JP5125317B2 - Polymerizable composition, crosslinkable resin and crosslinked product - Google Patents

Description

  The present invention relates to a polymerizable composition, a resin molded body, and a crosslinked resin molded body. More specifically, the present invention relates to a polymerizable composition having excellent dispersibility of a solid powder and a low viscosity, and a crosslinkable resin and a cross-linked product obtained by using the polymerizable composition and having excellent electrical properties and adhesion.

  With recent miniaturization of electronic devices and higher communication speed, electronic circuit boards are also required to be smaller and more multifunctional. As a small and multifunctional electronic circuit board, a board using a dielectric material having a large relative dielectric constant is known. Since the wavelength of the electromagnetic wave propagating in the dielectric material becomes shorter as the relative dielectric constant of the dielectric material is larger, the circuit board and the electronic component can be miniaturized by using the dielectric material having a larger relative dielectric constant. Because. It has also been proposed to use a high dielectric constant material for the circuit board so that the board has a capacitor function.

  Furthermore, since such a circuit board is often used in a high-frequency region and requires excellent high-frequency characteristics, the material used for the board is required to have not only a high dielectric constant but also a low dielectric loss. As such a material, a ceramic material such as a low temperature co-fired ceramic (LTCC) is used. However, circuit boards using ceramics have low productivity and workability, and are insufficient in impact resistance.

  Therefore, high dielectric materials formed by adding a solid powder (dielectric material) having a high dielectric constant to a resin have been studied. However, when a large amount of dielectric is used to obtain a high dielectric constant, there is a problem that productivity and workability deteriorate. That is, in melt molding such as injection molding, it is difficult to uniformly mix dielectrics. On the other hand, in the casting method using a solution, there is a problem that a step of drying the solvent is necessary and productivity is low. Further, since the solvent is volatilized from the upper surface of the cast solution, there are cases where the dispersion of the dielectric becomes non-uniform in the thickness direction of the obtained molded body or the surface of the molded body is not flat.

  There is also known a method of obtaining a resin molded body containing a solid powder by bulk polymerization of a polymerizable composition containing a bulk polymerizable monomer and a solid powder, which is a resin precursor. However, in this method, there is a problem that the strength of the resin molded body resulting from non-uniform dispersion of the solid powder in the monomer is lowered, or the viscosity of the polymerizable composition is increased and molding becomes difficult. .

  As a method for enhancing the dispersibility of the solid powder in the polymerizable composition, a method of using the surface of the solid powder treated with a silane coupling agent (Patent Document 1), or a silane coupling agent in the polymerizable composition A method of adding and using (Patent Document 2) has been proposed. However, even in these methods, when a large amount of a solid powder such as a metal oxide is used, the dispersion of the solid powder may be insufficient. If the dispersion of the solid powder is insufficient, the flatness of the surface of the resulting molded product may be impaired, or the adhesion with the conductor circuit may be insufficient.

Japanese Patent Laid-Open No. 10-17676 JP 2002-179889 A

  An object of this invention is to provide the polymeric composition which is excellent in the dispersibility of solid powder, has a low viscosity, and is excellent in molding processability. Another object of the present invention is to provide a resin molded body and a cross-linked resin molded body, which are obtained from such a polymerizable composition and have excellent electrical characteristics and adhesion.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by treating and using the surface of the solid powder in two steps in a specific order using two or more specific silane compounds. Based on the knowledge, the present invention has been completed.

