JP2009132840A - Resin composite and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composite containing a polymer and a reinforcing material having low linear expansion coefficient and high strength by improving the impregnation property and adhesivity of the polymer with the refinforcing material. <P>SOLUTION: The resin composite includes the polymer and the surface treated reinforcing material, wherein the surface treatment includes a first surface treatment step of: surface treating with a first surface treatment agent selected from a group of alkoxy silanes, titanate compounds and aluminate compounds; and a second surface treatment step of: surface treating with a second surface treatment agent selected from silazanes. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composite containing a surface-treated reinforcing material. In particular, the present invention relates to a resin composite that has high impregnation and adhesion between a reinforcing material and a polymer, a low coefficient of linear expansion, and high strength.

  With the recent miniaturization of semiconductor circuits and the increase in the number of layers, through via holes, blind via holes, etc., and the increased density of circuit boards due to the surface mounting of small chip components, electronic devices have become smaller and lighter and higher in size. Performance and multifunction are progressing. A multilayer circuit board, which is one of such high-density mounting boards, is a laminated body in which conductor circuits and electrical insulating layers are alternately stacked. As a method of stacking an electrical insulation layer on a conductor circuit (wiring layer), a film or sheet-like molding of an electrically insulating resin is performed on a substrate having a conductor circuit on the surface (hereinafter sometimes referred to as “substrate”). The method of laminating | stacking by stacking | stacking an object and heating and pressurizing is common.

  However, the adhesion between the glass cloth, which is generally used as a reinforcing material for suppressing the thermal expansion of the circuit board, and the resin forming the electrical insulating layer is low, and the strength of the resulting circuit board may be insufficient. there were.

  Further, when mounted on a circuit board, the printed wiring board is warped due to repeated heating by a stack of packages or chips. This is due to a slight difference in the coefficient of thermal expansion between the insulating layer and the conductor layer, and becomes more noticeable as the substrate becomes thinner. Therefore, the material used for the circuit board is also required to cope with a lower shrinkage rate.

  In order to solve such a problem, for example, in Patent Document 1, a cycloolefin monomer is polymerized using a ruthenium carbene complex catalyst in the presence of a reinforcing material surface-treated with a silane coupling agent that does not inhibit the polymerization reaction. Technology is disclosed.

  Patent Document 2 discloses a technique in which a reinforcing fiber having a low sizing agent adhesion rate is impregnated with a polymerizable composition containing a norbornene monomer and a ruthenium metathesis polymerization catalyst to obtain a prepreg in a semi-cured state. It describes that it adheres by the anchor effect of a norbornene-type monomer and a reinforced fiber because the sizing agent adhesion rate is low.

In Patent Document 3, glass fiber is treated using a composition containing a film forming agent such as an epoxy polymer, a lubricant, and a silane compound containing a linear alkenyl group having 5 or more carbon atoms as a sizing agent, and this is treated with cycloolefin. A technique for use as a reinforcing material for a polymer obtained by ring-opening metathesis polymerization is disclosed. It is described that this sizing agent does not substantially inhibit ring-opening metathesis polymerization and a composite having high adhesive strength between glass fiber and polymer can be obtained.
US Pat. No. 6,040,363 JP 2003-171479 A International Publication No. 2004/009507 Pamphlet

  However, these methods still have insufficient impregnation and adhesion between the polymer and the reinforcing material, and may cause bubbles at the interface between the reinforcing material and the polymer. As a result, the resulting resin composite has a linear expansion. The rate increased and the strength was not satisfactory.

  Accordingly, an object of the present invention is to provide a resin composite containing a polymer and a reinforcing material, improving the impregnation and adhesion between the polymer and the reinforcing material, providing a resin composite having a low linear expansion coefficient and high strength. It is said.

  The inventors of the present invention diligently investigated the improvement of the impregnation property and adhesion between the polymer and the reinforcing material. By performing two-step surface treatment on the reinforcing material, the impregnation property and the adhesion between the polymer and the reinforcing material are obtained. The inventors have found that the property and the linear expansion coefficient are improved and the above-mentioned problems can be solved, and the present invention has been completed.

  That is, the gist of the present invention to solve the above problems is as follows.

(1) A resin composite comprising a polymer and a surface-treated reinforcing material,
A first surface treatment step in which the surface treatment is carried out with a first surface treatment agent of an aqueous solution selected from the group consisting of alkoxysilane, titanate compound and aluminate compound;
And a second surface treatment step of surface treatment with a second surface treatment agent selected from silazanes in this order.

(2) The resin composite according to (1), wherein the first surface treatment agent is an alkoxysilane represented by the following formula (I).

^{_{SiR 1 m (OR 2) n}} X 4- (m + n) ··· (I)
(Wherein R ¹ and R ² each independently represent a hydrocarbon group, X represents a hydrolyzable group, m and n are integers of 1 to 3, and m + n is an integer of 2 to 4) is there.)
(3) The resin composite according to (2), wherein R ¹ in the formula (I) is a hydrocarbon group having a carbon-carbon double bond.

(4) The resin composite according to (1), wherein the second surface treatment agent is a hydrocarbon group-containing silazane represented by the following formula (II):

In the formula, R ³ and R ⁴ are each independently a hydrocarbon group, R ^{5 to} R ⁸ are each independently hydrogen or a hydrocarbon group, and n is an integer of 0 to 3.

(5) The resin composite according to any one of (1) to (4), wherein the polymer is a cycloolefin polymer or polyphenylene ether.

(6) The resin composite according to any one of (1) to (5), further comprising a crosslinking agent.

(7) A crosslinked resin composite obtained by crosslinking the resin composite according to (6).

(8) A polymerizable composition containing a block polymerizable monomer and a polymerization catalyst,
A method for producing a resin composite that undergoes bulk polymerization in the presence of a surface-treated reinforcing material,
A first surface treatment step in which the surface treatment is carried out with a first surface treatment agent of an aqueous solution selected from the group consisting of alkoxysilane, titanate compound and aluminate compound;
And a second surface treatment step of performing a surface treatment with a second surface treatment agent selected from silazanes in this order.

(9) The production method according to (8), wherein the bulk polymerizable monomer is a cycloolefin monomer.

(10) The production method according to (8) or (9), wherein the polymerizable composition further contains a crosslinking agent.

  According to the present invention, by applying a specific surface treatment to the reinforcing material, the impregnation and adhesion between the polymer and the reinforcing material are improved. For this reason, in the obtained resin composite, a resin composite having high strength can be obtained without generating bubbles at the interface between the polymer and the reinforcing material.

  The resin composite of the present invention contains a polymer and a reinforcing material.

(Reinforcing material)
As the reinforcing material, inorganic and / or organic fibers can be used. For example, glass fibers, metal fibers, ceramic fibers, carbon fibers, aramid fibers, polyethylene terephthalate fibers, vinylon fibers, polyester fibers, amide fibers, polyarylate Known liquid crystal fibers such as These can be used alone or in combination of two or more. Examples of the shape of the reinforcing material include mat, cloth, and non-woven fabric.

(Glass cloth)
As the reinforcing material of the present invention, glass cloth is preferably used. A preferred glass cloth is made by weaving glass yarn (referred to as glass yarn) obtained by twisting glass filaments having a diameter of 1 to 10 μm into strands. The thickness of the glass cloth is usually 5 to 200 μm, preferably 10 to 150 μm, more preferably 10 to 100 μm, and particularly preferably 20 to 80 μm. If it is smaller than this range, the strength of the resulting resin composite will be weak, and if it is larger than this range, it may be difficult to control the thickness during lamination.

(Reinforcement surface treatment)
The reinforcing material used in the present invention is a first surface treatment step for surface treatment with a first surface treatment agent selected from the group consisting of alkoxysilanes, titanate compounds and aluminate compounds, and a second surface selected from silazanes. Surface treatment is performed by a second surface treatment step of surface treatment with a treatment agent.

  Among the above, alkoxysilane is preferably used as the first surface treatment agent. The alkoxysilane is not limited as long as it is a silane compound in which at least one alkoxyl group is bonded to a silicon atom, but an alkoxysilane represented by the following formula (I) is preferable.

^{_{SiR 1 m (OR 2) n}} X 4- (m + n) ··· (I)
In formula (I), R ¹ and R ² each independently represent a hydrocarbon group, and X represents a hydrolyzable group.

Preferably carbon number of a hydrocarbon group is 2-30, More preferably, it is 2-20, More preferably, it is 2-10. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, a cycloalkyl group, and an aryl group. The cycloalkyl group and aryl group may have an alkyl group, alkenyl group, cycloalkyl group or aryl group as a substituent. Among them, R ¹ (when m is 2 or 3, at least one of them) is preferably a group having a carbon-carbon double bond. Here, the “group having a carbon-carbon double bond” is an alkenyl group or a cycloalkyl group or an aryl group having an alkenyl group as a substituent. More preferably, the group containing an alkenyl group has a conjugated system formed by the carbon-carbon double bond and another carbon-carbon double bond or an aromatic ring. It is most preferable to have a conjugated system formed by an aromatic ring because of high radical reactivity. Since such alkoxysilane bonds to the above-described reinforcing material, a crosslinking reaction occurs between the polymer and the reinforcing material during the polymerization or the crosslinking reaction, and the interfacial adhesion between the reinforcing material and the polymer is further improved.

