JP2006182985A - Polymerizable composition and molded item made by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition which can give a resin molded item, a cross-linked resin molded item, and a cross-linked resin composite material excellent in flame retardancy. <P>SOLUTION: The polymerizable composition contains a cycloolefin monomer, a metathesis polymerization catalyst, a metal hydroxide, and a specific organometallic compound. When polymerized, the composition gives a resin molded item. The composition may further contain a cross-linking agent or a chain-transfer agent, and when heated, this composition containing such an agent gives a cross-linked resin molded item. The cross-linked resin molded item may be a composite material with a base material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polymerizable composition containing a cycloolefin and a resin molded product obtained using the same, and more specifically, a polymerizable composition capable of providing a resin molded product or a crosslinked resin composite material having excellent flame retardancy. Product and resin molded body.

Cycloolefin resins obtained by ring-opening polymerization of cycloolefin monomers such as norbornene in the presence of a metathesis polymerization catalyst are widely used as resin molding materials. It is also known that a crosslinked resin molded product can be obtained by crosslinking this cycloolefin resin with a crosslinking agent such as an organic peroxide. The resin molded body and the crosslinked resin molded body are said to have excellent electrical characteristics such as low dielectric constant and low dielectric loss tangent in addition to mechanical strength and chemical resistance. Focusing on these characteristics, for example, in Patent Document 1, a resin composition is obtained by polymerizing a polymerizable composition containing a cyclic olefin monomer, which is a cycloolefin monomer, and a chain transfer agent in a mold having a split mold structure. A method for obtaining a molded body and a method for polymerizing after pouring onto a carrier are disclosed. Here, it is described that a flame retardant etc. may be mix | blended with a polymeric composition as needed.
As the flame retardant, a halogen-based flame retardant containing a halogen atom and a non-halogen flame retardant containing no halogen atom are known. Since halogen flame retardants cause environmental pollution such as dioxins, it is desired to use non-halogen flame retardants. However, since non-halogen flame retardants have low flame retardancy imparting ability, it is necessary to increase the blending amount in order to obtain sufficient flame retardancy. When the blending amount of the non-halogen flame retardant is increased, the formability and the electrical properties and heat resistance of the resulting molded product tend to be inferior. It is considered to add a third component such as. Consideration has been made (Patent Document 2).

JP 2004-035615 A JP 2003-026915 A

Under such conventional technology, the present inventors have used a metal hydroxide and a layered silicate as described in Patent Document 2 as a flame retardant in a polymerizable composition as disclosed in Patent Document 1. The resin molded body was formed by addition. As a result, it was found that only a molded body having low flame retardancy can be obtained.
Based on this knowledge, the present inventors ensure the flame retardancy of a resin molded article obtained from a polymerizable composition containing a cycloolefin monomer, a metathesis polymerization catalyst, and a metal hydroxide that is a non-halogen flame retardant. As a result of intensive studies, it is possible to obtain a resin molded article excellent in flame retardancy by using a metal hydroxide as a non-halogen flame retardant and further incorporating a specific metal compound into the polymerizable composition. As a result, the present invention has been completed.

Thus, according to the present invention, the following (1) to (4) are provided.
(1) A cycloolefin monomer, a metathesis polymerization catalyst, a metal hydroxide, and a compound represented by the general formula (1) ML _a X _b (where M is a metal atom, and L is coordinated to M And at least one L is a ligand having a cyclopentadienyl skeleton, and X is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, An alkylsilyl group, a SO ₃ R group (where R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent) or a hydrogen atom, a + b is a valence of M, and a is 1 or more , B is 0 to 5.) or a polymerizable composition comprising an organic acid metal salt.
In this polymerizable composition, the organic acid metal salt is preferably a carboxylic acid metal salt.
This polymerizable composition preferably further contains a chain transfer agent.
This polymerizable composition preferably further contains a crosslinking agent. As the crosslinking agent, a radical generator is preferable.
(2) A resin molded product obtained by ring-opening polymerization of the polymerizable composition.
This molded body is obtained by coating the polymerizable composition on a support and then ring-opening polymerization. The molded body is obtained by injecting the polymerizable composition into a space of a mold and then ring-opening polymerization. Furthermore, this molded body is obtained by impregnating the above-mentioned polymerizable composition into a fibrous reinforcing material and then ring-opening polymerization.
Here, the ring-opening polymerization is preferably carried out by bulk polymerization.
(3) A crosslinked resin molded article obtained by heating and crosslinking a resin molded article obtained by ring-opening polymerization of a polymerizable composition containing a crosslinking agent among the polymerizable compositions. Here, the ring-opening polymerization is preferably carried out by bulk polymerization.
(4) A crosslinked resin composite obtained by superposing a resin molded body obtained by ring-opening polymerization of a polymerizable composition containing a crosslinking agent among the polymerizable compositions on a base material and then crosslinking by heating. material. Here, the ring-opening polymerization is preferably carried out by bulk polymerization.
Hereinafter, in the present invention, the resin molded body (2), the crosslinked resin molded body (3), and the crosslinked resin composite material (4) may be collectively referred to as a unit “molded body”.

  According to the present invention, there is provided a polymerizable composition capable of giving a molded article excellent in electrical insulation and flame retardancy. This polymerizable composition has good moldability.

The polymerizable composition of the present invention contains a cycloolefin monomer, a metathesis polymerization catalyst, and a metal hydroxide, and is further a compound represented by the above formula (1) (hereinafter sometimes referred to as a specific metal complex) or An organic acid metal salt is contained as a specific metal compound.
The cycloolefin monomer used in the present invention is a compound having an alicyclic structure and a carbon-carbon double bond in the molecule. The cycloolefin monomer provides a cycloolefin resin by polymerization.
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 cycloolefin monomers include monocyclic cycloolefin monomers and norbornene monomers. 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. Moreover, you may have a double bond other than the double bond of a 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 [9.2.1.1 ^4,7. 0 ^2,10 . 0 ^3,8 ] pentadeca-5,12-diene and other cyclic olefins having four or more rings; and the like.
Of these monomers, a cycloolefin monomer having no polar group is advantageous for providing a molded article having a low dielectric loss tangent.
These cycloolefin monomers may be used alone or in combination of two or more to control the physical properties of the cycloolefin resin.

