymerizable composition includes a filler treated with a surface treatment agent represented by general formula (1) [wherein, M<SP>1</SP>is Ti, Si, Al or Zr; X<SP>1</SP>and X<SP>2</SP>are each independently a hydrolyzable group, hydroxy group or alkyl; X<SP>3</SP>is a hydrolyzable group or hydroxy group; Y is 1-30C straight-chain, branched or cyclic aliphatic hydrocarbon group which may have a substituent containing an oxygen atom or a sulfur atom, or aromatic hydrocarbon group which may have a substituent containing an oxygen atom or a sulfur atom]. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a polymerizable composition, a crosslinked body, and a crosslinked resin composite, and more specifically, a crosslinked body having low viscosity and excellent moldability, adhesion to a support, and crack resistance in a thermal shock test. The present invention also relates to a polymerizable composition that gives a crosslinked resin composite, and a crosslinked body and a crosslinked resin composite obtained by using the polymerizable composition.

  A circuit board is generally composed of a dielectric layer and a conductor layer. In recent years, with the advent of advanced information technology, information transmission has started to move toward higher speeds and higher frequencies, and microwave communication and millimeter wave communication have become a reality. The dielectric layers of circuit boards in these high frequency eras need to reduce noise and transmission loss at high frequencies to the limit. Therefore, as a material for forming such a dielectric layer, a dielectric having a low dielectric loss tangent (tan δ) The selection of body materials has become an important issue.

  A cycloolefin polymer obtained by bulk polymerization of a cycloolefin monomer has attracted attention as a resin material having such a low dielectric loss tangent. For example, Patent Document 1 discloses a polymerizable composition containing a cycloolefin monomer, a metathesis polymerization catalyst, a crosslinking agent, a chain transfer agent, and a specific liquid diene rubber. In this patent document 1, it aims at obtaining the polymeric composition which can give crosslinkable resin suitable as an electrical material etc. which are used for an electrical circuit board. In addition, in this patent document 1, while the point which may add the silica processed with the silane coupling agent to the polymerizable composition is described, the silica processed with the silane coupling agent is added. Further, there is no description about the purpose of the process, and furthermore, no specific example of the silane coupling agent used for treating the silica is described.

  Patent Document 2 discloses a cycloolefin composition containing a cycloolefin monomer capable of metathesis polymerization, a filler, a metal-containing coupling agent, and a metathesis polymerization catalyst. In addition, in this patent document 2, it aims at improving the mechanical characteristic at the time of filler addition. Moreover, in this patent document 2, only a mononuclear coupling agent (coupling agent containing only one metal element) is disclosed as a specific example of the metal-containing coupling agent.

JP 2008-133417 A JP 2000-309628 A

  However, as a result of studies by the present inventors, in the polymerizable composition described in Patent Document 1, in order to improve the mechanical properties and the like of the obtained molded body, silica treated with a silane coupling agent is simply increased. When added at a concentration, the viscosity of the polymerizable composition increases, making it difficult to mold and limiting the application to circuit boards. Furthermore, the molded product obtained by using the polymerizable composition described in Patent Document 1 is inferior in crack resistance at the time of repeated use under the assumed use environment of the circuit board, moldability, and adhesion to the support. Problems were also recognized. In addition, the molded body obtained using the cycloolefin composition described in Patent Document 2 has a problem that it is inferior in crack resistance and adhesion to a support during repeated use in an environment where a circuit board is assumed to be used. It was.

  An object of the present invention is to provide a crosslinked composition and a crosslinked resin composite having a low viscosity and excellent moldability, adhesion to a support and crack resistance in a thermal shock test, and It is to provide a crosslinked body and a crosslinked resin composite obtained by using the same.

  As a result of intensive investigations in view of the above problems, the present inventors have made a filler that has been surface-treated with a specific surface treatment agent as a filler in a polymerizable composition containing a block polymerizable monomer, a polymerization catalyst, and a filler. It is found that a polymerizable composition giving a crosslinked product and a crosslinked resin composite having a low viscosity and excellent moldability, adhesion to a support and crack resistance in a thermal shock test can be obtained. The present invention has been completed based on this finding.

（上記一般式（１）中、Ｍ^１は、Ｔｉ、Ｓｉ、ＡｌまたはＺｒを表し、Ｘ^１，Ｘ^２はそれぞれ独立して加水分解性基、水酸基またはアルキル基を表し、Ｘ^３は加水分解性基または水酸基を表し、Ｙは、窒素原子、酸素原子もしくは硫黄原子を含む置換基を有していても良い炭素数１〜３０の直鎖、分岐もしくは環状の脂肪族炭化水素基、または窒素原子、酸素原子もしくは硫黄原子を含む置換基を有していても良い芳香族炭化水素基を表す。）

（上記一般式（２）中、Ｍ ^２ は、Ｔｉ、Ｓｉ、ＡｌまたはＺｒを表し、Ｒ ^１ は末端に二重結合、メルカプト基またはアミノ基を有する炭化水素基を表し、Ｘ ^４ ，Ｘ ^５ はそれぞれ独立して加水分解性基、水酸基またはアルキル基を表し、Ｘ ^６ は加水分解性基または水酸基を表す。）
〔２〕架橋剤をさらに含む前記〔１〕に記載の重合性組成物、
〔３〕前記〔１〕または〔２〕に記載の重合性組成物を塊状重合してなる架橋性樹脂、
〔４〕前記〔１〕または〔２〕に記載の重合性組成物を支持体に塗布または含浸し、塊状重合してなる架橋性樹脂複合体、
〔５〕前記〔３〕に記載の架橋性樹脂を架橋してなる架橋体、ならびに、
〔６〕前記〔５〕に記載の架橋体と支持体とを含む架橋樹脂複合体、
が提供される。 That is, according to the present invention,
[1] Filler, polymerization catalyst, and bulk polymerization surface-treated with the surface treatment agent (A) represented by the following general formula (1) and the surface treatment agent (B) represented by the following general formula (2) look including the possible cycloolefin monomers, the ratio of the surface treatment agent used for the surface treatment of the filler with (a), the surface treatment agent and (B) is, in weight ratio, surface treatment agent (a) / A polymerizable composition having a surface treating agent (B) of 0.1 to 0.33 ,

(In the general formula (1), M ¹ represents Ti, Si, Al or Zr, X ¹ and X ² each independently represents a hydrolyzable group, a hydroxyl group or an alkyl group, and X ³ represents hydrolysis. Y represents a functional group or a hydroxyl group, and Y represents a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent containing a nitrogen atom, an oxygen atom or a sulfur atom, or nitrogen Represents an aromatic hydrocarbon group which may have a substituent containing an atom, oxygen atom or sulfur atom.)