  The hydrolyzable group X is not particularly limited as long as it is a group capable of forming a hydroxyl group by hydrolysis, and examples thereof include halogen atoms such as chlorine atom and bromine atom.

  In the above formula (I), m and n are integers of 1 to 3, and m + n is an integer of 2 to 4.

Specific examples of the alkoxysilane represented by the formula (I) include allyltrimethoxysilane, 3-butenyltrimethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, allyltrichlorosilane, allylmethyldichlorosilane, styryltri Examples include chlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltrichlorosilane, n-decyltrimethoxysilane, n-hexyltrimethoxysilane, and diphenyldimethoxysilane. . Among them, R ¹ is an alkoxysilane having a carbon-carbon double bond, allyltrimethoxysilane, 3-butenyltrimethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, allyltrichlorosilane, allylmethyldichlorosilane, More preferred are styryltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, and vinyltrichlorosilane.

  Other specific examples of alkoxysilanes that can be used include β-methacryloxyethyltrimethoxysilane, β-methacryloxyethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, δ-methacryloxybutyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- ( Aminoethyl) -γ-aminopropyltrimethoxysilane, (N (vinylbenzyl) -aminoethyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (N-vinyl) Benzyl Aminoethyl) -γ-aminopropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, n-decyltrimethoxysilane, n-hexyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane and the like.

  Moreover, a well-known titanate coupling agent can be used as a titanate compound. Specific examples include triisostearoyl isopropyl titanate, di (dioctyl phosphate) diisopropyl titanate, didodecylbenzenesulfonyl diisopropyl titanate, diisostearyl diisopropyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) Examples thereof include oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, tetraisopropyl bis (dioctyl phosphite) titanate, and tetraoctyl bis (ditridecyl phosphite) titanate.

  Moreover, as an aluminate compound, a well-known aluminate coupling agent can be used. Specific examples include acetoalkoxy aluminum diisopropylate, aluminum diisopropoxy monoethyl acetoacetate, aluminum trisethyl acetoacetate, aluminum trisacetylacetonate and the like.

  In the present invention, first, a first surface treatment step is performed in which the surface of the reinforcing material is treated with a first surface treatment agent selected from the group consisting of alkoxysilanes, titanate compounds, and aluminate compounds. The surface treatment is performed by bringing the first surface treatment agent into contact with the reinforcing material surface. The treatment condition of the first surface treatment step is not particularly limited, and a condition that allows the first surface treatment agent to contact the reinforcing material surface may be selected. Specifically, there are a dry method in which the first surface treatment agent is brought into contact with the surface of the reinforcing material directly by spraying, and a wet method in which the reinforcing material is brought into contact with a solution obtained by dissolving the first surface treatment agent in a solvent. However, since the surface treatment can be performed uniformly, the wet method is preferable.

  As a specific method of the wet method, the reinforcing material is immersed in a solution of the first surface treatment agent and then pulled up and dried, or the surface of the reinforcing material is coated with a roll coater, a die coater, a gravure coater, or the like. The method of apply | coating the solution of a 1st surface treating agent using a construction apparatus, and then drying is mentioned.

  As the solvent for dissolving the first surface treatment agent, both water and organic solvents can be used, but water is preferred. It is also preferable to use water and a water-soluble organic solvent in combination. By using water and a water-soluble organic solvent in combination, the solution of the first surface treatment agent can be easily made into a uniform solution, and the surface of the reinforcing material can be treated uniformly. The water-soluble organic solvent is an organic solvent that is uniformly mixed with water in the solution of the first surface treatment agent. Specifically, alcohols, ketones, pyrrolidones, furans, amines, carboxylic acids, and the like Is mentioned. Among these, alcohols and ketones are preferable, and alcohols are more preferable. Most preferred alcohols are methanol and ethanol. A solvent can be used in combination of 2 or more types.

  The solution of the first surface treatment agent may further contain a surfactant. By using a surfactant, even when a highly hydrophobic material is used as the first surface treatment agent, it can be uniformly dissolved in water. Moreover, since the hydrolysis and condensation of the first surface treatment agent can be suppressed, the storage stability of the solution can be improved.

  The pH of the solution of the first surface treatment agent is usually 3 to 10, preferably 3 to 6. When the pH is within this range, the condensation reaction due to hydrolysis of the first surface treatment agent is suppressed, and the storage stability of the solution can be increased. The solution of the first surface treatment agent may contain a pH adjuster for the purpose of adjusting its pH. As the pH adjuster, organic acids such as acetic acid, formic acid, oxalic acid, citric acid, and butyric acid, aqueous ammonia, and the like can be used.

  The concentration of the first surface treatment agent in the solution of the first surface treatment agent is usually 0.001% by weight or more, preferably 0.005 to 10% by weight, more preferably 0.01 to 1% by weight, and particularly preferably 0. 0.01 to 0.1% by weight. If the concentration is too low, adhesion failure with the polymer may occur, and if the concentration is too high, condensation due to hydrolysis may easily occur.

  Next, a second surface treatment step is performed on the reinforcing material that has undergone the first surface treatment step, in which a surface treatment is performed with a second surface treatment agent selected from silazanes.

The second surface treatment agent may be unsubstituted silazane, but is particularly preferably a hydrocarbon group-containing silazane represented by the following formula (II).

In the formula, R ³ and R ⁴ are each independently a hydrocarbon group, and the plurality of R ³ and R ⁴ may be the same or different. R ^{5 to} R ⁸ are each independently hydrogen or a hydrocarbon group. N is an integer of 0-3.

  Here, as a hydrocarbon group, the hydrocarbon group similar to what was demonstrated by the said (I) formula is mentioned.

  More specific examples of such silazanes include hexamethyldisilazane, divinyltetramethyldisilazane, tetramethyldibutyldisilazane, tetramethyldiphenyldisilazane and the like, particularly preferably hexamethyldisilazane and divinyl. Tetramethyldisilazane is mentioned.

  In the second surface treatment step, the reinforcing material after the first surface treatment step is further treated with the second surface treatment agent. The surface treatment is performed by bringing the second surface treatment agent into contact with the reinforcing material surface. The method of contacting is not particularly limited. For example, (a) a method of immersing the reinforcing material in the second surface treatment agent and then pulling it up; (b) a surface of the reinforcing material such as a roll coater, a die coater, or a gravure coater. And a method of applying the second surface treatment agent using a coating apparatus; and (c) a method of spraying the second surface treatment agent on the surface of the reinforcing material using a spraying apparatus.

  Subsequently, it is preferable to dry the surface-treated reinforcing material. Although the temperature of drying is not specifically limited, 40-200 degreeC is preferable. The drying time is not particularly limited, but is preferably 30 minutes to 6 hours. The apparatus used for drying is not particularly limited, and any known apparatus can be used. Moreover, you may dry under reduced pressure. By performing the drying, it is possible to prevent the polymerization reaction from being inhibited by the remaining unreacted second surface treatment agent.

  The resin composite of the present invention is formed by densely impregnating a polymer in the gap between the reinforcing materials. As a method for producing the resin composite of the present invention, (I) a method in which a polymer is dissolved in a suitable solvent to form a varnish, impregnated into the surface-treated reinforcing material, and dried to remove the solvent. And (II) a method in which a polymerizable composition containing a bulk polymerizable monomer and a polymerization catalyst is impregnated in the surface-treated reinforcing material, and the polymerizable composition is bulk polymerized. In particular, the latter method (II) is preferred because of excellent polymer impregnation and adhesion to the reinforcing material. Here, bulk polymerization is a polymerization method in which a polymerizable monomer is polymerized substantially without a diluting solvent.

(polymer)
As the polymer used in the present invention, any of a thermoplastic polymer and a thermosetting polymer can be used without any particular limitation.

More specific examples of such polymers include rubbers such as nitrile-butadiene rubber and styrene-butadiene rubber;
Polyolefins such as polyethylene, polypropylene, cycloolefin polymers;
General-purpose plastics such as polyvinyl chloride and polystyrene;
Poly-4-methylpentene, acrylonitrile-butadiene-styrene (ABS resin), acrylonitrile-styrene (AS resin), methacrylic resin, polyamide, polyacetal, polyalkylene terephthalate, polycarbonate, polyphenylene ether, modified polyphenylene oxide, polyphenylene sulfide, modified polyamide 6T, Various engineering plastics such as polysulfone; Furthermore, liquid crystal polymer, polyether ether ketone, wholly aromatic polyester, thermoplastic polyimide, thermoplastic fluororesin (PEA, ETFE), polyketone sulfide, polyarylate, polyetherimide, polyamideimide, poly Ether sulfone, polyimide, polyamino bismaleimide, triazine resin, cross-linked polyimide and And cross-linked polyamide imide.

  Among these polymers, cycloolefin polymer and polyphenylene ether (PPE) are particularly preferable.

(Cycloolefin polymer)
In the present invention, the cycloolefin polymer is obtained by polymerizing a cycloolefin monomer.

(Cycloolefin monomer)
The cycloolefin monomer is a compound having a ring structure formed of carbon atoms in the molecule and having a carbon-carbon double bond in the ring. A cycloolefin polymer is obtained by polymerizing a cycloolefin monomer.