  The metathesis polymerization catalyst used in the present invention is not particularly limited as long as it undergoes metathesis ring-opening polymerization of a 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, ruthenium and osmium complexes of group 8 of the long-period periodic table are preferable, and ruthenium carbene complexes coordinated with ruthenium carbene are particularly preferable for the following reasons. The ruthenium carbene complex is excellent in catalytic activity, so that the ring-opening polymerization reaction rate of the polymerizable composition can be increased and the productivity is excellent. Moreover, there is little odor (it originates in an unreacted cyclic olefin) in the resin molding obtained. Further, the ruthenium carbene complex has a characteristic that it is relatively stable against oxygen and moisture in the air and hardly deactivates.
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 in which an atom-containing carbene compound and a neutral electron-donating compound are bonded;

  Carbene compounds containing two heteroatoms as ligands such as benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride, benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride Ruthenium complex compound in which is bonded;

  (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.

  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 metal hydroxide used in the present invention has a function of imparting flame retardancy to the molded body. Specifically, water is not released at 150 ° C. or lower, but 800 ° C. at a temperature higher than 150 ° C. It is a compound that dehydrates and releases crystal water when heated in a temperature range below C, or a compound that releases water by chemical decomposition. The amount of water released is usually 10 to 70% by weight, preferably 20 to 60% by weight.
Specific examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, manganese hydroxide, and sodium tin hydroxide. Of these metal hydroxides, magnesium hydroxide and aluminum hydroxide are preferred because of their low toxicity.
The metal hydroxide used in the present invention may contain surface adsorbed water. The surface adsorbed water is measured as a loss on heating by drying in a hot air dryer at 150 ° C. for 1 hour. The content of surface adsorbed water is usually 0.01 to 5% by weight, preferably 0.1 to 3% by weight, particularly preferably 0.4 to 2% by weight.
When the metal hydroxide is a particle, the average value of the length in the longitudinal direction and the short direction when the particle is viewed three-dimensionally is usually 0.01 to 50 μm, preferably 0.01 to 20 μm, More preferably, it is 0.1-10 micrometers, Most preferably, it is 0.1-5 micrometers. It is preferable for the particle size of the metal hydroxide to be in this range since the productivity and flame retardancy of the molded product are excellent. The metal hydroxides may be used with the same particle size, or those mixed from a large particle size to a small particle size may be used. What is necessary is just to classify with a sieve as needed in order to arrange | equalize the particle size of a metal hydroxide.
The bulk specific gravity of the metal hydroxide is not particularly limited. The bulk specific gravity is preferably 0.2 to 3.0 g / cc, particularly preferably 0.3 to 2.0 g / cc. When the bulk specific gravity of the metal hydroxide is in this range, the productivity and flame retardancy of the molded product are excellent and preferable. Bulk specific gravity is measured as the ratio of metal hydroxides in a graduated cylinder by measuring the weight and volume without applying a weight.
These metal hydroxides are preferably surface-treated with a coupling agent containing Si, Ti, Al, Zr or the like.
The amount of the metal hydroxide is usually 50 to 300 parts by weight, preferably 50 to 200 parts by weight with respect to 100 parts by weight of the cycloolefin monomer. If the amount of the metal hydroxide is too small, the flame retardant effect cannot be obtained sufficiently, and conversely if too large, the moldability tends to be inferior.

The polymerizable composition of the present invention contains a specific metal complex or an organic acid metal salt as the specific metal compound, so that polymerization inhibition of the cycloolefin monomer is suppressed, and the amount of residual monomer in the resulting molded body As a result, a highly flame-retardant molded article can be secured.
These amounts are usually 0.0001 to 20 parts by weight, preferably 0.001 to 10 parts by weight, more preferably 0.005 to 10 parts by weight, particularly preferably 0 to 100 parts by weight of the cycloolefin monomer. 0.01 to 10 parts by weight, most preferably 0.1 to 10 parts by weight. If the amount is too small, a sufficient flame retardancy effect cannot be obtained. Conversely, if the amount is too large, the moldability tends to be lowered.

The specific metal complex used in the present invention is a compound represented by the general formula (1) ML _a X _b (where M is a metal atom, L is a ligand coordinated to M, and at least One L is a ligand having a cyclopentadienyl skeleton, and X is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, SO ₃ R, which are not cross-linked to each other. A group (where R is an optionally substituted hydrocarbon group having 1 to 8 carbon atoms) or a hydrogen atom, a + b is a valence of M, a is 1 or more, and b is 0-5. is there.)
The metal atom is preferably Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn, more preferably Ti, Fe or Ni, and particularly preferably Fe.
Examples of the ligand having a cyclopentadienyl skeleton include, for example, a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, Pentamethylcyclopentadienyl, ethylcyclopentadienyl, methylethylcyclopentadienyl, propylcyclopentadienyl, methylpropylcyclopentadienyl, butylcyclopentadienyl, methylbutylcyclopentadi Examples thereof include alkyl-substituted cyclopentadienyl groups such as enyl group and hexylcyclopentadienyl group; indenyl groups such as indenyl group and 4,5,6,7-tetrahydroindenyl group; fluorenyl group; and the like. The hydrogen atom of these groups may be substituted with a substituent containing oxygen, nitrogen, phosphorus, silicon, carbon, sulfur and the like.
Among these ligands, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the above general formula contains two or more groups having a cyclopentadienyl skeleton, the two groups having a cyclopentadienyl skeleton are alkylene groups such as ethylene and propylene, isopropyl It may be bonded via a substituted alkylene group such as lidene or diphenylmethylene, a silylene group or a dimethylsilylene group, a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group.