(In the above general formula (2), M ² represents Ti, Si, Al or Zr, R ¹ represents a hydrocarbon group having a double bond, a mercapto group or an amino group at the terminal, and X ⁴ , X ⁵ Each independently represents a hydrolyzable group, a hydroxyl group or an alkyl group, and X ⁶ represents a hydrolyzable group or a hydroxyl group.)
[ 2 ] The polymerizable composition according to [1] , further including a crosslinking agent,
[ 3 ] A crosslinkable resin obtained by bulk polymerization of the polymerizable composition according to [1] or [2] ,
[ 4 ] A crosslinkable resin composite obtained by coating or impregnating the polymerizable composition according to [1] or [2] on a support and performing bulk polymerization.
[ 5 ] A crosslinked product obtained by crosslinking the crosslinkable resin according to [ 3 ], and
[ 6 ] A crosslinked resin composite comprising the crosslinked body according to [ 5 ] and a support,
Is provided.

  According to the present invention, a polymerizable composition giving a crosslinked body and a crosslinked resin composite having a low viscosity and excellent in moldability, adhesion to a support and crack resistance in a thermal shock test, and A cross-linked body and a cross-linked resin composite obtained by use are provided. Since the crosslinked body and crosslinked resin composite of the present invention are excellent in moldability, adhesion to a support and crack resistance in a thermal shock test, a high-frequency circuit board such as microwave or millimeter wave for use in communication equipment, etc. Can be suitably used.

  The polymerizable composition of the present invention comprises a filler surface-treated with a surface treatment agent (A) described later, a polymerization catalyst, and a monomer capable of bulk polymerization.

(Block-polymerizable monomer)
The bulk polymerizable monomer used in the present invention is not particularly limited as long as it is capable of bulk polymerization. Examples of such bulk polymerizable monomers include epoxy compounds, acrylate compounds, styrenes, and cycloolefin monomers. Among these, since the dielectric loss tangent of the obtained crosslinked body and crosslinked resin composite can be lowered, styrenes and cycloolefin monomers which are nonpolar monomers are preferable, and cycloolefin monomers are particularly preferable.

  A cycloolefin monomer is a compound having a ring structure formed of carbon atoms and having one polymerizable carbon-carbon double bond in the ring structure. 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. In the present invention, it usually refers to metases ring-opening polymerization.

Examples of the ring structure of the cycloolefin monomer include monocycles, polycycles, condensed polycycles, bridged rings, and polycycles obtained by combining these. Although there is no limitation in particular in carbon number which comprises each ring structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces.
The cycloolefin monomer may have a hydrocarbon group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkylidene group or an aryl group, or a polar group such as a carboxyl group or an acid anhydride group as a substituent. However, from the viewpoint of making the obtained crosslinked body and crosslinked resin composite have a low dielectric loss tangent, those having no polar group, that is, those composed only of carbon atoms and hydrogen atoms are preferred.

  As the cycloolefin monomer, either a monocyclic cycloolefin monomer or a polycyclic cycloolefin monomer can be used. From the viewpoint of highly balancing the dielectric properties and heat resistance properties of the resulting crosslinked product and crosslinked resin composite, polycyclic cycloolefin monomers are preferred. As the polycyclic cycloolefin monomer, a norbornene-based monomer having a norbornene ring structure in the molecule is particularly preferable. Examples of norbornene monomers include norbornenes, dicyclopentadiene, tetracyclododecenes, and the like.

  Here, the cycloolefin monomer is classified into those having no crosslinkable carbon-carbon unsaturated bond and those having one or more crosslinkable carbon-carbon unsaturated bonds. 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. In the present invention, usually, a radical crosslinking reaction or a metathesis crosslinking reaction is performed. 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. In the cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds, the position of the unsaturated bond is not particularly limited, and within the ring structure formed of carbon atoms, any other than the ring structure For example, at the end or inside of the side chain.

  Examples of cycloolefin monomers having no crosslinkable carbon-carbon unsaturated bond include cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, and 3-chlorocyclopentene. , Cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene and other monocyclic cycloolefin monomers; norbornene, 5-methyl-2-norbornene, 5 -Ethyl-2-norbornene, 5-propyl-2-norbornene, 5,6-dimethyl-2-norbornene, 1-methyl-2-norbornene, 7-methyl-2-norbornene, 5,5,6-trimethyl-2 -Norbornene, 5-Fe Lu-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-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-1,4,5,8-di Tano-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-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-dicarboxyl-2-norbornene anhydrate, 5-dimethylamino-2-norbornene, 5-cyano-2 -Norbornene monomers such as norbornene; and the like, preferably norbornene monomers having no crosslinkable carbon-carbon unsaturated bond.

Examples of the cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds include 3-vinylcyclohexene, 4-vinylcyclohexene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4- Monocyclic cycloolefin monomers such as cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene; 5-ethylidene-2-norbornene, 5-methylidene -2-norbornene, 5-isopropylidene-2-norbornene, 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 5,6-diethylidene-2-norbornene, dicyclopentadiene, 2,5-norbornadiene, etc. Norbornene-based monomers; Sexual carbon - is a norbornene-based monomer having one or more carbon unsaturated bond.
These cycloolefin monomers can be used alone or in combination of two or more.

The cycloolefin monomer used in the present invention includes a cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds, and the resulting crosslinked product and reliability of the crosslinked resin composite such as crack resistance Can be improved, which is preferable.
A cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond and a cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond in the cycloolefin monomer to be blended in the polymerizable composition of the present invention. The blending ratio is appropriately selected as desired, but usually in a weight ratio (cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds / cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bonds). 0.01 / 99.9 to 100/0, preferably 1/90 to 90/10, more preferably 5/95 to 80/20. When these blending ratios are in such a range, it is possible to highly improve properties such as adhesion to the support of the obtained crosslinked product and crosslinked resin composite and crack resistance in a thermal shock test, Is preferred.

(filler)
The filler used in the present invention is surface-treated with a surface treatment agent (A) described later.

  As the filler, any particles that are insoluble in the block polymerizable monomer and the solvent used as necessary may be used, and any of inorganic fillers and organic fillers may be used, depending on the application to be used. What is necessary is just to select suitably. The shape of the filler is not particularly limited, and may be any shape such as a spherical shape, a granular shape, an indefinite shape, a dendritic shape, a needle shape, a rod shape, a flat shape, and a hollow shape.

Examples of the inorganic filler include metal particles such as iron, copper, nickel, gold, silver, aluminum, lead, and tungsten; carbon particles such as carbon black, graphite, activated carbon, and carbon balloon; silica, silica balloon, alumina, Inorganic oxide particles such as titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, beryllium oxide, barium ferrite, strontium ferrite; inorganic carbonate particles such as calcium carbonate, magnesium carbonate, sodium hydrogen carbonate; calcium sulfate, etc. Inorganic sulfate particles; inorganic silicate particles such as talc, clay, mica, kaolin, fly ash, montmorillonite, calcium silicate, glass, glass balloon; titanate particles such as calcium titanate and lead zirconate titanate; Aluminum nitride, silicon carbide particles Nitride particles such as boron nitride; and whiskers, and the like. Examples of the organic filler include compound particles such as wood powder, starch, organic pigments, polystyrene, nylon, polyolefins such as polyethylene and polypropylene, vinyl chloride, and waste plastics. These fillers can be used alone or in combination of two or more.
Among these, inorganic fillers are preferable, inorganic oxide particles, titanate particles, and nitride particles are more preferable, inorganic oxide particles such as silica and alumina, and titanate particles such as calcium titanate and barium titanate. Is particularly preferable because of its excellent electrical insulation.