  Examples of the alicyclic structure constituting the cycloolefin monomer include a monocyclic ring, a polycyclic ring, a condensed polycyclic ring, a bridged ring, and a combination polycyclic ring. Although there is no special restriction | limiting in carbon number which comprises an alicyclic structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces.

  Examples of the cycloolefin monomer include a monocyclic cycloolefin monomer and a norbornene monomer, and a norbornene monomer is preferable. The norbornene-based monomer is a cycloolefin monomer having a norbornene ring structure in the molecule. These may be substituted with a hydrocarbon group such as an alkyl group, an alkenyl group, an alkylidene group or an aryl group, or a polar group. Further, the norbornene-based monomer may have a double bond in addition to the double bond of the norbornene ring.

  Examples of the monocyclic cycloolefin monomer include cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, and the like.

Specific examples of the norbornene-based monomer include dicyclopentadiene such as dicyclopentadiene and methyldicyclopentadiene;
Tetracyclo [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-phenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid, tetracyclo [6.2.1.1 ^3,6 . ^{Tetracyclododecenes} such as 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic anhydride;
2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-phenyl-2-norbornene, 5-norbornen-2-yl acrylate, 5-norbornen-2-yl methacrylate, 5- Norbornenes such as norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic anhydride;
Oxanorbornenes such as 7-oxa-2-norbornene and 5-ethylidene-7-oxa-2-norbornene;
Tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8] tetradec -3,5,7,12- tetraene (1,4-methano -1,4,4a, also referred to as a 9a- tetrahydro -9H- fluorene), pentacyclo [6.5.1.1 ^{3 , 6} . 0 ^2,7 . 0 ^9,13] pentadeca-4,10-diene, pentacyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] pentadeca-5,12-diene and other cyclic olefins having four or more rings; and the like.

  Among these cycloolefin monomers, a cycloolefin monomer having no polar group is preferable because a resin complex having a low dielectric loss tangent can be obtained.

  The cycloolefin polymer may be a ring-opening polymer or an addition polymer of a cycloolefin monomer, or a hydride thereof. The addition polymer may be a copolymer of a cycloolefin monomer and an α-olefin such as ethylene or propylene, or a chain non-conjugated diene such as 1,4-hexadiene.

  The polymerization method may be bulk polymerization or solution polymerization, but it is preferable to perform bulk ring-opening polymerization of the cycloolefin monomer in the presence of the surface-treated reinforcing material. According to such a method, since the monomer is uniformly impregnated in the glass fiber reinforcing material in a relatively short time, a homogeneous resin composite can be easily obtained.

  As a catalyst for ring-opening polymerization, a metathesis catalyst is used. The metathesis catalyst is not particularly limited as long as it can metathesis polymerize the cycloolefin monomer. 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. The transition metal atom is a metal after the fifth period of the long-period periodic table, and includes Group 5, Group 6 and Group 8 atoms. The atoms in each group are not particularly limited. For example, the group 5 atom includes tantalum, the group 6 atom includes molybdenum and tungsten, and the group 8 atom includes ruthenium and osmium.

  Among these, a complex of ruthenium or osmium belonging to Group 8 of the long periodic table is preferable, and a ruthenium carbene complex is particularly preferable for the following reason. The ruthenium carbene complex is excellent in catalytic activity, so that the ring-opening polymerization reaction rate can be increased and the productivity is excellent. Further, the obtained resin composite has little odor (derived from unreacted cyclic olefin). Furthermore, ruthenium carbene complexes are relatively stable against oxygen and moisture in the air and are not easily deactivated, and therefore can be suitably used particularly for bulk polymerization.

  The ruthenium carbene complex can be produced, for example, by a method described in Organic Letters, Vol. 1, page 953, 1999, Tetrahedron Letters, Vol. 40, page 2247, 1999, and the like.

Examples of ruthenium carbene complexes include benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesitylimidazolidine-2-ylidene) (3- Methyl-2-butene-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-dihydrobenzimidazol-2-ylidene) (tricyclohexyl) Phosphine) 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, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) pyridine ruthenium dichloride A ruthenium complex compound having an atom-containing carbene compound and a neutral electron-donating compound;
Carbene compounds containing two heteroatoms as ligands such as benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride and benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride A ruthenium complex compound having:
(1,3-Dimesityrylimidazolidin-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene) (1,3-diisopropyl-4-imidazoline-2-ylidene) (tri Cyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylideneruthenium dichloride, and the like.

  Among these ruthenium carbene complexes, a ruthenium complex compound having, as a ligand, substituted imidazoline-2-ylidene substituted at the 4th and 5th positions exemplified by JP-A-2005-104922 with a halogen atom is preferable.

  These may be used alone or in combination of two or more. The amount of the metathesis polymerization catalyst is usually 1: 2,000 to 1: 2,000,000, preferably 1: 5,000 to 1, in a molar ratio of (transition metal atom in the catalyst) :( cycloolefin monomer). : 1,000,000, more preferably in the range of 1: 10,000 to 1: 500,000.

  The metathesis polymerization catalyst can be used in combination with an activator. The activator is added for the purpose of controlling the polymerization activity or improving the polymerization reaction rate. Examples of the activator include aluminum, scandium, tin alkylates, halides, alkoxylates, and aryloxylates.

  Preferred activators include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium, tetra Examples thereof include alkoxy tin and tetraalkoxy zirconium.

  When the activator is used, the amount used is usually a molar ratio of (metal atom in the metathesis polymerization catalyst: activator) of 1: 0.05 to 1: 100, preferably 1: 0.2 to 1: 20, more preferably in the range of 1: 0.5 to 1:10.

  In addition, when a complex of a transition metal atom of group 5 or 6 is used as a metathesis polymerization catalyst, it is preferable that both the metathesis polymerization catalyst and the activator are used by dissolving in a cycloolefin monomer. As long as the properties are not inherently impaired, they can be suspended or dissolved in a small amount of solvent.

  Catalysts used for addition polymerization of cycloolefin monomers include catalysts comprising titanium, zirconium or vanadium compounds and organoaluminum compounds; metallocene compounds of group 4 transition metal atoms such as titanium and zirconium; Group 10 transition metal atom complexes; and the like.

  The solvent used for the solution polymerization is not particularly limited as long as it is inert to the catalyst. Examples of the solvent include chain aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; cycloaliphatic groups such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, hexahydroindenecyclohexane, and cyclooctane. Hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; oxygen-containing hydrocarbons such as diethyl ether and tetrahydrofuran;

  In the metathesis polymerization, aromatic hydrocarbons, chain aliphatic hydrocarbons, and alicyclic hydrocarbons, which are excellent in solubility of the metathesis polymerization catalyst and are widely used industrially, are preferable. In addition, a liquid antioxidant, a liquid plasticizer, and a liquid modifier may be used as a solvent as long as the activity of the metathesis polymerization catalyst is not lowered. These may be used singly or in combination of two or more.

  Also in the bulk polymerization, the above-mentioned solvent can be used in a small amount in order to dissolve the polymerization catalyst and other components as required. The amount used is usually 10 parts by weight or less, preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and still more preferably 2 parts by weight or less with respect to 100 parts by weight of the cycloolefin monomer.

  In the polymerization reaction, it is preferable to use a chain transfer agent. By using a chain transfer agent, it is possible to prevent the reaction from proceeding excessively due to heat generation during polymerization, and to adjust the molecular weight of the polymer to be produced. As the chain transfer agent in the metathesis polymerization of the cycloolefin monomer, a compound having at least one vinyl group can be used.

As the chain transfer agent, those having a group that contributes to crosslinking described later in addition to the vinyl group are preferable. The group that contributes to the crosslinking is specifically a group having a carbon-carbon double bond, and examples thereof include a vinyl group, an acryloyl group, and a methacryloyl group. These groups are preferably at the end of the molecular chain. In particular, the _{formula: CH 2 = CH-Q-} Y compounds represented by are preferred. In the formula, Q represents a divalent hydrocarbon group, and Y represents a vinyl group, an acryloyl group, or a methacryloyl group. Examples of the divalent hydrocarbon group represented by Q include an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and a group formed by bonding them. Among these, a phenylene group and an alkylene group having 4 to 12 carbon atoms are preferable. By using the chain transfer agent having this structure, it is possible to obtain a crosslinked body or crosslinked resin composite having higher strength.

  Preferred examples of such chain transfer agents include compounds in which Y is a methacryloyl group, such as allyl methacrylate, 3-buten-1-yl methacrylate, hexenyl methacrylate, undecenyl methacrylate, decenyl methacrylate; A compound in which Y is an acryloyl group such as 3-buten-1-yl acrylate; a compound in which Y is a vinyl group such as divinylbenzene; Of these, undecenyl methacrylate, hexenyl methacrylate and divinylbenzene are particularly preferred.

  In addition to the above, compounds that can be used as chain transfer agents include aliphatic olefins such as 1-hexene and 2-hexene; olefins having an aromatic group such as styrene; alicyclic hydrocarbons such as vinylcyclohexane Olefins having a group; vinyl ethers such as ethyl vinyl ether; vinyl ketones such as methyl vinyl ketone, 1,5-hexadien-3-one and 2-methyl-1,5-hexadien-3-one; styryl acrylate, ethylene Acrylic esters such as glycol diacrylate; silanes such as allyltrivinylsilane, allylmethyldivinylsilane, allyldimethylvinylsilane; glycidyl acrylate, allyl glycidyl ether; allylamine, 2- (diethylamino) ethanol vinyl ether, 2- Diethylamino) ethyl acrylate, 4-vinyl aniline; and the like.