Specific examples of X include the following. Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. More specifically, examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. , An isopropyl group, a butyl group and the like, examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group, examples of the aryl group include a phenyl group and a tolyl group, and examples of the aralkyl group include a benzyl group, An example is a neophyll group. Further, examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group, and examples of the aryloxy group include a phenoxy group.
Examples of the ligand represented by SO ₃ R include a p-toluenesulfonate group and a methanesulfonate group.

As specific metal complexes of the general formula ^{_{(2) R 2 k R 3}} l R 4 m R 5 those represented by _n M are preferred.
In the above formula (2), M is Ti, Fe or Ni (preferably Fe), R ² is a group (ligand) having a cyclopentadienyl skeleton, and R ³ , R ⁴ and R ⁵ are A group (ligand) having a cyclopentadienyl skeleton, a group other than the group having a cyclopentadienyl skeleton, or a hydrogen atom, k is an integer of 1 or more, and k + l + m + n = 2-4.
A compound in which at least two of R ² , R ³ , R ⁴ and R ⁵ , that is, R ² and R ³ are groups (ligands) having a cyclopentadienyl skeleton is particularly preferable.

Examples of metallocene compounds in which the metal is iron include di-π-cyclopentadienyl iron (ferrocene), bisindenyl iron (II), 1,1′-diacetyl ferrocene, 1,2-diacetyl ferrocene, 1,1-diferro. Senylethane, dimethylaminoethylferrocene, methylaminomethylferrocene, ferrocenylacetonitrile, ferrocenylcarbonal, ferrocenesulfonic acid, 1,2-diferrocenylethane, diferrocenylmethane, phenylferrocene, ferrocenecarboxy Compound such as aldehyde, Ω-ferrocenyl fatty acid, phenylsilocpentaferrocene, 1,1 ′-(1,3-cyclopentylene) ferrocene, phenylsilocpentylferrocene and similar compounds, benzoylferrocene and acetylferrocene, azaferrocene Cyclic π complexes.
In the above examples, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product includes 1,2,3- and 1,2,4-substituted products. Including. In addition, alkyl groups such as propyl and butyl may be linear or branched.

  Examples of metallocene compounds in which the metal is nickel include di-π-cyclopentadienyl nickel (nickelocene), bisindenyl nickel (II), 1,1′-diacetyl nickelocene, 1,2-diacetyl nickelocene, 1,1-diferrocenyl ethane, dimethylaminoethyl nickelocene, methylaminomethyl nickelocene, ferrocenyl acetonitrile, ferrocenyl carbonal, nickelocene sulfonic acid, 1,2-diferrocenyl ethane, diferro Senylmethane, phenyl nickelocene, nickelocene carboxaldehyde, Ω-ferrocenyl fatty acid, phenyl siloxane pentanickelocene, 1,1 ′-(1,3-cyclopentylene) nickel erocene, phenyl siloxane pentyl nickelocene and similar compounds, benzoyl Nickeloce And nickel complexes such as a heterocyclic π complex having a nickel atom such as nicknickelocene and anicknickelocene such as acetylnickelocene.

  Examples of metallocene compounds whose metal is titanium include di-π-cyclopentadienyldimethyltitanium, bisindenyldimethyltitanium, 1,1′-diacetyl-di-π-cyclopentadienyldimethyltitanium, 1,2-diacetyl. -Titanium complexes such as analogous compounds such as di-π-cyclopentadienyldimethyltitanium.

Such a specific metal complex may be used independently and may be used in combination of 2 or more type. Among the specific metal complexes, it is preferable to select one that is stable at room temperature or in air. If the stability at room temperature is low, it is gradually decomposed and a sufficient flame retardant effect cannot be obtained. If the stability in air is low, handling at the time of preparing the polymerizable composition may be difficult.
The specific metal complex may be soluble or insoluble in the cycloolefin monomer, but is preferably soluble in the cycloolefin monomer. The specific metal complex soluble in the cycloolefin monomer can be easily dispersed uniformly and can give a molded article excellent in flame retardancy. The specific metal complex insoluble in the cycloolefin monomer can function as a filler as it is.

The organic acid metal salt used in the present invention is a salt of an organic acid and a metal. An organic acid is an organic compound having a carboxylic acid structure, a sulfonic acid structure, or a sulfate ester structure in one molecule. The portion other than the above functional groups of the organic acid is a saturated or unsaturated, linear, branched or cyclic alkyl group; an aromatic hydrocarbon group such as a benzyl group, a naphthyl group or a fluorenyl group; a furanyl group or a thiophenyl group heteroaromatic ring Containing groups; These may contain a functional group other than a carboxyl group, a sulfonyl group, and a sulfate group, such as a hydroxyl group, an amino group, a mercapto group, a sulfide group, and a silyl group. In addition, nitrogen, oxygen, phosphorus, sulfur, silicon atoms, etc. may be included.
Examples of organic acids having a carboxylic acid structure include stearic acid, oleic acid, oxalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, succinic acid, sorbic acid, 2-ethylhexanoic acid, hydroxystearic acid, ricinoleic acid, Examples include phthalic acid, citric acid, tartaric acid, naphthenic acid, and oxalic acid.
Examples of the organic acid having a sulfonic acid structure include aromatic sulfonic acids such as benzenesulfonic acid and alkylbenzenesulfonic acid, and aliphatic sulfonic acids. Specific examples include dodecylbenzenesulfonic acid, laurylbenzenesulfonic acid, p-toluenesulfonic acid, and the like.
The organic acid having a sulfate ester structure is an ester of sulfuric acid and alcohol, and may be a compound in which one hydrogen atom of sulfuric acid is substituted with an alkyl group or aryl, specifically, lauryl sulfuric acid, etc. Is mentioned.
There are no particular restrictions on the metal constituting the organic acid and the salt, but from the viewpoint of moldability, preferred examples are sodium, potassium, magnesium, calcium, strontium, barium, iron, copper, manganese, nickel, aluminum, tin, and zinc. As mentioned.