  The average particle diameter of the filler is not particularly limited, but is usually 0.001 to 70 μm, preferably 0.01 to 50 μm, as a median diameter containing 50% by volume of all particles measured by a laser scattering diffraction particle size distribution meter. More preferably, it is 0.05-15 micrometers, Most preferably, it is 0.1-5 micrometers.

The surface treatment agent (A) used for the surface treatment of the filler used in the present invention is a compound represented by the following general formula (1).

In the general formula (1), M ¹ is Ti, Si, Al or Zr, preferably Si. X ¹ and X ² are each independently a hydrolyzable group, a hydroxyl group or an alkyl group, X ³ is a hydrolyzable group or a hydroxyl group, and these X ¹ , X ² and X ³ are hydrolyzable. It is preferably a group, and more preferably an alkoxyl group from the viewpoint of easy adjustment of the hydrolysis rate. Y is a linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 30 carbon atoms, and a linear aliphatic hydrocarbon group or aromatic carbon group having 2 to 15 carbon atoms. A hydrogen group is preferred. In addition, these aliphatic hydrocarbon groups or aromatic hydrocarbon groups may have a substituent containing a nitrogen atom, an oxygen atom, or a sulfur atom. When Y is an aromatic hydrocarbon group, the aromatic hydrocarbon group may be directly bonded to M ¹ or via an alkylene group having 1 to 10 carbon atoms. , M ¹ may be bonded. Even when the filler is surface-treated with the surface treatment agent (A) represented by the above general formula (1), the amount of the filler in the polymerizable composition is relatively high, so that the polymerizability is high. The viscosity of the composition can be reduced, and the obtained crosslinked body and crosslinked resin composite should be excellent in moldability, adhesion to the support and crack resistance in the thermal shock test. it can. In particular, the viscosity of the polymerizable composition can be lowered, whereby the moldability can be improved, and furthermore, the viscosity can be lowered, whereby the fluidity can be improved, and thereby the support surface can be obtained. The embedding property of can be improved. That is, for example, even when a substrate having irregularities is used as the support, the embeddability can be improved.

  Specific examples of the surface treatment agent (A) represented by the general formula (1) include bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (tripropoxysilyl) ethane, and bis (trimethoxy Silyl) methane, bis (triethoxysilyl) methane, bis (tripropoxysilyl) methane, bis (trimethoxysilyl) hexane, bis (trimethoxysilyl) octane, bis (triethoxysilyl) octane, bis (triethoxysilyl) Nonane, bis (triethoxysilyl) octadiene, 1,2-bis (trimethoxysilyl) decane, 1,3-bis (triethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,4- Bis (triethoxysilyl) benzene, 1,4-bis (triethoxysilylmethyl) benzene Zen, 1,4-bis (triethoxysilylethyl) benzene, bis [(3-methyldimethoxysilyl) propyl] polypropylene oxide, bis [3- (triethoxysilyl) propyl] disulfide, bis [m- (2-tri Methoxysilylethyl) tolyl] polysulfide, bis [3- (triethoxysilyl) propyl] thiourea, bis (triethoxysilylethyl) vinylmethylsilane, bis (triethoxysilyl) ethylene, 1,3- [bis (3-tri Ethoxysilylpropyl) polyethyleneoxy] -2-methylenepropane, bis (4-triethoxysilylpropyl-3-methoxyphenyl) -1,6-heptane and the like. These may be used alone or in combination of two or more.

Further, the filler used in the present invention is surface-treated with a surface treatment agent (B) represented by the following general formula (2) in addition to the surface treatment agent (A) represented by the above general formula (1). Preferably it is. That is, the filler used in the present invention is preferably surface-treated with the surface treatment agent (A) and the surface treatment agent (B). By using the surface treatment agent (A) and the surface treatment agent (B) in combination, and using these to perform the surface treatment of the filler, the effects of the present invention can be made more remarkable.

In the general formula (2), M ² is Ti, Si, Al, or Zr, preferably Si. R ¹ is a hydrocarbon group having a double bond, a mercapto group or an amino group at the terminal, and is more preferably a hydrocarbon group having a double bond at the terminal from the viewpoint of good reactivity. A vinyl group or a styryl group is more preferable. X ⁴ and X ⁵ are each independently a hydrolyzable group, a hydroxyl group or an alkyl group, X ⁶ is a hydrolyzable group or a hydroxyl group, and these X ⁴ , X ⁵ and X ⁶ are A decomposable group is preferred, and an alkoxyl group is more preferred. The surface treatment agent (B) represented by the general formula (2) acts as a surface treatment agent having radical reactivity.

  Specific examples of the surface treatment agent (A) represented by the general formula (2) include allyltrimethoxysilane, 3-butenyltrimethoxysilane, styryltrimethoxysilane, N-β- (N- (vinylbenzyl) ) Aminoethyl) -γ-aminopropyltrimethoxysilane and salts thereof, allyltrichlorosilane, allylmethyldichlorosilane, styryltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) ) Silane, vinyltrichlorosilane, β-methacryloxyethyltrimethoxysilane, β-methacryloxyethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, δ-methacryloxybutyltrimethoxysilane, γ-acryloxypropi Trimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ -Aminopropyltrimethoxysilane etc. are mentioned. These may be used alone or in combination of two or more.

  When the surface treatment agent (A) and the surface treatment agent (B) are used in combination, the ratio of the surface treatment agent (A) to the surface treatment agent (B) is “surface treatment agent (A) / surface treatment agent ( B) "is preferably 0.001 to 2.0, more preferably 0.01 to 1.0, still more preferably 0.05 to 0.5, and particularly preferably 0.1 to 0. .3. Whether the value of the surface treatment agent (A) / surface treatment agent (B) is too low or too high, the moldability of the resulting crosslinked product and crosslinked resin composite, adhesion to the support and thermal shock test There is a tendency for the crack resistance of the steel to decrease.