  These chain transfer agents may be used singly or in combination of two or more. When a chain transfer agent is used, the amount thereof is usually 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polymerizable monomer. It is. When the amount of the chain transfer agent is within this range, the crosslinking reaction during the polymerization is sufficiently suppressed, so that a polymer having excellent fluidity can be obtained.

  The reaction conditions for performing the solution polymerization may be any known method and are not particularly limited. For example, the polymerization reaction temperature is usually −50 to 100 ° C., and the pressure during the polymerization reaction is usually 0 to 5 MPa. The reaction conditions for the hydrogenation may be any known method and are not particularly limited.

  In bulk polymerization, a metathesis polymerization retarder may be blended in the polymerizable composition. The metathesis polymerization retarder is blended for the purpose of controlling the polymerization activity of the metathesis polymerization catalyst, extending the gelation time (pot life) of the polymerizable composition, and improving processability. Examples of such metathesis polymerization retarders include triphenylphosphine, triethylphosphine, tri-n-butylphosphine, methyldiphenylphosphine, dicyclohexylphosphine, vinyldiphenylphosphine, allyldiphenylphosphine, triallylphosphine, and styryldiphenylphosphine. Phosphines; Lewis bases such as aniline; and the like.

  Furthermore, a cycloolefin monomer having a diene structure or a triene structure in the ring or a cycloolefin monomer having an unsaturated bond outside the ring also acts as a polymerization retarder. Examples of such cycloolefin monomers include 1,5-cyclooctadiene and 5-vinyl-2-norbornene.

  Among these polymerization reaction retarders, a phosphine compound is preferable because of its great effect of suppressing the progress of the polymerization reaction at room temperature or lower, and triphenylphosphine, triethylphosphine, dicyclohexylphosphine, and vinyldiphenylphosphine are more preferable. These metathesis polymerization retarders may be used alone or in a combination of two or more. When a metathesis polymerization retarder is used, the amount is arbitrarily set depending on the compound used and the purpose, but it is usually 1: 0 in molar ratio of (transition metal atom in the metathesis polymerization catalyst: polymerization retarder). 0.05 to 1: 100, preferably 1: 0.2 to 1:20, more preferably 1: 0.5 to 1:10.

(Method for producing polymerizable composition)
The manufacturing method of a polymerizable composition consists of the process of mixing each said component, and the order of mixing etc. are not restrict | limited in particular. That is, the polymerizable composition may be obtained by simply mixing the components. The polymerizable composition containing a cycloolefin monomer is preferably prepared by preparing a liquid in which a polymerization catalyst is dissolved or dispersed in an appropriate solvent (hereinafter sometimes referred to as “catalyst liquid”), and separately linking to the polymerizable monomer. By preparing a liquid (hereinafter sometimes referred to as “monomer liquid”) containing additives such as a transfer agent and a crosslinking agent, which will be described later, as necessary, adding a catalyst liquid to the monomer liquid, and stirring. Can be prepared. The catalyst solution is preferably added immediately before the polymerization described below.

In this case, the temperature of the monomer solution when adding the catalyst solution is usually -10 ° C to 25 ° C, preferably -5 ° C to 20 ° C, more preferably -5 to 15 ° C, particularly preferably -5 ° C to 10 ° C. It is preferable that If it is higher than this temperature, the polymerization proceeds rapidly at the moment when the polymerization catalyst is added, and the viscosity of the polymerizable composition may increase and impregnation may not be possible.
Further, the temperature of the polymerizable composition from the addition of the catalyst solution to the start of polymerization is preferably -10 ° C to 25 ° C, more preferably -5 ° C to 20 ° C, and -5 to 15 ° C, particularly preferably. Is preferably −5 to 10 ° C. If it is higher than this temperature, the polymerization proceeds rapidly, and the viscosity of the blended liquid may increase, making impregnation impossible. If the temperature is lower than this temperature, the monomer liquid may freeze or the economy may be deteriorated. The addition of the catalyst solution is preferably performed in an inert gas atmosphere such as nitrogen.

The method for cooling the monomer solution before the addition of the catalyst solution and the polymerizable composition after the addition of the catalyst solution is not particularly limited and is performed by a commonly used method. For example, it can cool with cold water, an ice bath, an ice salt bath, a methanol-dry ice bath, etc.
In preparing the monomer liquid, the order in which the polymerization retarder and other additives are added to the cycloolefin monomer is not particularly limited. Moreover, the mixing apparatus etc. which are used for preparation of a monomer liquid are not specifically limited, What is necessary is just to select suitably according to the viscosity of a monomer liquid, etc. Examples thereof include wheel type, ball type, blade type, roll type devices such as a mix muller, ball mill, kneader, Henschel mixer, roll mill, Banbury mixer, ribbon mixer, homogenizer, twin-screw extruder, rakai machine and the like.
Bulk polymerization can be performed by impregnating the reinforcing composition with the polymerizable composition and heating the impregnated product to a predetermined temperature.

  As a method for impregnating the polymerizable composition into the reinforcing material, for example, a predetermined amount of the polymerizable composition is poured on a cloth, mat, etc. of the reinforcing material, and a protective film is stacked on the reinforcing material, if necessary. And a method of pressing with a roller or the like.

  The bulk polymerization reaction is started by heating the polymerizable composition to a predetermined temperature. As a heating method, for example, an impregnated material is placed on a support, and a polymerizable composition applied to the support is placed on a heating plate and heated. Heating while applying pressure using a press (hot press) ), A method of pressing a heated roller, a method of using a heating furnace, a method of heating after impregnating a polymerizable composition by previously installing a reinforcing material in a mold, and the like.

  The heating temperature for bulk polymerization of the polymerizable composition is usually 30 to 250 ° C, preferably 50 to 200 ° C. The polymerization time may be appropriately selected, but is usually 1 second to 20 minutes, preferably 10 seconds to 5 minutes or less.

  When the bulk polymerization reaction starts, the temperature of the polymerizable composition rapidly increases due to the heat of reaction, and reaches the peak temperature in a short time (for example, about 10 seconds to 5 minutes). Further, the bulk polymerization reaction proceeds, but the polymerization reaction gradually stops and the temperature decreases. It is preferable to control the peak temperature so as to be equal to or higher than the glass transition temperature of the polymer constituting the composite obtained by this polymerization reaction, since the polymerization proceeds completely. The peak temperature can be controlled by the heating temperature. In the case of a composite obtained from a polymerizable composition containing a chain transfer agent, the polymerization reaction rate of the polymer is usually 80% or more, preferably 90% or more, more preferably 95% or more. The polymerization reaction rate of the polymer can be determined, for example, by analyzing a solution obtained by dissolving the polymer in a solvent by gas chromatography. A polymer in which bulk polymerization has progressed almost completely has few residual monomers and generates less odor.

  Moreover, the range of the weight average molecular weight of the cycloolefin polymer used for this invention becomes like this. Preferably it is 5,000-80,000, More preferably, it is 10,000-50,000, Most preferably, it is 15,000-30,000. is there. The molecular weight distribution is a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), and is preferably 3 or less, more preferably 2.3 or less, and most preferably 2 or less. If the molecular weight is too low, the fluidity is too high, and therefore it may be difficult to control the resin embedding property or flatness in the support. On the other hand, if the molecular weight is too high, it may not flow in the temperature range during crosslinking.

(Polyphenylene ether)
Polyphenylene ether is a polymer having a repeating unit formed by 1,4-bonding phenyleneoxy groups which may have a substituent. Such a repeating unit is represented by the following formula (1).

In the formula, each of R ^{1 to} R ⁴ independently represents a hydrogen atom, a halogen atom, or an alkyl group, alkenyl group, alkynyl group, aryl group, or haloalkyl group having 1 to 20 carbon atoms. Among these, R ¹ and R ⁴ are preferably an alkyl group or an alkenyl group, and more preferably a methyl group. R ² and R ³ are preferably hydrogen atoms.

  The content of the repeating unit represented by the formula (1) in the polyphenylene ether is preferably 80% by weight or more, more preferably 90% by weight or more. The polyphenylene ether used in the present invention may have a repeating unit other than the repeating unit represented by the formula (1). Such a repeating unit is not particularly limited as long as it is a divalent organic group. Specific examples include an alkylene group, an arylene group, and an oxygen atom.

  The polyphenylene ether may be a linear polymer formed from these repeating units, or may be a branched polymer having a structure in which a plurality of such polymers are bonded.

  The molecular weight of the polyphenylene ether is a number average molecular weight in terms of standard polystyrene measured by gel permeation chromatography, and is preferably 2,000 to 15,000, more preferably 2,000 to 10,000. When the number average molecular weight is within this range, both fluidity and heat resistance are excellent.

(Production method of polyphenylene ether)
Any known method can be adopted as a method for producing polyphenylene ether, and is not particularly limited, but an oxidative polymerization method is preferred. The oxidative polymerization method is a method in which monovalent phenol represented by formula (2) and / or divalent phenol represented by formula (3) is oxidatively polymerized in the presence of a catalyst. According to the oxidative polymerization method, a polyphenylene ether resin having the above molecular weight range can be easily obtained. Examples of the oxidation method include a method using oxygen gas or air directly, or an electrode oxidation method.