Carboxylic acid metal salts include potassium benzoate, dipotassium phthalate, potassium stearate, potassium oleate, potassium sorbate, tripotassium citrate, sodium benzoate, sodium phthalate, sodium stearate, rubidium benzoate, phthalate Cesium acid, cesium stearate, aluminum stearate (including mono-, di-, and tri-substituted products), zinc stearate, aluminum acetate, ferric fumarate, calcium oxalate, barium oxalate, ferrous oxalate, sulphur In particular, it has good compatibility with the resin and is difficult to decompose during processing of the resin. For this reason, potassium benzoate, potassium stearate, potassium sorbate, tripotassium citrate, fumaric acid Ferric iron, ferrous oxalate and copper oxalate are preferred.
Examples of the sulfonic acid metal salt include sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, sodium p-toluenesulfonate, and potassium p-toluenesulfonate.
Specific examples of the sulfate metal salt include sodium lauryl sulfate and potassium lauryl sulfate.

  The polymerizable composition of the present invention can contain a crosslinking agent. The cross-linking agent cross-links with the functional group of the cycloolefin resin to form a cross-linked structure. Examples of the functional group include a carbon-carbon double bond, a carboxylic acid group, an acid anhydride group, a hydroxyl group, an amino group, an active halogen atom, and an epoxy group. 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, use of a radical generator, an epoxy compound, an isocyanate group-containing compound, a carboxyl group-containing compound, and an acid anhydride group-containing compound is preferable, and use of a radical generator, an epoxy compound, and an isocyanate group-containing compound is more preferable. The use of generators or epoxy compounds is particularly preferred.

  The radical generator has a function of generating radicals by heating and thereby crosslinking the cycloolefin resin. The site where the radical generator undergoes a crosslinking reaction is mainly the carbon-carbon double bond of the cycloolefin resin, but it may also be crosslinked at the saturated bond portion.

Examples of the radical generator include organic peroxides and diazo compounds. Examples of the organic peroxide include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; dialkyl peroxides such as dicumyl peroxide and t-butylcumyl peroxide; dipropionyl peroxide, Diacyl peroxides such as benzoyl peroxide; 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 1 Peroxyketals such as 1,3-di (t-butylperoxyisopropyl) benzene; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropylcarbonate, di (isopropyl) Alkylsilyl pel oxa Sid such t- butyl trimethylsilyl peroxide; peroxy carbonate such as Piruperuokishi) dicarbonate and the like. Of these, dialkyl peroxides are particularly preferable in that there are few obstacles to the metathesis polymerization reaction in bulk polymerization.
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.

The epoxy cross-linking agent causes a cross-linking reaction to proceed using a polar group such as a carboxyl group as a cross-linking point. Epoxy crosslinking agents include bisphenol A bis (ethylene glycol glycidyl ether) ether, bisphenol A bis (diethylene glycol glycidyl ether) ether, bisphenol A bis (triethylene glycol glycidyl ether) ether, bisphenol A bis (propylene glycol glycidyl ether) ether, etc. Glycidyl ether type epoxy compounds such as bisphenol A glycidyl ether type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, cresol type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, hydrogenated bisphenol Glycidyl ether type epoxy compounds such as A type epoxy compounds; Cyclic epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compound, a polyvalent epoxy compound such as isocyanurate type epoxy compound; a compound having two or more epoxy groups in the molecule, and the like.
Examples of the isocyanate group-containing compound include compounds having two or more isocyanate groups in the molecule, such as paraphenylene diisocyanate, 2,6-toluene diisocyanate, and hexamethylene diisocyanate. Examples of the carboxyl group-containing compound include compounds having two or more carboxyl groups in the molecule such as fumaric acid, phthalic acid, maleic acid, trimellitic acid, hymic acid, terephthalic acid, isophthalic acid, adipic acid, and sebacic acid. Can be mentioned. Examples of the acid anhydride group-containing compound include maleic anhydride, phthalic anhydride, pyroperitic acid, benzophenone tetracarboxylic acid anhydride, nadic acid anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, maleic anhydride modified polypropylene. Etc. Examples of the Lewis acid include silicon tetrachloride, hydrochloric acid, sulfuric acid, ferric chloride, aluminum chloride, stannic chloride, titanium tetrachloride, and the like.
Examples of the amino group-containing compound include aliphatic diamines such as trimethylhexamethylenediamine, ethylenediamine, and 1,4-diaminobutane; aliphatic polyamines such as triethylenetetramine, pentaethylenehexamine, and aminoethylethanolamine; phenylenediamine , 4,4′-methylenedianiline, toluenediamine, aromatic amines such as diaminoditolylsulfone; and the like, and compounds having two or more amino groups in the molecule.
Examples of the Lewis acid include silicon tetrachloride, hydrochloric acid, sulfuric acid, ferric chloride, aluminum chloride, stannic chloride, titanium tetrachloride, and the like.
Examples of the amino group-containing compound include aliphatic diamines such as trimethylhexamethylenediamine, ethylenediamine, and 1,4-diaminobutane; aliphatic polyamines such as triethylenetetramine, pentaethylenehexamine, and aminoethylethanolamine; phenylenediamine , 4,4′-methylenedianiline, toluenediamine, aromatic amines such as diaminoditolylsulfone; and the like, and compounds having two or more amino groups in the molecule.
The amount of the crosslinking agent is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the cycloolefin monomer. If the amount of radical generator is too small, crosslinking may be insufficient and a crosslinked resin molded product having a high crosslinking density may not be obtained. On the contrary, if the radical generator is too much, the productivity is inferior, and the crosslinking effect is saturated and only an insufficient effect may be obtained.