The method for treating the filler is not particularly limited. For example, the filler may be treated by adding the surface treatment agent (A) and the surface treatment agent (B) to a dry, wet or bulk polymerizable monomer. The dry method is preferable from the viewpoint of simplicity and uniformity of treatment.
When the surface treatment of the filler is performed by a dry method, a small amount of water or an organic solvent may be added to the surface treatment agent (A) and the surface treatment agent (B) used as necessary. Alternatively, when the filler is surface-treated in a wet manner, the surface treatment agent (A) and the surface treatment agent (B) used as necessary are dispersed or dissolved in water or an organic solvent, thereby treating the filler. The containing solution may be prepared and the filler surface may be treated using the prepared treating agent-containing solution. Examples of the organic solvent used in these cases include alcohols, ketones, pyrrolidones, furans, amines, and carboxylic acids. Among these, alcohols and ketones are preferable, and alcohols Are more preferable, and methanol and ethanol are particularly preferable.
What is necessary is just to select the usage-amount of these solvents suitably according to the kind of filler to be used. When the surface treatment of the filler is performed in a dry process, the amount of these solvents used is usually 100 parts by weight of the total amount of the surface treatment agent (A) and the surface treatment agent (B) used as necessary. 0.01 parts by weight or more and less than 100 parts by weight. In addition, when the surface treatment of the filler is performed in a wet manner, the amount of these solvents used is 100 parts by weight in total of the surface treatment agent (A) and the surface treatment agent (B) used as necessary. , 100 to 5000 parts by weight.
The order of addition of the surface treatment agent (A) and the surface treatment agent (B) used as necessary is not particularly limited. The atmosphere for surface treatment is not particularly limited. Nitrogen, air, or vacuum may be selected as appropriate, but air is simple and preferable.
The surface treatment is preferably performed under heating conditions. By heating, the surface treatment agent and the filler can be more closely bonded, thereby improving adhesion and reliability. Further, when water or an organic solvent is used, these can be removed by heating, and it is not necessary to remove water or the organic solvent after blending with a block polymerizable monomer, so that the operation is simplified. Conditions for heating may be selected as appropriate, and are not particularly limited during and after the addition of the surface treatment agent (A) and the surface treatment agent (B) used as necessary. The heating temperature may be appropriately selected depending on the surface treatment agent to be used, but is usually 50 to 300 ° C, preferably 80 to 200 ° C. The heating time is usually 0.01 to 10 hours, preferably 0.05 to 5 hours, more preferably 0.1 to 3 hours after the addition of the surface treatment agent. The apparatus used for the surface treatment is not particularly limited, and a Henschel mixer, a ball mill, a pot mill, a ribbon mixer, a mortar, or the like may be appropriately selected. Among these, a Henschel mixer, a ribbon mixer, and the like are preferable.

  Moreover, the total content of the surface treatment agent (A) and the surface treatment agent (B) in the filler after the surface treatment is preferably 0.01 to 20 weights with respect to the entire filler after the surface treatment. %, More preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, and 0.1 to 3% by weight. When the total content ratio of the surface treatment agent (A) and the surface treatment agent (B) is too low, the surface treatment of the filler becomes insufficient, the viscosity of the polymerizable composition becomes high, and the resulting crosslinked product and crosslinked product are obtained. The mechanical strength of the resin composite may be reduced. On the other hand, if the content ratio is too high, the unreacted surface treatment agent (A) and / or the surface treatment agent (B) may bleed, and the heat resistance of the resulting crosslinked product and crosslinked resin composite may decrease. is there.

  The blending amount of the filler in the polymerizable composition is preferably 1 to 1,000 parts by weight, more preferably 10 to 500 parts by weight, and still more preferably 50 to 350 parts with respect to 100 parts by weight of the monomer capable of bulk polymerization. The range is parts by weight. When the blending amount of the filler is too small, the effect of adding the filler tends not to be obtained. On the other hand, when there is too much compounding quantity of a filler, it exists in the tendency for a compounding liquid to thicken and to become difficult to shape | mold.

(Polymerization catalyst)
The polymerization catalyst can be appropriately selected depending on the type of the monomer capable of bulk polymerization and the polymerization reaction mode. For example, when the bulk polymerizable monomer is a cycloolefin monomer, a metathesis polymerization catalyst can be selected as a suitable polymerization catalyst. Examples of the metathesis polymerization catalyst include a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds with a transition metal atom as a central atom. 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 ruthenium and osmium. Can be mentioned. 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 that it is excellent in productivity of the crosslinkable resin, has low odor derived from the unreacted monomer of the resulting crosslinkable resin, and is excellent in workability. 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 (3) or general formula (4).

In the general formula (3) and the general formula (4), R ² and R ³ each independently represent 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. The C1-C20 hydrocarbon group which may be included is represented.

Z ¹ and Z ² each independently represents 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 represents a hetero atom-containing carbene compound or a neutral electron donating compound. A hetero atom means an atom of Group 15 and Group 16 of the Periodic Table, and specific examples thereof include N, O, P, S, As, and Se atoms. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, S atoms and the like are preferable, and N atoms are particularly preferable.

Examples of the heteroatom-containing carbene compound include compounds represented by the following general formula (5) or general formula (6).

In the formula, R ^{4 to} R ⁷ are each independently 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 ^{4 to} R ⁷ may be bonded to each other in any combination to form a ring.

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

In the above formulas (3) and (4), R ² and R ³ may be bonded to each other to form a ring, and further R ² , R ³ , Z ¹ , Z ² , L ¹ and L ² May be bonded together in any combination to form a multidentate chelating ligand.

  In the present invention, the use of a ruthenium catalyst having a compound having a heterocyclic structure as a ligand as a metathesis polymerization catalyst can highly balance the high-frequency characteristics and heat resistance characteristics of the obtained composite material. Therefore, it is preferable. Examples of the hetero atom constituting the heterocyclic structure include an O atom and an N atom, and an N atom is preferable. Moreover, as a heterocyclic structure, an imidazoline structure and an imidazolidine structure are preferable.

As a ruthenium catalyst having such a compound having a heterocyclic structure as a ligand, a ligand composed of a heteroatom-containing carbene compound represented by the above formula (3) or (4) is used as L ¹ or L ^2. The ruthenium catalyst which has can be used suitably. As a hetero atom constituting the hetero atom-containing carbene compound, an N atom is preferable. Specific examples of such heteroatom-containing carbene compounds include, for example, 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1 , 3-di (1-phenylethyl) -4-imidazoline-2-ylidene, benzylidene (1,3-dimesitylimidazolidin-2-ylidene), 1,3-dimesitylimidazolidin-2-ylidene, Examples include 1,3-dicyclohexylimidazolidine-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene, and the like.

  Specific examples of the ruthenium catalyst having a ligand composed of a heteroatom-containing carbene compound 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 complex compound in which a hetero atom-containing carbene compound and a neutral electron donating compound are bonded as a ligand, such as pyridine ruthenium dichloride.

  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: 1, in a molar ratio of (metal atom in catalyst: cycloolefin monomer). In the range of 1: 10,000 to 1: 500,000.

  If necessary, 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 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 aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and hydrocarbons having an alicyclic ring and an aromatic ring.