In formula (2) and formula (3), R ^{1 to} R ⁴ represent the same meaning as in formula (1). In the formula (3) represent the same meaning as ^R 1 to R ⁴ of R ^'1 to ^{R' 4} each formula (1).

As a catalyst for oxidative polymerization using oxygen gas or air, a catalyst in which a copper salt and an amine are combined is used. Examples of the copper salt include CuCl, CuBr, Cu ₂ SO ₄ , CuCl ₂ , CuBr ₂ , CuSO ₄ , and CuI. Examples of amines include pyridine, methylpyridine, N, N-dimethyl-4-aminopyridine, poly-4-vinylpyridine, piperidine, morpholine, triethanolamine, n-butylamine, octylamine, dibutylamine, N, N- Dimethyl-n-hexylamine, N, N-dimethyl-n-butylamine, triethylamine, (N, N-di-tert-butyl) ethylenediamine 2-aminoethanethiol, 2-mercapto-1-ethanol, 1,2-dimercapto -4-methylbenzene and the like.

  The solvent used in the polymerization is not particularly limited, and the temperature of the polymerization reaction is not limited, but it is preferably performed at 0 to 50 ° C.

  The high molecular weight polyphenylene ether can be used in the above molecular weight range by reducing the molecular weight by a redistribution reaction disclosed in The Journal of Organic Chemistry, 1969, Vol. 34, 297. The redistribution reaction is a method of reducing the molecular weight by reacting polyphenylene ether with phenols in the presence of a radical initiator.

  The phenols used in the redistribution reaction include phenol, o-bromophenol, m-bromophenol, p-bromophenol, p-chlorophenol, 2,6-dichlorophenol, pentachlorophenol, o-cresol, and m-cresol. P-cresol, 2,6-xylenol, mesitol, 2,6-dimethyl-4- (benzoyloxy) phenol, p-methoxyphenol, p-phenoxyphenol, hydroquinone monobenzoate, β-naphthol, p-hydroxybenzonitrile, Examples include 2,6-dimethylphenol, p-nitrophenol, methyl p-hydroxybenzoate, methyl salicylate, bisphenol A, 2,6-dimethylphenol, 4,4′-dihydroxydiphenyl ether. Although the usage-amount of phenols can be suitably adjusted according to the molecular weight of desired polyphenylene ether, 0.5-10 weight part is preferable with respect to 100 weight part of polyphenylene ether resin.

  As radical initiators, benzoyl peroxide, 3,3 ′, 5,5′-tetramethyl-1,4-diphenoquinone, chloranil, 2,4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl Examples thereof include monocarbonate and azobisisobutyronitrile. The amount of the radical initiator used is preferably 0.5 to 5.0 parts by weight with respect to 100 parts by weight of the polyphenylene ether resin. Moreover, it is preferable to use metal carboxylates such as cobalt naphthenate and manganese naphthenate as the reaction accelerator.

  The redistribution reaction is preferably performed in a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction, but aromatic hydrocarbons such as toluene, benzene and xylene are preferable. The redistribution reaction can be carried out by dissolving or dispersing the polyphenylene ether resin, the phenols, the radical initiator, and the carboxylic acid metal salt used as required in a solvent and heating them. The reaction temperature is preferably 60 to 120 ° C., and the reaction time is preferably 10 minutes to 6 hours.

  The polyphenylene ether obtained as described above usually has a hydroxyl group at the terminal or a phenyl group which may have a substituent at the ortho or meta position. A polyphenylene ether having a substituent other than the above may be used by modifying the terminal of the polyphenylene ether resin. In particular, it preferably has an unsaturated hydrocarbon group.

  As a method for introducing an unsaturated hydrocarbon group by modifying the molecular chain terminal of polyphenylene ether, halogenation having a carbon-carbon unsaturated bond in the presence of a basic hydroxide in an unmodified polyphenylene ether resin. The method of making a hydrocarbon compound react is mentioned. Examples of the basic hydroxide include sodium hydroxide, potassium hydroxide and tetraalkylammonium hydroxide. Examples of the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond include p-chloromethylstyrene, m-chloromethylstyrene, p-bromomethylstyrene, m-bromomethylstyrene, and allyl bromide. . Further, in order to accelerate the reaction, a quaternary ammonium salt such as tetra-n-butylammonium bromide may be used as a phase transfer catalyst. Although reaction conditions are not specifically limited, Reaction temperature is 30-100 degreeC normally, and reaction time is 0.5 to 20 hours normally. Since the polar structure in the polyphenylene ether is reduced by modifying the terminal, the cross-linked resin obtained using this has excellent electrical characteristics.

  In the present invention, a bulk polymerizable monomer other than the above-mentioned cycloolefin monomer can also be preferably used.

As a specific example of such a bulk polymerizable monomer,
Addition polymerization type carbon multiple bond monomers such as olefins, halogenated olefins, dienes, acetylenes, styrene, vinyl compounds and acrylic acids;
Cyclic ether, lactone, lactam, cyclic amine, cyclic sulfide, cyclic carbonate, cyclic acid anhydride, cyclic imino ether, amino acid-N-carboxylic acid anhydride, cyclic imide, cyclic phosphorus-containing compound, cyclic silicon-containing compound, cyclic olefin, etc. A ring-opening polymerization type or polycondensation type cyclic monomer;
Phenol, melamine, urea, diamine, dicarboxylic acids, oxycarboxylic acid, aminocarboxylic acid, diol, diisocyanate, sulfur-containing compound, phosphorus-containing compound, aromatic ether, dihalogen compound, aldehyde, diketone compound, carbonic acid derivative, etc. Condensation-type or polyaddition-type bifunctional monomers; and aniline derivatives, silicon compounds, epoxy compounds, macromers, and the like.

  Among these bulk polymerizable monomers, aromatic vinyl monomers and acrylic monomers are preferable from the viewpoints of availability, uniformity of reaction, and physical properties of the resulting polymer.

(Aromatic vinyl monomer)
Specific examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene, vinylethylbenzene, vinylxylene, pt-butylstyrene, α-methyl-p-methylstyrene, vinylnaphthalene, and the like.

(Acrylic monomer)
In the present invention, the acrylic monomer represents acrylic acid, methacrylic acid, or esters thereof. The acrylic acid or methacrylic acid ester is preferably an alkyl ester, and specific examples thereof include acrylic acid or methacrylic acid methyl ester, acrylic acid or methacrylic acid ethyl ester, acrylic acid or methacrylic acid n-butyl ester, acrylic acid. Alternatively, methacrylic acid 2-ethylhexyl ester, acrylic acid, methacrylic acid n-octyl ester, or the like can be given. Acrylic acid or methacrylic acid hydroxyethyl ester, acrylic acid or methacrylic acid N, N-dimethylaminomethyl ester, acrylic acid or glycidyl methacrylate acrylic acid or methacrylic acid ester, Polyvalent acrylic acid (or methacrylic acid) esters such as methacrylate and trimethylolpropane trimethacrylate can also be used.

  In addition to the polymerizable monomer, the polymerizable composition contains a polymerization catalyst, and may further contain a chain transfer agent or the like as necessary.

(Polymerization catalyst)
The polymerization catalyst is appropriately selected according to the type of polymerizable monomer to be used, and the amount used is also appropriately set according to the catalyst type and reaction system. As such a polymerization catalyst, a polymerization initiator such as a photopolymerization initiator, a radical polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator,
Examples include transition metal catalysts such as platinum catalysts, metallocene catalysts, and metathesis catalysts, and organic acids, inorganic acids, inorganic alkalis, and amines.

  Among these, when the polymerizable monomer is an aromatic vinyl monomer, examples of the polymerization catalyst include radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators, metallocene catalysts, phenoxyimine catalysts, and the like. , Metallocene catalysts, phenoxyimine catalysts and the like are preferable.

  When the polymerizable monomer is an acrylic monomer, a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator are preferably used as the polymerization catalyst.

  Known radical initiators can be used. For example, persulfates such as potassium persulfate and ammonium persulfate; hydrogen peroxide; lauroyl peroxide, benzoyl peroxide, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate, cumene hydroperoxide, etc. These can be used alone or in combination, or as a redox system in combination with a reducing agent such as acidic sodium sulfite, sodium thiosulfate, and ascorbic acid. 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), Azo compounds such as dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis (4-cyanopentanoic acid); 2,2′-azobis (2-aminodipropane) dihydrochloride, 2, Amidine compounds such as 2'-azobis (N, N'-dimethyleneisobutylamidine) and 2,2'-azobis (N, N'-dimethyleneisobutylamidine) dihydrochloride can also be used.

  The polymerizable composition may further contain a chain transfer agent. By blending the chain transfer agent, it is possible to prevent the reaction due to heat generation during the polymerization from proceeding and to adjust the molecular weight of the polymer to be produced.

  When an acrylic monomer or an aromatic vinyl monomer is used as the polymerizable monomer, examples of the chain transfer agent include lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-propion mercapto acid and α-methylstyrene dimer. Can be used.