The polymerizable composition of the present invention can contain a chain transfer agent. By containing a chain transfer agent, it is possible to prevent the reaction due to heat generation during ring-opening polymerization from proceeding. In particular, when the polymerizable composition contains a crosslinking agent, the resin molded product after ring-opening polymerization of the polymerizable composition containing the chain transfer agent is higher than the maximum temperature (peak temperature) when the ring-opening polymerization proceeds. By heating to a temperature, a crosslinking reaction proceeds and a crosslinked resin molded article having excellent physical properties can be provided.
When the high-temperature resin molded body is overlaid with another base material such as a metal foil and then heated, the degree of adhesion at the interface between the resin molded body and the other base material is significantly improved.
Specific examples of chain transfer agents include aliphatic olefins such as 1-hexene and 2-hexene; aromatic olefins such as styrene, vinylstyrene, stilbene, vinylbenzene, and divinylbenzene; vinyl alicyclic compounds such as vinylcyclohexane Vinyl ethers such as ethyl vinyl ether and allyl glycidyl ether; vinyl ketones such as methyl vinyl ketone; ethylenically unsaturated esters such as allyl acetate and allyl methacrylate; vinyltrimethoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane Alkoxysilanes such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 3,3-dimethyl-1,4-pentadiene, 3,5-dimethyl-1,6-heptadiene, 3, 5-Dimetoki -1,6-heptadiene, 1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane, 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, divinyl Hydrocarbon chain transfer agents having two or more vinyl groups such as cyclopentane, diallylbenzene, divinylnaphthalene, divinylanthracene, divinylphenanthrene, trivinylbenzene, polybutadiene (with 1,2-addition of 10% or more); diallyl ether 1,5-hexadien-3-one, diallyl maleate, diallyl oxalate, diallyl malonate, diallyl succinate, diallyl glutarate, diallyl adipate, diallyl phthalate, diallyl fumarate, diallyl terephthalate, triallyl cyanurate, I Triallyl cyanurate, divinyl ether, allyl vinyl ether, divinyl maleate, divinyl oxalate, divinyl malonate, divinyl succinate, divinyl glutarate, divinyl adipate, divinyl phthalate, divinyl fumarate, divinyl terephthalate, trivinyl cyanurate, isocyanuric Examples include a heteroatom-containing chain transfer agent having two or more vinyl groups such as acid trivinyl. The amount of the chain transfer agent is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the cycloolefin monomer. When the amount of the chain transfer agent is within this range, the crosslinking reaction at the time of ring-opening polymerization is sufficiently suppressed, so that a resin molded article having excellent fluidity can be obtained.

  Among the chain transfer agents, when a hydrocarbon chain transfer agent having two or more vinyl groups in the molecule and not having a hetero atom such as oxygen, nitrogen, sulfur, etc. is used, the resulting crosslinked resin molded product or The cross-linked resin composite material has a low electrical property value such as relative dielectric constant and dielectric loss tangent, which is preferable as an electrical insulating material when handling high-frequency signals. In addition to the compound having two or more vinyl groups in the molecule, other chain transfer agents can be used in combination. Other chain transfer agents include compounds having only one vinyl group. When a chain transfer agent having only one vinyl group in the molecule is used, the amount is usually 50 mol% or less, preferably 40 mol% or less, based on the chain transfer agent having two or more vinyl groups in the molecule. Preferably it is 30 mol% or less, Most preferably, it is 10 mol% or less.

  In the polymerizable composition of the present invention, various additives can be blended as necessary within a range not inhibiting the effects of the present invention. Examples of such additives include activators (cocatalysts), polymerization retarders, crosslinking aids, radical crosslinking retarders, solvents, modifiers, antioxidants, colorants, light stabilizers, and the like.

The activator (co-catalyst) and the polymerization retarder are blended for the purpose of controlling the polymerization activity of the metathesis polymerization catalyst or improving the polymerization reaction rate. Examples of the activator include aluminum, scandium, tin, titanium, zirconium (partial) alkylated products, (partial) halides, (partial) alkoxylated products, and (partial) aryloxylated products.
Specific examples of the activator include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium. , Tetraalkoxytin, tetraalkoxyzirconium and the like.

  Examples of the polymerization retarder include 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, (cis, cis) -2,6-octadiene, (cis, trans) -2,6-octadiene, Chain diene compounds such as (trans, trans) -2,6-octadiene; (trans) -1,3,5-hexatriene, (cis) -1,3,5-hexatriene, (trans) -2, Linear triene compounds such as 5-dimethyl-1,3,5-hexatriene and (cis) -2,5-dimethyl-1,3,5-hexatriene; triphenylphosphine, tri-n-butylphosphine, methyl Phosphines such as diphenylphosphine; Lewis bases such as aniline; and the like.

  Furthermore, a cycloolefin having a diene structure or a triene structure in the ring can be used as a polymerization retarder. Examples of such cycloolefin include 1,5-cyclooctadiene, 1,5-dimethyl-1,5-cyclooctadiene, 1,3,5-cycloheptatriene, (cis, trans, trans)- And monocyclic cycloolefins such as 1,5,9-cyclododecatriene. Since the cycloolefin having a diene structure or a triene structure in the ring is a polymerization retardant and also a cycloolefin, it can also function as a polymerization retardant while being used as a part of the cycloolefin mixture.

  The amount of the activator and the polymerization retarder is arbitrarily set according to the compound to be used and the purpose. However, the molar ratio of (transition metal atom in the metathesis polymerization catalyst: activator or polymerization retarder) is usually 1: The range is 0.05 to 1: 100, preferably 1: 0.2 to 1:20, more preferably 1: 0.5 to 1:10.