(Polymerizable composition)
The polymerizable composition of the present invention comprises the above bulk polymerizable monomer and filler. Moreover, a crosslinking agent, a chain transfer agent, a polymerization regulator, a polymerization reaction retarder, an antiaging agent, other compounding agents, and the like can be added to the polymerizable composition of the present invention as desired.

  The crosslinking agent is used for the purpose of inducing a crosslinking reaction in a crosslinkable resin obtained by bulk polymerization of the polymerizable composition of the present invention. Therefore, by using a crosslinking agent, the crosslinkable resin obtained by bulk polymerization of the polymerizable composition of the present invention can be used as a postcrosslinkable thermoplastic resin. In the present invention, a radical generator is usually preferably used as the crosslinking agent. 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 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-methyl Peroxyketals such as chlorocyclohexane 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 , 6,9-trimethyl-1,4,7-triperoxonane, cyclic peroxides such as 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 and 2,6-bis (4'-azidobenzal) cyclohexanone.

  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 half-life temperature for 1 minute is the condition for curing (crosslinking of the crosslinkable resin and the crosslinkable resin composite obtained by bulk polymerization of the polymerizable composition of the present invention). However, it is usually in the range of 100 to 300 ° C, preferably 150 to 250 ° C, more preferably 160 to 230 ° C. 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.

  These crosslinking agents can be used alone or in combination of two or more. The amount of the crosslinking agent to be added to the polymerizable composition of the present invention is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the block polymerizable monomer. Preferably it is the range of 0.5-5 weight part.

  The chain transfer agent is not particularly limited as long as it can participate in metathesis ring-opening polymerization, but is an aliphatic carbon that can be bonded to the terminal of the crosslinkable resin obtained by polymerizing the polymerizable composition of the present invention. -Compounds having one carbon double bond are preferred. Examples of such bondable aliphatic carbon-carbon double bonds include terminal vinyl groups. Moreover, the chain transfer agent may have one or more crosslinkable carbon-carbon unsaturated bonds.

  Specific examples of such chain transfer agents include 1-hexene, 2-hexene, styrene, vinylcyclohexane, allylamine, glycidyl acrylate, allyl glycidyl ether, ethyl vinyl ether, methyl vinyl ketone, 2- (diethylamino) ethyl acrylate, A chain transfer agent having no crosslinkable carbon-carbon unsaturated bond, such as 4-vinylaniline; divinylbenzene, vinyl methacrylate, allyl methacrylate, styryl methacrylate, allyl acrylate, undecenyl methacrylate, styryl acrylate, Chain transfer agent having one crosslinkable carbon-carbon unsaturated bond, such as ethylene glycol diacrylate; chain transfer having two or more crosslinkable carbon-carbon unsaturated bonds, such as allyltrivinylsilane and allylmethyldivinylsilane Agent Etc., and the like. Among these, from the viewpoint that the moldability of the obtained crosslinked body and crosslinked resin composite, adhesion to the support and crack resistance in the thermal shock test can be highly balanced, a crosslinkable carbon-carbon Those having one or more unsaturated bonds are preferred, and those having one crosslinkable carbon-carbon unsaturated bond are more preferred. Among these chain transfer agents, chain transfer agents having one vinyl group and one methacryl group are preferable, and vinyl methacrylate, allyl methacrylate, styryl methacrylate, undecenyl methacrylate, and the like are particularly preferable.

  These chain transfer agents can be used alone or in combination of two or more. The blending amount of the chain transfer agent to the polymerizable composition of the present invention is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the block polymerizable monomer. is there.

  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. When the polymerization regulator is used, the blending amount of the polymerization regulator is preferably a molar ratio (metal atom in the polymerization catalyst: polymerization regulator), preferably 1: 0.05 to 1: 100, more preferably 1: 0. .2 to 1:20, more preferably in the range of 1: 0.5 to 1:10.

  The polymerization reaction retarder can suppress an increase in viscosity caused by the progress of the polymerization reaction of the polymerizable composition of the present invention. Polymerization 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. What is necessary is just to adjust suitably the compounding quantity of a polymerization reaction retarder in the case of using a polymerization reaction retarder as needed.

  Examples of the anti-aging agent include phenol-based anti-aging agents, amine-based anti-aging agents, phosphorus-based anti-aging agents, sulfur-based anti-aging agents and the like. By blending these anti-aging agents, a crosslinking reaction can be performed. It is preferable because the heat resistance of the resulting crosslinked body and crosslinked resin composite can be improved to a high degree without hindering. Among these, a phenolic antiaging agent and an amine antiaging agent are preferable, and a phenolic antiaging agent is more preferable. These anti-aging agents can be used alone or in combination of two or more. In the case of using an anti-aging agent, the amount of the anti-aging agent used is preferably 0.0001 to 10 parts by weight, more preferably 0.001 to 5 parts by weight, with respect to 100 parts by weight of the block polymerizable monomer. More preferably, it is the range of 0.01-2 weight part.

  Moreover, other compounding agents other than the above-mentioned compounding agents can be blended in the polymerizable composition of the present invention. As other compounding agents, colorants such as pigments and dyes, light stabilizers, foaming agents and the like can be used. There are various kinds of colorants, and known ones may be appropriately selected and used. These other compounding agents can be used alone or in combination of two or more, and the amount used is appropriately selected within a range not impairing the effects of the present invention.

  The polymerizable composition of the present invention can be obtained by mixing the above components. As a mixing method, a conventional method may be used. For example, a liquid (catalyst liquid) in which a polymerization catalyst is dissolved or dispersed in an appropriate solvent is prepared, and essential components such as bulk polymerizable monomers and fillers, and It can be prepared by preparing a liquid (monomer liquid) containing other compounding agents as desired, adding a catalyst liquid to the monomer liquid, and stirring.

(Crosslinkable resin, crosslinkable resin composite)
The crosslinkable resin of the present invention can be obtained by bulk polymerization of the above-described polymerizable composition of the present invention. As a method for bulk polymerization of the polymerizable composition, (a) a method of pouring or coating the polymerizable composition on a support and bulk polymerization, (b) pouring the polymerizable composition into a mold, Examples thereof include a polymerization method, (c) a method in which a polymerizable composition is impregnated into a support made of a fiber material, and bulk polymerization is performed.

  According to the method (a), a crosslinkable resin composite formed from a crosslinkable resin and a support is obtained. Although it does not specifically limit as a support body, A metal foil or a resin film is preferable. Examples of the material constituting the metal foil include iron, stainless steel, copper, aluminum, nickel, chromium, gold, and silver. Examples of the material constituting the resin film include polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, and nylon. In the case of using a metal foil or a resin film as the support, these thicknesses are preferably 1 to 150 μm, more preferably 2 to 100 μm, and still more preferably 3 to 75 μm from the viewpoint of workability and the like. The surface of these supports is preferably smooth. In addition, the surface of these supports is preferably surface-treated with a silane coupling agent such as styryltrimethoxysilane.