  These chain transfer agents may be used singly or in combination of two or more. When a chain transfer agent is used, the amount thereof is usually 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polymerizable monomer. It is. When the amount of the chain transfer agent is within this range, the crosslinking reaction at the time of polymerization is sufficiently suppressed, so that a resin molded article having excellent fluidity can be obtained.

  In the polymerizable composition, a polymer may be further blended for initial viscosity adjustment. The polymer to be blended is preferably a polymer formed from a monomer contained in the polymerizable composition or a derivative thereof. For example, when an acrylic monomer is used as a monomer, a polymer obtained by polymerizing an acrylic monomer is preferable as the viscosity adjusting polymer.

  Although the manufacturing method of polymeric composition and the method of block polymerization are not specifically limited, The method similar to the case where a cycloolefin monomer is used can be taken.

(Manufacture of resin composite)
As described above, the resin composite (prepreg) of the present invention can be obtained by impregnating the polymerizable composition into a reinforcing material and heating the impregnated product to a predetermined temperature to perform bulk polymerization. Alternatively, the polymer can be obtained by dissolving the polymer in a suitable solvent, forming a varnish, impregnating the reinforcing material, and drying to remove the solvent.

  The solvent used for the preparation of the varnish is not limited as long as it can dissolve the polymer, but the boiling point is preferably 30 to 250 ° C, more preferably 50 to 200 ° C. When a solvent having a boiling point in such a range is used, it is suitable for heating and volatilizing and drying later. As such a solvent, those exemplified as the solvent for the solution polymerization can be used.

  The amount of the solvent used is appropriately selected according to the thickness and surface flatness of the desired molded article, but the solid content concentration of the varnish is usually 5 to 70% by weight, preferably 10 to 65% by weight, more preferably. Is in the range of 20 to 60% by weight.

  There is no special limitation in the preparation method of a varnish, For example, what is necessary is just to mix the said polymer and the arbitrary components mix | blended as needed according to a conventional method.

Examples of the mixer used for mixing include a magnetic stirrer, a high-speed homogenizer, a disper, a planetary stirrer, a twin-screw stirrer, a ball mill, and a three-roller.

  The mixing temperature is preferably within a range that does not cause a crosslinking reaction by a crosslinking agent described later and below the boiling point of the solvent.

  In order to impregnate the reinforcing material with the varnish, for example, a predetermined amount of varnish is poured onto the reinforcing material cloth, mat, etc., if necessary, a protective film is layered thereon, and pressed from above with a roller or the like. Can be performed.

  The drying conditions for the varnish are appropriately selected depending on the type of solvent. Specifically, the drying temperature is usually 20 to 300 ° C, preferably 30 to 200 ° C. If the drying temperature is too high, the crosslinking reaction proceeds, and the resulting resin composite may become non-uniform or the solvent may remain. The drying time is usually 30 seconds to 1 hour, preferably 1 minute to 30 minutes.

(Crosslinking agent)
The resin composite of the present invention preferably further contains a crosslinking agent in addition to the polymer and the reinforcing material.

  The cross-linking agent causes a cross-linking reaction with a functional group in the polymer to form a cross-linked structure. Examples of such functional groups involved in the crosslinking reaction include carbon-carbon double bonds, carboxylic acid groups, acid anhydride groups, hydroxyl groups, amino groups, active halogen atoms, and epoxy groups. In the case of having these functional groups, the crosslinkability can be imparted to the resulting resin composite by adding a crosslinking agent.

  Examples of the crosslinking agent include radical generators, epoxy compounds, isocyanate group-containing compounds, carboxyl group-containing compounds, acid anhydride group-containing compounds, amino group-containing compounds, Lewis acids, and the like. These crosslinking agents can be used alone or in combination of two or more. Among these, a radical generator, an epoxy compound, an isocyanate group-containing compound, a carboxyl group-containing compound, and an acid anhydride group-containing compound are preferable, and a radical generator is particularly preferable.

  Examples of the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators. 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; 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2 , 5-Di (t-butylperoxy) hexyne-3,1,3-di Peroxyketals such as (t-butylperoxyisopropyl) benzene; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; peroxycarbonates such as t-butylperoxyisopropylcarbonate and di (isopropylperoxy) dicarbonate And alkylsilyl peroxides such as t-butyltrimethylsilyl peroxide; and the like.

  Examples of the diazo compound include 4,4′-bisazidobenzal (4-methyl) cyclohexanone, 4,4′-diazidochalcone, 2,6-bis (4′-azidobenzal) cyclohexanone, and 2,6-bis. (4′-azidobenzal) -4-methylcyclohexanone, 4,4′-diazidodiphenylsulfone, 4,4′-diazidodiphenylmethane, 2,2′-diazidostilbene and the like.

  Non-polar radical generators include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diphenylbutane, 1,4-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1, 1,2,2-tetraphenylethane, 2,2,3,3-tetraphenylbutane, 3,3,4,4-tetraphenylhexane, 1,1,2-triphenylpropane, 1,1,2- Triphenylethane, triphenylmethane, 1,1,1-triphenylethane, 1,1,1-triphenylpropane, 1,1,1-triphenylbutane, 1,1,1-triphenylpentane, 1, Examples include 1,1-triphenyl-2-propene, 1,1,1-triphenyl-4-pentene, 1,1,1-triphenyl-2-phenylethane, and the like.

Of these, dialkyl peroxides and nonpolar radical generators are preferred in that they have less obstacles to the ring-opening bulk polymerization reaction of the metathesis catalyst.

  The cross-linking agent to be used can be properly used depending on which functional group (cross-linking site) in the resin composite is used for cross-linking. For example, in the case of crosslinking at a carbon-carbon double bond portion, it is preferable to use a radical generator. In addition, an epoxy compound can be used for crosslinking a thermoplastic resin having a carboxyl group or an acid anhydride group, and a compound containing an isocyanate group is used for crosslinking a thermoplastic resin having a hydroxyl group. In the case where a thermoplastic resin containing an epoxy group is crosslinked, a carboxyl group-containing compound or an acid anhydride group-containing compound can be used. In addition, when it is desired to crosslink cationically, Lewis acid can be used as a crosslinking agent.

  The amount of the crosslinking agent is not particularly limited, and can be appropriately set according to the type of the crosslinking agent used. For example, when a radical generator is used as the crosslinking agent, the amount of the crosslinking agent used is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the polymerizable monomer. It is. If the addition amount of the crosslinking agent is too small, crosslinking may be insufficient, and a crosslinked molded product having a high crosslinking density may not be obtained. When the amount used is too large, the crosslinking effect is saturated, but there is a possibility that a crosslinkable molded article and a crosslinked molded article having desired physical properties cannot be obtained.

  The resin composite of the present invention can further contain a crosslinking aid, a radical crosslinking retarder, a modifier, an antioxidant, a flame retardant, a filler, a colorant, a light stabilizer and the like. The crosslinking agent and these additives can be used by adding to the polymerizable composition or varnish.

  When a radical generator is used as the crosslinking agent, a crosslinking aid can be used to accelerate the crosslinking reaction. Crosslinking aids include hydrocarbon compounds having two or more isopropenyl groups such as diisopropenylbenzene; methacrylate compounds such as lauryl methacrylate and trimethylolpropane trimethacrylate; cyanuric acids such as triallyl cyanurate and triallyl isocyanurate Compounds; imide compounds such as maleimide; and the like.

  A radical crosslinking retarder can also be used. Examples of the radical crosslinking retarder include alkoxyphenols, catechols, and benzoquinones, and alkoxyphenols such as 3,5-di-t-butyl-4-hydroxyanisole are preferable.

  Examples of the flame retardant include phosphorus flame retardants, nitrogen flame retardants, halogen flame retardants, metal hydroxide flame retardants such as aluminum hydroxide, and antimony compounds such as antimony trioxide. Although the flame retardant may be used alone, it is preferable to use a combination of two or more.

  Examples of the filler include glass powder, ceramic powder, silica, and metal powder. Two or more of these fillers may be used in combination. As the filler, one that has been surface-treated with a silane coupling agent or the like can also be used.

  As the colorant, dyes, pigments and the like are used. There are various kinds of dyes, and known ones may be appropriately selected and used.

  The blending amount of each component is such that the viscosity of the polymerizable composition is usually 10,000 mPa · s or less, preferably 5,000 mPa · s or less, more preferably 1,000 mPa · s or less, and particularly preferably 500 mPa · s or less. It is particularly desirable to set so that If the viscosity is higher than this range, impregnation into the reinforcing material may be difficult.

(Crosslinked resin composite)
Although the crosslinkable resin composite contains the above-mentioned crosslinking agent, the crosslinking reaction does not proceed unless heated. Therefore, the surface hardness of the crosslinkable resin composite hardly changes during storage, and the storage stability is excellent.

  In the case of obtaining a resin composite by bulk polymerization, when the polymerizable composition contains a crosslinking agent, if the peak temperature during the bulk polymerization reaction becomes too high, not only the bulk polymerization reaction but also crosslinking at once. The reaction may also proceed. Therefore, in order to completely advance only the bulk polymerization reaction and prevent the crosslinking reaction from proceeding, it is necessary to control the peak temperature of the polymerizable composition in the polymerization to preferably less than 200 ° C. However, from the viewpoint of productivity and the like, the bulk polymerization reaction and the crosslinking reaction may proceed simultaneously.