  A crosslinking aid may be added for the purpose of improving the crosslinking reaction rate when the resin molded body is crosslinked. Cross-linking aids include dioxime compounds such as p-quinonedioxime; methacrylate compounds such as lauryl methacrylate and trimethylolpropane trimethacrylate; fumaric acid compounds such as diallyl fumarate: phthalic acid compounds such as diallyl phthalate, triallylcia And cyanuric acid compounds such as nurate; imide compounds such as maleimide; and the like. The amount of the crosslinking aid is not particularly limited, but is usually 0 to 100 parts by weight, preferably 0 to 50 parts by weight with respect to 100 parts by weight of the cycloolefin monomer.

It is preferable to further contain a radical crosslinking retarder in the polymerizable composition, since the fluidity and storage stability of the resin molded product can be improved.
Examples of the radical crosslinking retarder include 3-t-butyl-4-hydroxyanisole, 2-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyanisole, 2,5- Hydroxyanisols such as di-t-butyl-4-hydroxyanisole and bis-1,2- (3,5-di-t-butyl-4-hydroxyphenoxy) ethane; 2,6-dimethoxy-4-methylphenol Dialkoxyphenols such as 2,4-dimethoxy-6-t-butylphenol; hydroquinone, 2-methylhydroquinone, 2,5-dimethylhydroquinone, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydrquinone, 2,5-bis (1,1-dimethylbutyl) hydroquinone, 2,5-bis Hydroquinones such as 1,1,3,3-tetramethylbutyl) hydroquinone; catechols such as catechol, 4-t-butylcatechol, 3,5-di-t-butylcatechol; benzoquinone, naphthoquinone, methylbenzoquinone, etc. Benzoquinones; and the like. Among these, hydroxyanisoles, catechols, and benzoquinones are preferable, and hydroxyanisoles are particularly preferable.
The content of the radical crosslinking retarder is usually 0.001 to 1 mol, preferably 0.01 to 1 mol, with respect to 1 mol of the radical generator.

  A small amount of the solvent is used to dissolve the metathesis polymerization catalyst and the radical generator as required. The solvent can be used as a medium when solution polymerization of the polymerizable composition is performed. In either case, the solvent must be inert to the catalyst. Examples of such solvents 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; Among these, aromatic hydrocarbons, chain aliphatic hydrocarbons, and alicyclic hydrocarbons that are excellent in solubility of the metathesis polymerization catalyst and are widely used in industry are preferable. In addition, a liquid antioxidant, a liquid plasticizer, or a liquid modifier may be used as a solvent as long as it does not decrease the activity of the metathesis polymerization catalyst.

Examples of the modifier include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene copolymer, and acrylonitrile-butadiene-styrene copolymer. , Acrylonitrile-butadiene copolymer, ethylene-propylene-diene terpolymer, ethylene-vinyl acetate copolymer, polysulfur synthetic rubber, acrylic rubber, urethane rubber, fluorine rubber, silicone rubber, polyester elastomer, polyolefin thermoplastic elastomer And elastomers such as polyvinyl chloride-based thermoplastic elastomers.
Examples of the antioxidant include various plastic and rubber antioxidants such as phenol, phosphorus, amine, and sulfur. These antioxidants may be used alone or in combination of two or more.

  The polymerizable composition of the present invention comprises a cycloolefin monomer, a metathesis polymerization catalyst, a metal hydroxide, and a specific metal compound, more preferably a crosslinking agent, a chain transfer agent, and other additives blended as necessary. It is obtained by mixing. The apparatus, means, and procedure for mixing are not particularly limited. For example, there is a method in which a metathesis polymerization catalyst is mixed with a solvent as described above to prepare a catalyst solution, and this is mixed with a cycloolefin monomer or other components.

The resin molded body of the present invention is obtained by ring-opening polymerization of the polymerizable composition. The ring-opening polymerization of the polymerizable composition is performed by a bulk polymerization method or a solution polymerization method, preferably a bulk polymerization method.
Although there is no limitation on the method of obtaining the resin molded product by ring-opening polymerization of the polymerizable composition of the present invention, for example, (a) a method of coating the polymerizable composition on a support and then ring-opening polymerization, (B) A method of injecting a polymerizable composition into a space of a mold and then ring-opening polymerization, (c) a method of impregnating the polymerizable composition into a fibrous reinforcing material, and then ring-opening polymerization. .
Since the polymerizable composition of the present invention has a low viscosity, the application in the method (a) can be smoothly carried out, and the injection in the method (b) does not rapidly cause foaming even in a complex-shaped space. In the method (c), the fibrous reinforcing material can be impregnated quickly and uniformly.

According to the method (a), a resin molded body such as a film or plate can be obtained. The thickness of the molded body is usually 15 mm or less, preferably 10 mm or less, more preferably 5 mm or less.
Examples of the support include films and plates made of resins such as polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, and nylon; iron, stainless steel, copper, aluminum, nickel, chromium, gold, silver, and the like. Examples include films and plates made of metal materials. Especially, use of metal foil or a resin film is preferable. The thickness of these metal foils or resin films is usually 1 to 150 μm, preferably 2 to 100 μm, more preferably 3 to 75 μm from the viewpoint of workability and the like.

  Examples of the method for applying the polymerizable composition of the present invention on the support include known coating methods such as spray coating, dip coating, roll coating, curtain coating, die coating, and slit coating.

  The polymerizable composition coated on the support is dried as necessary, and then subjected to ring-opening polymerization. The polymerizable composition is heated for ring-opening polymerization. As a heating method, a method of placing and heating the polymerizable composition applied to a support on a heating plate, a method of heating while applying pressure using a press (hot pressing), a method of pressing a heated roller, Examples include a method using a heating furnace.

The shape of the resin molding obtained by the method (b) can be arbitrarily set by a molding die. For example, a film shape, a column shape, other arbitrary three-dimensional shapes, etc. are mentioned.
The shape, material, size, etc. of the mold are not particularly limited. As such a mold, a conventionally known mold, for example, a split mold structure, that is, a mold having a core mold and a cavity mold; a mold having a spacer between two plates; and the like can be used.