  In the method (a), the method for applying the polymerizable composition onto the support is not particularly limited, and may be 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 the like. A well-known coating method is mentioned.

  In the above method (a), bulk polymerization is started by heating the polymerizable composition to a temperature at which a monomer capable of bulk polymerization starts polymerization (when the polymerization catalyst is used, the temperature at which the polymerization catalyst functions). Is done. The method of heating the polymerizable composition to a predetermined temperature is not particularly limited, and is a method of heating by placing on a heating plate, a method of heating (hot pressing) while applying pressure using a press, and pressing with a heated roller. Examples thereof include a method and a method using a heating furnace.

  Moreover, according to the method (b), a molded article of a crosslinkable resin having an arbitrary shape can be obtained. Examples of the shape include a sheet shape, a film shape, a column shape, a columnar shape, and a polygonal column shape. As the mold used here, a conventionally known mold, for example, a split mold structure, that is, a mold having a core mold and a cavity mold, can be used, and a polymerizable composition is formed in these voids (cavities). Is injected to cause bulk polymerization. The core mold and the cavity mold are produced so as to form a gap that matches the shape of the target molded product. Further, the shape, material, size and the like of the mold are not particularly limited. Alternatively, a plate-shaped mold such as a glass plate or a metal plate and a spacer having a predetermined thickness are prepared, and the polymerizable composition is injected into a space formed by sandwiching the spacer between two plate-shaped molds. As a result, a sheet-like or film-like molded product of the crosslinkable resin can be obtained.

  In the method (b), the filling pressure (injection pressure) when filling the polymerizable composition into the cavity of the mold is usually 0.01 to 10 MPa, preferably 0.02 to 5 MPa. If the filling pressure is too low, transfer of the transfer surface formed on the inner peripheral surface of the cavity tends not to be performed well. On the other hand, if the filling pressure is too high, it is not economical because the rigidity of the mold must be increased. The mold clamping pressure is usually in the range of 0.01 to 10 MPa.

According to the method (c), a prepreg that is a crosslinkable resin composite formed by impregnating reinforcing fibers with a crosslinkable resin can be obtained. Although it does not specifically limit as a reinforced fiber, For example, organic fibers, such as PET (polyethylene terephthalate) fiber, aramid fiber, ultra high molecular polyethylene fiber, polyamide (nylon) fiber, and liquid crystal polyester fiber; Glass fiber, carbon fiber, alumina fiber , Tungsten fibers, molybdenum fibers, budene fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, silica fibers, and other inorganic fibers. 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.
These reinforcing fibers can be used alone or in combination of two or more, and the amount used is appropriately selected as desired, but is preferably 10 to 90 in the prepreg (crosslinkable resin composite). % By weight, more preferably 20 to 80% by weight, still more preferably 30 to 70% by weight. When the use amount of the reinforcing fiber is within this range, the dielectric property and mechanical strength of the obtained prepreg are highly balanced, which is preferable.

  In the method (c), the impregnation of the polymerizable composition into the reinforcing fiber may be performed by, for example, applying a predetermined amount of the polymerizable composition by spray coating, dip coating, roll coating, curtain coating, die coating, It can apply by applying to a fiber material by well-known methods, such as a slit coat method, putting a protective film on it as needed, and pressing with a roller etc. from the upper side. After impregnating the polymerizable composition into the fiber material, the polymerizable composition can be bulk polymerized by heating the impregnated product to a predetermined temperature, thereby obtaining a prepreg impregnated with the crosslinkable resin. Moreover, when impregnation is performed in a mold, reinforcing fibers are placed in the mold, and the polymerizable composition is poured into the mold. As the mold used in this case, the same mold as used in the method (b) can be used, and the filling pressure when filling the polymerizable composition into the cavity of the mold is also the above ( What is necessary is just to be the same as the method of b).

  In the method (c), the heating method of the impregnated product is not particularly limited, and the same method as the method (a) can be adopted, and the impregnated product may be placed on the substrate and heated. Alternatively, the polymerizable composition may be poured into a mold provided with a fiber material and impregnated with the polymerizable composition, and then bulk polymerization may be performed according to the method (b). Since the polymerizable composition of the present invention has a low viscosity and is excellent in impregnation properties for reinforcing fibers, the reinforcing fibers can be uniformly impregnated with a crosslinkable resin. In addition, since the polymerizable composition of the present invention has a low content of a solvent that does not participate in the reaction, a step of removing the solvent after impregnating the reinforcing fiber is unnecessary, and the productivity is excellent and the residual solvent Odors and blisters do not occur.

  The thickness of the prepreg obtained by the method (c) is appropriately selected according to the purpose of use, but is usually 0.001 to 10 mm, preferably 0.005 to 1 mm, more preferably 0.01. It is the range of -0.5mm. If it exists in this range, since the shapeability at the time of lamination | stacking and characteristics, such as a mechanical strength and toughness of the crosslinked resin composite obtained by bridge | crosslinking, are fully exhibited, it is suitable. The amount of volatile components of the prepreg obtained by the method (c) is an amount that volatilizes when heated at 200 ° C. for 1 hour, and is usually 30% by weight or less, preferably 10% by weight or less, more preferably 5% by weight. Hereinafter, it is particularly preferably 1% by weight or less. When the amount of volatile components in the prepreg is excessively large, the prepreg becomes sticky and the operability and storage stability tend to be poor.

  In any of the above methods (a), (b) and (c), the heating temperature for polymerizing the polymerizable composition is usually 50 to 250 ° C, preferably 80 to 200 ° C, more preferably 90. In the range of ˜150 ° C., less than 1 minute half-life temperature of the crosslinking agent, usually radical generator, preferably less than 10 ° C. of 1 minute half-life temperature, more preferably less than 20 ° C. of 1 minute half-life temperature. is there. The polymerization time may be appropriately selected, but is usually 10 seconds to 60 minutes, preferably within 20 minutes. Heating the polymerizable composition under the above conditions is preferable because a crosslinkable resin and a crosslinkable resin composite with little unreacted monomer can be obtained.

  The crosslinkable resin of the present invention and the crosslinkable resin portion constituting the crosslinkable resin composite of the present invention have substantially no crosslink structure, for example, are soluble in toluene, and the molecular weight thereof is gel- The weight average molecular weight in terms of polystyrene measured by permeation chromatography (eluent: toluene) is usually 1,000 to 1,000,000, preferably 5,000 to 500,000, more preferably 10,000. The range is from 000 to 100,000.

(Crosslinked product)
The crosslinked product of the present invention is obtained by crosslinking the crosslinkable resin of the present invention.
Crosslinking of the crosslinkable resin can be carried out, for example, by heating and melting the crosslinkable resin of the present invention to maintain the crosslinkable resin at a temperature at which the crosslinkable reaction occurs or higher. For example, when a radical generator is used as the crosslinking agent, the heating temperature for crosslinking the crosslinkable resin is usually at least 1 minute half-life temperature of the radical generator, preferably at least 5 ° C. higher than the 1-minute half-life temperature. The temperature is more preferably 10 ° C. or more higher than the 1 minute half-life temperature. Specifically, 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 1 to 120 minutes, more preferably 2 to 60 minutes.