Thus, according to the present invention, the following (1) to (9) are provided.
(1) A polymerizable composition comprising a block polymerizable monomer, a polymerization catalyst, and a surface-treated solid powder,
The first surface treatment step in which the surface treatment is performed with a first surface treatment agent selected from tetraalkoxysilane compounds, and the second surface treatment agent selected from silane compounds represented by the following formula (I) A second surface treatment step for surface treatment;
A polymerizable composition comprising:
SiR ¹ (OR ² ) _n X _3-n (I)
(In the formula, R ¹ and R ² each independently represent a hydrocarbon group, X represents a halogen atom, and n represents an integer of 0 to ^3. )

(2) The polymerizable composition according to (1), wherein the second surface treatment agent includes a silane compound in which R ¹ in the formula (I) is an alkyl group having 5 to 200 carbon atoms.
(3) The polymerizable composition according to (1) or (2), wherein the second surface treatment agent includes a silane compound in which R ¹ in the formula (I) is a hydrocarbon group having a carbon-carbon double bond. .
(4) The polymerizable composition according to any one of (1) to (3), wherein the solid powder is a metal oxide.
(5) The polymerizable composition according to any one of (1) to (4), wherein the bulk polymerizable monomer is a cycloolefin monomer.
(6) The polymerizable composition according to any one of (1) to (5), further including a crosslinking agent.

(7) A resin molded body obtained by bulk polymerization of the polymerizable composition of any one of (1) to (4).
(8) A crosslinkable resin molded article obtained by bulk polymerization of the polymerizable composition of (6).
(9) A crosslinked resin molded product obtained by crosslinking the crosslinkable resin molded product of (8).

  According to the present invention, a polymerizable composition having excellent dispersibility of a solid powder and low viscosity is provided. When the polymerizable composition is used, a resin molded body and a crosslinked resin molded body having excellent electrical characteristics and adhesiveness can be obtained. In particular, since the present invention exhibits an excellent effect when a dielectric is used as the solid powder, the resin molded body and the crosslinked resin molded body of the present invention are useful as a high dielectric material used for a multilayer circuit board and the like.

  The polymerizable composition of the present invention contains a bulk polymerizable monomer, a polymerization catalyst, and a surface-treated solid powder.

(Block-polymerizable monomer)
The monomer used in the present invention is not particularly limited as long as it can be bulk polymerized. For example, an epoxy compound, an acrylate compound, styrenes, a cycloolefin monomer, etc. are mentioned. Of these, styrenes and cycloolefin monomers, which are nonpolar monomers, are preferable from the viewpoint of obtaining a molded article having a low dielectric loss.
In addition, a cycloolefin monomer is more preferable because a crosslinkable resin molded product capable of post-crosslinking can be easily obtained and the laminate property is excellent.

  The cycloolefin monomer has a ring structure formed of carbon atoms, has a carbon-carbon double bond in the ring, the carbon-carbon double bond is opened by a metathesis reaction, and the ring is formed in the main chain. It is a compound that can produce a polymer having a structure. Examples thereof include norbornene monomers and monocyclic cycloolefins, and preferred examples include norbornene monomers.

  The norbornene-based monomer is a monomer containing a norbornene ring. Specific examples include norbornenes, dicyclopentadiene, and tetracyclododecenes. These may contain a hydrocarbon group such as an alkyl group, an alkenyl group, an alkylidene group or an aryl group, or a polar group such as a carboxyl group or an acid anhydride group as a substituent. Moreover, in addition to the double bond of the norbornene ring, it may have another double bond. Among these, norbornene-based monomers that do not contain a polar group, that is, are composed only of carbon atoms and hydrogen atoms, are preferable because a resin molded body with low dielectric loss can be obtained. The number of rings constituting the norbornene-based monomer is preferably 3 to 6, more preferably 3 or 4, and particularly preferably 4.

Examples of the norbornene-based monomer not containing a polar group include 2-norbornene, 5-cyclohexyl-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-phenyl-2-norbornene, and tetracyclo [9 .2.1.0 ^2,10. 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), tetracyclo [10.2.1.0. ^2,11 . Norbornenes such as 0 ^4,9 ] pentadeca-4,6,8,13-tetraene (also referred to as 1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene);

Norbornenes having 3 rings such as 5-cyclopentyl-2-norbornene, 5-cyclohexenyl-2-norbornene, 5-cyclopentenyl-2-norbornene;
Dicyclopentadiene having 3 rings such as dicyclopentadiene, methyldicyclopentadiene, dihydrodicyclopentadiene (also referred to as tricyclo [5.2.1.0 ^2,6 ] dec-8-ene);

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-vinyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-phenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] tetracyclododecenes such as 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 . 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic anhydride, methyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, 5-norbornene-2- And norbornene monomers containing polar groups such as all, 5-norbornene-2-carbonitrile, 7-oxa-2-norbornene, and the like.