The pressure (injection pressure) for injecting the polymerizable composition of the present invention into the space (cavity) of the mold is usually 0.01 to 10 MPa, preferably 0.02 to 5 MPa. If the injection pressure is too low, the filling may be insufficient and the transfer surface formed on the inner surface of the cavity may not be transferred well.If the injection pressure is too high, the mold may have high rigidity. Needed and not economical. The mold clamping pressure is usually in the range of 0.01 to 10 MPa.
Ring-opening polymerization can be performed by heating the polymerizable composition filled in the space. Examples of the method for heating the polymerizable composition include a method using a heating means such as an electric heater and steam disposed in a mold, and a method for heating the mold in an electric furnace.

  Examples of the resin molded body obtained by the method (c) include a prepreg formed by filling a ring-opening polymer in a gap between fibrous reinforcing materials. As the fibrous reinforcement, 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, etc. The well-known thing is mentioned. These can be used alone or in combination of two or more. Examples of the shape of the fibrous reinforcing material include mat, cloth, and non-woven fabric.

  In order to impregnate the fibrous reinforcing material with the polymerizable composition of the present invention, for example, a predetermined amount of the polymerizable composition is poured onto a cloth reinforcing material, such as a cloth, a mat, and the like. It can be performed by stacking a protective film on top and pressing with a roller or the like from above. After impregnating the fibrous reinforcing material with the polymerizable composition, the prepreg impregnated with the cycloolefin resin can be obtained by heating to a predetermined temperature and subjecting the impregnated product to ring-opening polymerization. As a heating method, for example, a method in which an impregnated material is placed on a support and heated as in the method (a) above, a fibrous reinforcing material is set in a mold in advance, and a polymerizable composition is used. After impregnation, a method of heating as in the method (b) is used.

  In any of the methods (a), (b) and (c), the heating temperature for ring-opening polymerization of the polymerizable composition (the mold temperature in the method (b)) is usually 30 to 250. ° C, preferably 50-200 ° C. The polymerization time may be appropriately selected, but is usually 1 second to 20 minutes, preferably 10 seconds to 5 minutes or less.

  The ring-opening polymerization reaction is started by heating the polymerizable composition to a predetermined temperature. When the ring-opening 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 ring-opening 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 resin constituting the resin molded body obtained by this polymerization reaction, since the polymerization proceeds completely. The peak temperature can be controlled by the heating temperature. Moreover, in the case of the resin molding obtained from the polymeric composition which mix | blended the chain transfer agent, the polymerization reaction rate of a resin molding is 80% or more normally, Preferably it is 90% or more, More preferably, it is 95% or more. In addition, the polymerization reaction rate of a resin molding can be calculated | required by analyzing the solution obtained by melt | dissolving the resin molding in a solvent by a gas chromatography, for example. A resin molded body in which ring-opening polymerization has almost completely progressed has few residual monomers and is excellent in flame retardancy.

If the peak temperature during the ring-opening polymerization reaction becomes too high, not only the ring-opening polymerization reaction but also the crosslinking reaction may proceed at once. Therefore, it is necessary to control the peak temperature of the ring-opening polymerization to be preferably less than 200 ° C. so that only the ring-opening polymerization reaction proceeds completely and the crosslinking reaction does not proceed.
When a polymerizable composition containing a radical generator is used, it is preferable that the peak temperature in 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. For example, it is 186 ° C. for di-t-butyl peroxide and 194 ° C. for 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3.

  The crosslinked resin molded product of the present invention can be obtained by heating and crosslinking a resin molded product obtained using a polymerizable composition containing a crosslinking agent. The temperature at which the resin molded body is crosslinked by heating is usually 170 to 250 ° C, preferably 180 to 220 ° C. This temperature is preferably higher than the peak temperature in the ring-opening polymerization, and more preferably 20 ° C. or higher. The time for crosslinking by heating is not particularly limited, but is usually from several minutes to several hours.

  The method for heating and crosslinking the resin molded product of the present invention is not particularly limited. When the resin molded body is in the form of a film, a method of laminating a plurality of sheets as necessary 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.

  The crosslinked resin composite material of the present invention comprises a base material and a crosslinked resin molded body. There is no particular limitation on the method for obtaining the crosslinked resin composite material. For example, (1) a resin molded body obtained by using a polymerizable composition containing a crosslinking agent is superimposed on a base material, and then heated to be crosslinked. (2) A method of laminating a polymerizable composition on a base material and causing ring-opening polymerization and crosslinking reaction to proceed.

  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; 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.

  In order to obtain a cross-linked resin composite material by the method (1), for example, the resin molded body of the present invention and a metal foil as a base material are superposed and cross-linked by heating with a hot press or the like. A metal foil-clad laminate that adheres firmly to the foil 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 crosslinkable resin composite material by the method (2), the ring-opening polymerization temperature of the polymerizable composition is set high and heated at a temperature at which a crosslinking reaction occurs. However, in the case of producing a crosslinked resin composite material, the peel strength at the interface increases once the resin molded body is passed through. Moreover, the cross-linked resin composite material of the present invention has an advantage that it can be manufactured very easily because a step of evaporating a large amount of solvent as in the conventional casting method is unnecessary.
The heating method for producing the cross-linked resin composite material of the present invention is not limited, but the method of heat-pressing a resin molded body and a base material such as a metal foil or a printed wiring board manufacturing substrate is highly productive. It is preferable from the height. The conditions for hot pressing are the same as in the case of producing the crosslinked resin molded body.