  In the case where the crosslinkable resin is a sheet-like or film-like molded body, a method of laminating the crosslinkable resin on the substrate and hot pressing as necessary is preferable. The pressure at the time of hot pressing is usually 0.5 to 20 MPa, preferably 3 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).

(Crosslinked resin composite)
The crosslinked resin composite of the present invention comprises a crosslinked body and a support, and is obtained by crosslinking the crosslinkable resin composite produced by the method (a) or (c). can get. Alternatively, the cross-linked resin composite of the present invention is obtained by laminating the cross-linkable resin composite produced by the method (a) or (c) above on another support by hot pressing. It can also be obtained by heating and crosslinking. Furthermore, the crosslinked resin composite of the present invention can also be obtained by laminating the crosslinkable resin produced by the method (b) above on a support by hot pressing and crosslinking by heating on the support. Can do. Note that a plurality of cross-linked resin composites may be laminated.

  Examples of the support used in this case include copper foil, aluminum foil, nickel foil, chrome foil, gold foil, silver foil and other metal foils; printed wiring boards; conductive polymer films, films such as other resin films; Can be mentioned. Moreover, when a printed wiring board is used as the support, a multilayer printed wiring board can be manufactured. The surface of the conductive layer on the metal foil such as copper foil or printed wiring board is preferably treated with a silane coupling agent, a thiol coupling agent, a titanate coupling agent, or various adhesives. Of these, those treated with a silane coupling agent are particularly preferred.

  The cross-linked body and cross-linked resin composite of the present invention thus obtained are excellent in moldability, adhesion to a support and crack resistance in a thermal shock test, and thus are widely and suitably used as a high-frequency substrate material. be able to. Specifically, the crosslinked body and crosslinked resin composite of the present invention can be suitably used for microwave or millimeter wave high frequency circuit boards for communication equipment applications.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on weight unless otherwise specified.
The test and evaluation were as follows.

(1) Viscosity of polymerizable composition The viscosity of the polymerizable composition was measured using a high shear rate viscometer (model CAP2000 + L, manufactured by Brookfield), and the viscosity at a rotation speed of 10 rpm / 25 ° C was measured. Evaluation was made according to criteria.
A: Over 0.01 Pa · s, 1 Pa · s or less B: Over 1 Pa · s, 2 Pa · s or less C: Over 2 Pa · s, 3 Pa · s or less D: Over 3 Pa · s, 5 Pa · s or less

(2) Formability (surface shape of molded body)
The thickness of the laminated plate was measured at 10 points with a micrometer, and the thickness at each point was determined by subtracting the thickness of the copper foil from the measured thickness. And the maximum variation amount from the average value of thickness was calculated | required by percentage (%), and the moldability was evaluated according to the following references | standards.
A: 5% or less B: Over 5% to 10% or less C: Over 10% to 20% or less D: Over 20%

(3) Peel strength (adhesion)
The strength when peeling the copper foil from the laminate was measured according to JIS C6481, and the peel strength (adhesion) was evaluated according to the following criteria.
A: Over 0.6 kN / m B: Over 0.4 kN / m, 0.6 kN / m or less C: Over 0.2 kN / m, 0.4 kN / m or less D: 0.2 kN / m or less

(4) Crack resistance The laminated plate was subjected to a thermal shock test a predetermined number of times in the temperature range of −40 ° C. to + 150 ° C., the appearance of the laminated plate after the thermal shock test was visually observed, and the laminate plate was resistant to The crack property was evaluated. In addition, the thermal shock test was done with the thermal shock test apparatus (The product made by ESPEC company, model number; TSA-71H-W).
A: Generation of cracks was not confirmed in the sample after 300 cycles.
B: In the sample after 300 cycles, occurrence of cracks was confirmed.
C: Cracks were confirmed in the sample after the end of 200 cycles.
D: Generation of cracks was confirmed in the sample after the end of 100 cycles.

Example 1
1 part of bis (trimethoxysilyl) octane (SIB1824.0, manufactured by Asmax Co.) as the surface treating agent (A) represented by the above general formula (1), the surface treating agent represented by the above general formula (2) (B ) P-styryltrimethoxysilane (KBM-1403, manufactured by Shin-Etsu Chemical Co., Ltd.) 10 parts and methanol 11 parts were prepared to prepare a treating agent-containing solution ("bis (trimethoxysilyl) octane"/"P-styryltrimethoxysilane"=0.10 (weight ratio)). In a Henschel mixer, 500 parts of silica (SO-C2, manufactured by Admatechs, average particle diameter of 0.5 μm) as a filler is added, and 10 parts of the treating agent-containing solution prepared above is added thereto. Surface treatment silica was obtained by treating at 120 ° C. for 30 minutes.

  Separately from the above, in a glass flask, 51 parts of benzylidene (1,3-dimethyl-4-imidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and 79 parts of triphenylphosphine were added to 952 parts of toluene. To prepare a catalyst solution.

Further, in addition to the above, in a polyethylene bottle, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7] dodeca-4-ene (TCD) 80 parts, and also tetracyclic as cycloolefin monomers ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (MTF) 20 parts, where 2.5 parts of allyl methacrylate as a chain transfer agent and di-t-butyl peroxide (half a minute for 1 minute) A monomer solution was prepared by adding 1.2 parts of an initial temperature of 186 ° C. and 150 parts of the surface-treated silica prepared above and mixing them. And the catalyst liquid prepared above was added to the obtained monomer liquid in the ratio of 0.12 mL per 100 g of cycloolefin monomers, and it stirred, and prepared the polymeric composition.

  Next, 100 parts of the obtained polymerizable composition was cast on a polyethylene naphthalate film (type Q51, thickness 75 μm, manufactured by Teijin DuPont Films), and a glass cloth (product number 2116, thickness 92 μm) was spread thereon. Further, 80 parts of the polymerizable composition was cast thereon. Then, a polyethylene naphthalate film was further covered from above, and the entire glass cloth was impregnated with the polymerizable composition using a roller. Subsequently, this was heated for 1 minute in the heating furnace heated at 145 degreeC, and the polymerizable composition was bulk-polymerized, and the prepreg with a thickness of 0.13 mm was obtained.

  Next, the obtained prepreg was cut out to a size of 100 mm square, the polyethylene naphthalate film was peeled off, 8 sheets thereof were stacked, and heat-pressed for 15 minutes under conditions of 3 MPa and 200 ° C. with a hot press, Was made. And according to the said method, each evaluation of a moldability (surface shape of a molded object), peel strength (adhesion), and crack resistance was performed about the obtained laminated board. Moreover, the viscosity was measured about the obtained polymeric composition according to the said method. The results are shown in Table 1.