  When a polymerizable composition containing a radical generator is used, it is preferable that the peak temperature in the bulk ring-opening polymerization is not higher than the 1 minute half-life temperature of the radical generator. Here, the 1-minute half-life temperature is a temperature at which half of the radical generator decomposes in 1 minute.

  The crosslinked resin composite of the present invention can be obtained by heating and crosslinking a crosslinkable resin composite obtained using a varnish or a polymerizable composition containing a crosslinking agent. The temperature at which the crosslinkable resin composite is heated to be crosslinked is usually 170 to 250 ° C, preferably 180 to 220 ° C. This temperature is preferably higher than the peak temperature in the bulk polymerization, and more preferably 20 ° C. or higher. The time for crosslinking by heating is not particularly limited, but is usually from 1 minute to 10 hours.

  When the crosslinkable resin composite is in the form of a sheet or a film, the crosslinkable resin composite is laminated as necessary, and hot-pressed to maintain a constant shape and crosslink. It is preferable to do. The pressure at the time of hot pressing is usually 0.5 to 20 MPa, preferably 3 to 10 MPa. The hot pressing can be performed, for example, using a known press having a press frame mold for flat plate molding, a press molding machine such as a sheet mold compound (SMC) or a bulk mold compound (BMC), and productivity. Excellent.

  As described above, from the viewpoint of productivity and the like, the bulk polymerization reaction and the crosslinking reaction may be simultaneously performed to obtain the crosslinked composite directly from the polymerizable composition. The method for heating, polymerizing and crosslinking the polymerizable composition is not particularly limited. For example, a method of injecting a polymerizable composition into a mold and applying pressure simultaneously with heating by a hot press is preferable. The pressure at the time of hot pressing is usually 0.5 to 20 MPa, preferably 3 to 10 MPa.

(Laminate)
The complex or the crosslinked complex may be used as a laminate. The laminate has a constituent layer composed of the resin composite or the crosslinked resin composite, more specifically, has at least two or more layers, and at least one of the layers is the resin composite or the crosslinked resin. It is formed of a complex. A more specific example of such a laminate includes a laminate including a base material such as a copper foil and a constituent layer formed from the resin composite or the crosslinked resin composite of the present invention. Further, the laminated body may be a composite material in which a base material such as a copper foil and a resin layer made of a resin composite or a crosslinked resin composite are alternately laminated like a multilayer laminated substrate. Here, when a plurality of resin layers made of a resin composite or a crosslinked resin composite are included, the composition of each resin layer may be the same or different.

  Examples of the base material include copper foils, aluminum foils, nickel foils, chrome foils, gold foils, silver foils and other metal foils; printed wiring board manufacturing substrates; resins such as polytetrafluoroethylene (PTFE) films and conductive polymer films Film: Noise suppression sheet, radio wave absorber and the like. The surface of the base material may be treated with a silane coupling agent, a thiol coupling agent, a titanate coupling agent, various adhesives, or the like.

  There is no particular limitation on the method for obtaining the laminate. For example, the laminate may be obtained by superimposing the composite on an appropriate substrate material, or the composite may be obtained by superimposing the composites. Furthermore, a polymerizable composition can be coated on a suitable substrate material or composite, and the polymerizable composition can be polymerized to obtain a laminate.

  Moreover, when obtaining the laminated body containing the structural layer which consists of a crosslinked resin composite of this invention, for example, (1) The crosslinkable resin composite obtained using the varnish or polymeric composition containing a crosslinking agent is used. (2) Laminating the polymerizable composition on the substrate material to advance bulk ring-opening polymerization and crosslinking reaction, (3) Varnish containing a crosslinking agent or Examples include a method in which two or more crosslinkable resin composites obtained using the polymerizable composition are superposed and then heated to crosslink.

  In order to obtain a laminate by the above method (1), for example, a crosslinkable resin composite and a metal foil as a base material are superposed and crosslinked by heating with a hot press or the like, so that the metal foil is strong. A metal foil-clad laminate that is in close contact with the substrate can be obtained. When the copper foil is used as the metal foil, the peel strength of the metal foil of the obtained metal foil-clad laminate is a value measured based on JIS C6481, and is 0.5 kN / m or more, preferably 0.8 kN / m or more, more preferably 1.2 kN / m or more.

  In order to obtain a laminate by the above method (2), the bulky ring-opening polymerization temperature of the polymerizable composition is set high and heated at a temperature at which a crosslinking reaction occurs. However, as in the method (1), once the crosslinkable resin composite is passed, the peel strength at the interface increases.

The resin composite and cross-linked resin composite according to the present invention having such characteristics include a prepreg; a copper foil with resin; a printed wiring board, an insulating sheet, an interlayer insulating film, an overcoat, an antenna substrate, an electromagnetic wave absorber, and an electromagnetic wave shield. It is suitable as an electronic component material.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto. In the following examples and comparative examples, “parts” and “%” are based on weight unless otherwise specified.

(Molecular weight of polymer)
The measurement result by gel permeation chromatography using tetrahydrofuran as a developing solvent was obtained by converting to the molecular weight of standard polystyrene.

(Measurement of thermal expansion coefficient)
The double-sided copper-clad laminate was immersed in a ferric chloride solution (manufactured by Sanhayato Co., Ltd.) at 40 ° C. to remove the surface copper foil. Subsequently, this was cut out into 5 mm square, the linear expansion ((alpha) z) of the Z direction (thickness direction) of the obtained test piece was measured, and the following references | standards evaluated.

A: αz <50 ppm / ° C
B: 50 ppm / ° C. ≦ αz <60 ppm / ° C.
C: 60 ppm / ° C. ≦ αz <70 ppm / ° C.
D: 70 ppm / ° C. ≦ αz
(Impregnation)
The double-sided copper-clad laminate was immersed in a ferric chloride solution (manufactured by Sanhayato Co., Ltd.) at 40 ° C. to remove the surface copper foil. The inside of the obtained laminate was observed with a microscope and evaluated according to the following criteria.

A: No bubbles are observed by microscopic observation B: A few bubbles are observed by microscopic observation C: Bubbles are observed by microscopic observation D: Many bubbles are observed by microscopic observation (peel strength) )
The peel strength test was performed on the copper foil of the peel strength measurement sample according to JIS-C6481, using a tensile tester with a crosshead speed set to 50 mm / min, to measure the peel strength of the conductor.

(Example 1)
Acetic acid is added dropwise to 700 ml of ion-exchanged water to adjust the pH to 4.0, and further styryltrimethoxysilane (trade name: KBM-1403, manufactured by Shin-Etsu Silicone) is dissolved to a concentration of 1.0 g / liter, A silane coupling agent aqueous solution was prepared.

An untreated glass cloth (thickness: 80 μm, weight per unit area: 85 g / m ² , E glass) was heat cleaned at a temperature of 400 ° C. for 27 hours. As the first surface treatment step, the heat-treated glass cloth was immersed in the silane coupling agent aqueous solution, and the excess was squeezed and dried. Further, as the second surface treatment step, the glass cloth treated with the silane coupling agent is immersed in divinyltetramethyldisilazane (product name: ZHMDS100, manufactured by Nippon Zeon Co., Ltd.) as silazane, and the excess is reduced to 100 ° C. And dried to produce a surface-treated glass cloth.

  As a metathesis catalyst, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) (2-pyrrolidone-1-ylmethylene) (tricyclohexylphosphine) ruthenium dichloride 0.127 parts, triphenylphosphine 0 197 parts were placed in a flask, vacuum degassing and nitrogen filling were repeated, and finally nitrogen filling was performed. While flowing nitrogen, 2.38 parts of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was added and dissolved to prepare a tetrahydrofuran solution of the metathesis catalyst.

As the cycloolefin monomer, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-ene (TCD) 80 parts and 2-norbornene (NB) 20 parts, and a mixture containing 0.28 parts 2,6-ditertiarybutylhydroxytoluene as an antioxidant 100 parts of silica (manufactured by Admatechs, product name SO-E1, styryltrimethoxysilane treated average particle size 0.2 μm) was added as a filler and stirred with a stirrer. This was cooled with ice water, and 1.7 parts of undecenyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a chain transfer agent and di-t-butyl peroxide (manufactured by Kayaku Akzo Co., Ltd.) as a crosslinking agent for organic peroxide. The product name Kayabutyl D) 1.14 parts was added to obtain a monomer solution. Into this monomer solution, 0.26 ml of the metathesis catalyst solution per 100 parts of the cycloolefin monomer was added and stirred to obtain a polymerizable composition.

  80 parts of the polymerizable composition thus prepared was cast on a polyethylene naphthalate (PEN) film (manufactured by Teijin DuPont Films Co., Ltd., thickness 75 μm), and the surface-treated glass cloth was laid thereon. Further, 80 parts of the polymerizable composition was cast thereon. A PEN film was further covered from above, and the entire glass cloth was impregnated with the polymerizable composition with a roller. It was confirmed that the polymerizable composition exudes from the edge of the glass cloth, and it was confirmed that a sufficient amount of the polymerizable composition was impregnated into the glass cloth. Next, this was left on a hot plate set at 135 ° C. for 1 minute, the polymerizable composition was bulk polymerized, and the upper and lower PEN films were peeled off to obtain a prepreg having a thickness of about 0.1 mm.