The resin molded body, cross-linked resin molded body and cross-linked resin composite material of the present invention have the conventional characteristics of cycloolefin resins such as low linear expansion coefficient, high mechanical strength, and low dielectric loss tangent as they are. It has excellent heat resistance and adhesion as compared with a molded body made of cycloolefin resin.
The cross-linked resin molded article and cross-linked resin composite material according to the present invention having such characteristics are used as electronic parts materials such as prepregs; resin-coated copper foils; printed wiring boards, insulating sheets, interlayer insulating films, overcoats, and antenna substrates. Is preferred.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
Preparation of catalyst solution In a glass flask, 51 parts of benzylidene (1,3-dimesityrylimidazolidine-2-ylidene) (tricyclophosphine) ruthenium dichloride and 79 parts of triphenylphosphine are dissolved in 952 parts of toluene. To prepare a catalyst solution.

Example 1
In a polyethylene bottle, 0.2089 parts by weight of 3,5-di-t-butylphenol and tetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] dodec-4-ene 22.5 parts by weight, 2-norbornene 7.5 parts by weight, styrene 0.74 parts by weight, di-t-butyl peroxide (1 minute half-life temperature 186 ° C.) 0.43 ml was added, 1.1 parts by weight of Plenact AL-M (Ajinomoto Fine Techno Co., Ltd.) was added as a dispersant, 47.4 parts by weight of magnesium hydroxide (particle size 0.4 μm), and ferrocene 0.3% by weight A polymerizable composition was prepared by adding 0.12 ml of the catalyst solution and stirring.
One sheet of glass cloth (thickness 0.092 mm) was laid, and the polymerizable composition 1 was poured and impregnated. This was heated and polymerized at 150 ° C. to obtain a prepreg (thickness: 0.1 mm).
The obtained prepregs were stacked and hot-pressed at 5.0 MPa and 200 ° C. to obtain a laminated plate (thickness: 1.6 mm) as a crosslinked resin molded body, and evaluated.
It was visually confirmed that the obtained laminate had no voids.
This cross-linked resin molded product was cut into strip-shaped test pieces having dimensions of 5 inches (12.7 cm) × 1/2 inch (1.3 cm) × thickness 1.6 mm, and flame retardancy was evaluated according to UL-94 standards. did.
Further, the dielectric loss tangent was measured with an impedance analyzer (model number: E4991 manufactured by Agilent).
Moreover, about the sample extract | collected from the resin part of the single-sided copper clad laminated board, the glass transition temperature (Tg) was measured with the differential scanning calorimeter based on JISC6481, and 125 degreeC or more is (circle), Less than 125 degreeC-120 or more were made into (triangle | delta), and less than 120 degreeC was made into x.
As a heat resistance test, the resin portion of the single-sided copper-clad laminate was floated in a solder bath at 260 ° C. for 20 seconds, a heat resistance test was conducted according to JIS C6481, and evaluation was performed according to the following criteria.
○: No swelling △: Slightly bloating ×: Swelling

Example 2
A test piece was obtained in the same manner as in Example 1 except that copper oxalate was used instead of ferrocene, and evaluation was performed in the same manner.

Comparative Examples 1-5
A test piece was obtained in the same manner as in Example 1 except that each component was blended as shown in Table 1, and evaluated in the same manner.
The results are shown in Table 1.

As can be seen from the above examples and comparative examples, magnesium hydroxide is effective for imparting flame retardancy (Examples 1 and 2 and Comparative Examples 2 and 3), but if the amount is increased, the flame retardancy is excellent. It can be seen that the dielectric loss tangent of the product was lowered (Comparative Example 5), and there was heat resistance and voids such as glass transition point and solder heat resistance test, and the moldability was also lowered. However, even if magnesium hydroxide is reduced to 80%, it can be seen that when ferrocene or copper oxalate is used in combination, excellent flame retardancy and heat resistance are exhibited (Examples 1 and 2 and Comparative Example 1). Further, it can be seen that when layered silicate is used instead of the organometallic compound, sufficient flame retardancy and heat resistance cannot be obtained (Comparative Example 4).

Claims (14)

Cycloolefin monomer, metathesis polymerization catalyst, metal hydroxide, and compound represented by general formula (1) ML _a X _b (where M is a metal atom and L is a ligand coordinated to M And at least one L is a ligand having a cyclopentadienyl skeleton, and X is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, or a trialkylsilyl group that are not cross-linked with each other. , SO ₃ R group (where R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent) or a hydrogen atom, a + b is a valence of M, a is 1 or more, b is 0-5) or a polymerizable composition comprising an organic acid metal salt. The polymerizable composition according to claim 1, wherein the organic acid metal salt is a carboxylic acid metal salt. Furthermore, the polymerizable composition of Claim 1 or 2 containing a chain transfer agent. Furthermore, the polymeric composition in any one of Claims 1-3 containing a crosslinking agent. The polymerizable composition according to claim 4, wherein the crosslinking agent is a radical generator. A resin molded article obtained by ring-opening polymerization of the polymerizable composition according to claim 1. The resin molding obtained by apply | coating the polymeric composition in any one of Claims 1-5 on a support body, and carrying out ring-opening polymerization then. A resin molded product obtained by injecting the polymerizable composition according to claim 1 into a space of a mold and then ring-opening polymerization. A resin molded article obtained by impregnating a fibrous reinforcing material with the polymerizable composition according to claim 1 and then ring-opening polymerization. The resin molded body according to claim 6, wherein the ring-opening polymerization is performed by bulk polymerization. A crosslinked resin molded article obtained by heating and crosslinking a resin molded article obtained by ring-opening polymerization of the polymerizable composition according to claim 4 or 5. The crosslinked resin molded article according to claim 11, wherein the ring-opening polymerization is carried out by bulk polymerization. A crosslinked resin composite material obtained by superposing a resin molded body obtained by ring-opening polymerization of the polymerizable composition according to claim 4 or 5 on a base material and then crosslinking by heating. The crosslinked resin composite material according to claim 13, wherein the ring-opening polymerization is carried out by bulk polymerization.