Examples 2-4
When preparing the surface-treated silica, the ratio of bis (trimethoxysilyl) octane as the surface treatment agent (A) and p-styryltrimethoxysilane as the surface treatment agent (B), respectively, by weight ratio, Except for “bis (trimethoxysilyl) octane” / “p-styryltrimethoxysilane” = 0.20 (Example 2), 0.33 (Example 3), and 0.50 (Example 4), In the same manner as in Example 1, a polymerizable composition and a laminate were obtained and evaluated in the same manner. In Examples 2 to 4, as in Example 1, the total amount of bis (trimethoxysilyl) octane as the surface treatment agent (A) and styryltrimethoxysilane as the surface treatment agent (B) is 11 parts. The results are shown in Table 1.

Example 5
In preparing the surface-treated silica, vinyltrimethoxysilane (KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the surface treatment agent (B) instead of p-styryltrimethoxysilane, and the ratio of the surface treatment agent Was obtained in the same manner as in Example 1 except that “bis (trimethoxysilyl) octane” / “vinyltrimethoxysilane” = 0.20 (weight ratio) was obtained. Evaluation was performed in the same manner. The results are shown in Table 1.

Example 6
When preparing the surface-treated silica, 1,4-bis (triethoxysilylethyl) benzene (SIB1831.0, manufactured by Azmax) was used as the surface treatment agent (A) instead of bis (trimethoxysilyl) octane. The ratio of the surface treatment agent used was the same as in Example 1 except that “1,4-bis (triethoxysilylethyl) benzene” / “p-styryltrimethoxysilane” = 0.20 (weight ratio). Thus, a polymerizable composition and a laminate were obtained and evaluated in the same manner. The results are shown in Table 1.

Example 7
Instead of p-styryltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (KBM-575, manufactured by Shin-Etsu Chemical Co., Ltd., methanol-containing, active ingredient 60%) ) And the ratio of the surface treatment agent is “bis (trimethoxysilyl) octane” / “N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride” = 0.30 ( Except for the weight ratio, a polymerizable composition and a laminate were obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Example 8
When preparing the surface-treated silica, 11 parts of bis (triethoxysilyl) vinylmethylsilane (SIB1818.0, manufactured by Azmax) instead of 1 part of bis (trimethoxysilyl) octane as the surface treatment agent (A) The polymerizable composition and the laminate were obtained in the same manner as in Example 1 except that p-styryltrimethoxysilane was not used as the surface treating agent (B), and evaluation was performed in the same manner. . The results are shown in Table 1.

Comparative Example 1
When preparing the surface-treated silica, except for using 11 parts of p-styryltrimethoxysilane as the surface treatment agent (B) without using bis (trimethoxysilyl) octane as the surface treatment agent (A), In the same manner as in Example 1, a polymerizable composition and a laminate were obtained and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 2
When preparing the surface-treated silica, Examples were used except that bis (trimethoxysilyl) octane as the surface treating agent (A) was not used and 11 parts of vinyltrimethoxysilane as the surface treating agent (B) was used. In the same manner as in No. 1, a polymerizable composition and a laminate were obtained and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 3
In preparing the surface-treated silica, bis (trimethoxysilyl) octane as the surface treating agent (A) and p-styryltrimethoxysilane as the surface treating agent (B) are not used, but instead octadesilyl A polymerizable composition and a laminate were obtained and evaluated in the same manner as in Example 1 except that 11 parts of trimethoxysilane (SIB1824.0, manufactured by Asmax Co.) was used. The results are shown in Table 1.

Comparative Example 4
In preparing the surface-treated silica, bis (trimethoxysilyl) octane as the surface treating agent (A) and p-styryltrimethoxysilane as the surface treating agent (B) were not used, but instead a titanate cup A polymerizable composition and a laminate were obtained and evaluated in the same manner as in Example 1 except that 11 parts of a ring agent (Plenact-TTS, manufactured by Ajinomoto Fine Techno Co., Ltd.) was used. The results are shown in Table 1.

As shown in Table 1, the polymerizable composition obtained by using the filler surface-treated with the surface treatment agent (A) according to the present invention and blending the filler has a low viscosity, The laminate obtained using the polymerizable composition was excellent in moldability, adhesion to the support (peel strength), and crack resistance in the thermal shock test (Examples 1 to 8).
On the other hand, when the surface treatment agent (A) according to the present invention was not used, the viscosity of the polymerizable composition was increased (Comparative Examples 1 and 2).
Further, when octadecyltrimethoxysilane is used as the surface treatment agent instead of the surface treatment agent (A) and the surface treatment agent (B) according to the present invention, the viscosity of the polymerizable composition is increased. The resulting laminate had inferior moldability, adhesion to the support (peel strength) and crack resistance in the thermal shock test (Comparative Example 3).
Furthermore, when a titanate coupling agent is used as the surface treatment agent in place of the surface treatment agent (A) and the surface treatment agent (B) according to the present invention, the resulting laminate is adhered to the support. (Crack strength) and crack resistance in the thermal shock test were inferior (Comparative Example 4).

Claims (6)

Surface treatment agent represented by the following general formula (1) (A) and surface treated filler with a surface treating agent represented by the following general formula (2) (B), a polymerization catalyst, and bulk polymerization can be cyclo viewing including the olefin monomer,
The ratio of the surface treatment agent (A) used for the surface treatment of the filler and the surface treatment agent (B) is, by weight ratio, surface treatment agent (A) / surface treatment agent (B) = 0. A polymerizable composition that is 1 to 0.33 .

(In the general formula (1), M ¹ represents Ti, Si, Al or Zr, X ¹ and X ² each independently represents a hydrolyzable group, a hydroxyl group or an alkyl group, and X ³ represents hydrolysis. Y represents a functional group or a hydroxyl group, and Y represents a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent containing a nitrogen atom, an oxygen atom or a sulfur atom, or nitrogen Represents an aromatic hydrocarbon group which may have a substituent containing an atom, oxygen atom or sulfur atom.)

(In the above general formula (2), M ² represents Ti, Si, Al or Zr, R ¹ represents a hydrocarbon group having a double bond, a mercapto group or an amino group at the terminal, and X ⁴ , X ⁵ Each independently represents a hydrolyzable group, a hydroxyl group or an alkyl group, and X ⁶ represents a hydrolyzable group or a hydroxyl group.) The polymerizable composition according to claim 1 , further comprising a crosslinking agent. Claim 1 or 2 the polymerizable composition according to obtained by bulk polymerization crosslinkable resin. A crosslinkable resin composite obtained by coating or impregnating the polymerizable composition according to claim 1 or 2 on a support and performing bulk polymerization. A crosslinked product obtained by crosslinking the crosslinkable resin according to claim 3 . A crosslinked resin composite comprising the crosslinked body according to claim 5 and a support.