  The prepreg produced as described above was cut into a size of 100 mm square, and six of these were stacked, and both surfaces thereof were copper foil (Type GTS, thickness 35 μm, silane coupling agent surface-treated product, manufactured by Furukawa Circuit Foil Co., Ltd.). It was sandwiched and pressed by hot pressing at 3 MPa and a substrate surface temperature of 200 ° C. for 15 minutes to produce a double-sided copper clad laminate having a thickness of about 0.8 mm. Using this double-sided copper-clad laminate, the impregnation property and the coefficient of thermal expansion were measured. The results are shown in Table 1.

  Next, the obtained double-sided copper clad laminate was cut into 25 mm × 100 mm, and the copper foil on the surface was subjected to alkali degreasing, soft etching, and 10% sulfuric acid treatment. A dry film resist (RY-3215 manufactured by Hitachi Chemical Co., Ltd.) is laminated on the treated surface of the copper foil, and a film photomask printed with the peel strength pattern of JIS C6481 reversed is overlaid on the resist. Then, exposure was performed using an exposure apparatus for photoresist (EXP-2805 manufactured by Oak Seisakusho). Next, the resist is developed with a 1% aqueous sodium carbonate solution, the copper foil is etched with an aqueous copper (II) chloride solution, and the remaining resist is peeled off with a 5% aqueous sodium hydroxide solution to provide a sample for peel strength measurement. Was made. The results of measuring the peel strength of this sample are shown in Table 1.

(Example 2)
The same experiment as in Example 1 was performed except that 1 part of hexamethyldisilazane was used as the second surface treatment agent instead of 1 part of divinyltetramethyldisilazane. The results are shown in Table 1.

Example 3
The same experiment as in Example 1 was performed except that the polymerization method of the cycloolefin polymer resin composition was changed. The adjustment method is shown below.

  Under a nitrogen atmosphere, 100 parts of dehydrated cyclohexane, 0.34 part of undecenyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a chain transfer agent, 0.06 part of diisopropyl ether and 0.04 part of triisobutylaluminum as a promoter and stabilizer, In addition, 0.015 parts by weight of isobutyl alcohol was mixed in a reactor at room temperature. Thereto, 80 parts of TCD and 20 parts of NB as cycloolefin monomers and 15 parts of a 1.0 wt% toluene solution of tungsten hexachloride as a metathesis catalyst were continuously added over 2 hours while maintaining the reactor temperature at 55 ° C. Added and polymerized.

  To the resulting solution, 0.056 part of 2,6-ditertiarybutylhydroxytoluene as an antioxidant and di-t-butyl peroxide (product name: Kayabutyl D, manufactured by Kayaku Akzo Co., Ltd.) as a crosslinking agent for organic peroxides. 1.14 parts are added and dissolved, and 100 parts of silica (manufactured by Admatechs, product name SO-E1, treated with styryltrimethoxysilane, average particle size 0.2 μm) is added as a filler and stirred with a stirrer. Thus, a resin composition was obtained.

  Subsequently, the surface-treated glass cloth obtained in the same manner as in Example 1 was placed on a polyethylene naphthalate (PEN) film (manufactured by Teijin DuPont Films, Inc., thickness 75 μm). The resin composition obtained above was immersed here, and thickness unevenness was adjusted with a roller. Next, this was left in an inert oven at 135 ° C. for 2 minutes to remove the solvent of the resin composition, and the PEN film was peeled off to obtain a prepreg having a thickness of about 0.1 mm.

(Example 4)
An experiment similar to that of Example 3 was performed except that the surface-treated glass cloth was not dried. The results are shown in Table 1.

(Example 5)
An experiment similar to that of Example 3 was performed except that an ethenylbenzylated polyphenylene ether-based resin composition was used in place of the cycloolefin polymer. The adjustment method is shown below.

  First, 2,000 parts of toluene was placed in a flask equipped with a stirrer and heated until the toluene reached 80 ° C. Here, 100 parts of polyphenylene ether (PPE, trade name: Noryl PX9701, GE Plastics, Mn = 14,000), bisphenol A, t-butyl peroxyisopropyl monocarbonate (trade name: Perbutyl I, manufactured by NOF Corporation) ), And a toluene solution prepared by adjusting 0.0042 part of cobalt naphthenate to a concentration of 8%, and stirred until the solution was completely dissolved to lower the molecular weight of PPE. After completion of the reaction, a large amount of methanol was added to reprecipitate PPE to remove impurities, followed by drying at 80 ° C. under reduced pressure for 3 hours to completely remove the solvent. Mn of the obtained PPE was 9,000.

  Next, 2,000 parts of toluene was placed in a flask equipped with a stirrer and heated until the toluene reached 75 ° C. Here, 100 parts of the above-mentioned low molecular weight PPE, 7.3 parts of chloromethylstyrene, 0.41 part of tetra-n-butylammonium bromide, and 200 parts of toluene are added to dissolve these, and the concentration is adjusted here. 10 parts of 50% aqueous sodium hydroxide solution was added dropwise. Thereafter, this mixed solution was filtered and washed to obtain a modified PPE having a terminal vinylbenzylated.

  The resin composition was prepared as follows. First, 2,000 parts of toluene was placed in a flask equipped with a stirrer and heated until the toluene reached 80 ° C. The above modified PPE was added and stirred until it was completely dissolved. After complete dissolution, 5.0 parts of triallyl isocyanate (manufactured by NOF Corporation) and 0.4 part of α, α'-di (t-butylperoxy) diisopropylbenzene (manufactured by NOF Corporation) were added. The resin composition was obtained by stirring this. Using this resin composition, a prepreg having a thickness of about 0.1 mm was obtained in the same manner as in Example 3.

(Example 6)
The same experiment as in Example 2 was performed except that 1 part of hexyltrimethoxysilane was used as the first surface treatment agent instead of 1 part of styryltrimethoxysilane. The results are shown in Table 1.

(Example 7)
The same experiment as in Example 5 was performed except that no crosslinking agent was added to the polymerizable composition. The results are shown in Table 1.

(Comparative Example 1)
The same experiment as in Example 1 was performed except that the second surface treatment agent was not used. The results are shown in Table 1.

(Comparative Example 2)
The same experiment as in Example 1 was performed except that the silane compound as the first surface treatment agent was not used and two parts of hexamethyldisilazane as the second surface treatment agent were used. The results are shown in Table 1.

(Comparative Example 3)
The same experiment as in Example 4 was performed except that 2 parts of hexamethyldisilazane as the second surface treatment agent was used without using the silane compound as the first surface treatment agent. The results are shown in Table 1.
(Comparative Example 4)
An experiment similar to Example 2 was performed except that a mixture of 1 part vinyltrimethoxysilane and 1 part hexamethyldisilazane was used as the surface treatment agent, and the surface treatment step was performed once. The results are shown in Table 1.

(Comparative Example 5)
The same experiment as in Example 2 was performed except that the surface treatment step of 1 part vinyltrimethoxysilane and 1 part hexamethyldisilazane was used as the surface treatment agent. The results are shown in Table 1.

  As can be seen from the above Examples and Comparative Examples, by sequentially treating the reinforcing material surface with the specific first surface treatment agent and the second surface treatment agent, the impregnation and adhesion of the polymer are high, and the thermal expansion coefficient is high. A low and high strength resin composite was obtained.

Claims (10)

A resin composite comprising a polymer and a surface-treated reinforcing material,
A first surface treatment step in which the surface treatment is carried out with a first surface treatment agent of an aqueous solution selected from the group consisting of alkoxysilane, titanate compound and aluminate compound;
And a second surface treatment step of surface treatment with a second surface treatment agent selected from silazanes in this order. The resin composite according to claim 1, wherein the first surface treating agent is an alkoxysilane represented by the following formula (I).
^{_{SiR 1 m (OR 2) n}} X 4- (m + n) ··· (I)
(Wherein R ¹ and R ² each independently represent a hydrocarbon group, X represents a hydrolyzable group, m and n are integers of 1 to 3, and m + n is an integer of 2 to 4) is there.) The resin composite according to claim 2, wherein R ¹ in the formula (I) is a hydrocarbon group having a carbon-carbon double bond. The resin composite according to claim 1, wherein the second surface treatment agent is a hydrocarbon group-containing silazane represented by the following formula (II):

In the formula, R ³ and R ⁴ are each independently a hydrocarbon group, R ^{5 to} R ⁸ are each independently hydrogen or a hydrocarbon group, and n is an integer of 0 to 3.   The resin composite according to any one of claims 1 to 4, wherein the polymer is a cycloolefin polymer or polyphenylene ether.   Furthermore, the resin complex in any one of Claims 1-5 containing a crosslinking agent.   A cross-linked resin composite obtained by cross-linking the resin composite according to claim 6. A polymerizable composition comprising a bulk polymerizable monomer and a polymerization catalyst,
A method for producing a resin composite that undergoes bulk polymerization in the presence of a surface-treated reinforcing material,
A first surface treatment step in which the surface treatment is carried out with a first surface treatment agent of an aqueous solution selected from the group consisting of alkoxysilane, titanate compound and aluminate compound;
And a second surface treatment step of performing a surface treatment with a second surface treatment agent selected from silazanes in this order.   The production method according to claim 8, wherein the bulk polymerizable monomer is a cycloolefin monomer. The production method according to claim 8 or 9, wherein the polymerizable composition further contains a crosslinking agent.