  Examples of the monocyclic cycloolefin include monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, and derivatives thereof having a substituent. These cycloolefin monomers can be used alone or in combination of two or more. It is possible to freely control the glass transition temperature and the melting temperature of the resulting polymer and crosslinked product by using two or more monomers in combination and changing the mixing ratio. The amount of monocyclic cycloolefins and derivatives thereof is preferably 40% by mass or less, more preferably 20% by mass or less, based on the total amount of cycloolefin monomer. If it exceeds 40% by mass, the heat resistance of the polymer and the crosslinked product may be insufficient.

  In this invention, an acrylate compound represents acrylic acid, methacrylic acid, acrylic acid (or methacrylic acid) ester. The acrylic acid (or methacrylic acid) ester is preferably an alkyl ester or alkenyl ester. Carbon number of the alkyl group or alkenyl group of the alkyl ester or alkenyl ester is usually 1 to 20, preferably 4 to 18, more preferably 4 to 12, and particularly preferably 4 to 8.

  Specific examples of acrylic acid (or methacrylic acid) esters include methyl acrylate (or methacrylic acid), acrylic acid (or methacrylic acid) ethyl, acrylic acid (or methacrylic acid) n-butyl, and acrylic acid (or methacrylic acid). Acrylic acid (such as 2-ethylhexyl, acrylic acid (or methacrylic acid) n-octyl, acrylic acid (or methacrylic acid) isooctyl, acrylic acid (or methacrylic acid) n-decyl, acrylic acid (or methacrylic acid) n-dodecyl ( Or methacrylic acid) alkyl ester; acrylic acid (or methacrylic acid) allyl, acrylic acid (or methacrylic acid) butenyl, acrylic acid (or methacrylic acid) pentenyl, acrylic acid (or methacrylic acid) hexenyl, acrylic acid (or methacrylate) Acrylic acid (or methacrylic acid) alkenyl esters such as acid) heptenyl, acrylic acid (or methacrylic acid) octenyl, acrylic acid (or methacrylic acid) nonenyl, acrylic acid (or methacrylic acid) decenyl, acrylic acid (or methacrylic acid) undecenyl ;

  Acrylic acid (or methacrylic acid) hydroxyethyl, acrylic acid (or methacrylic acid) hydroxypropyl ester such as hydroxypropyl ester; acrylic acid (or methacrylic acid) N, N-dimethylaminomethyl, acrylic acid ( Or acrylic acid (or methacrylic acid) N, N-dimethylaminoalkyl ester, such as methacrylic acid (N, N-dimethylaminoethyl); epoxy group-containing acrylic acid (or methacrylic acid), such as acrylic acid (or methacrylic acid) glycidyl Esters; Diacrylates such as polyethylene glycol diacrylate and 1,3-butylene glycol diacrylate; Ethylene dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate Dimethacrylates such as rate; triacrylate esters such as trimethylol propane triacrylate; tri methacrylates such as trimethylolpropane trimethacrylate; and the like.

  In the present invention, styrenes are compounds having an aromatic ring and a vinyl group or isopropenyl group bonded thereto. Specific examples thereof include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylethylbenzene, vinylxylene, pt-butylstyrene, α-methyl-p-methylstyrene, Examples thereof include vinyl naphthalene, and among these, styrene is preferable. Further, as styrenes, compounds having two or more vinyl groups or isopropenyl groups such as o-divinylbenzene, p-divinylbenzene and m-divinylbenzene can be used. Use of such a compound is preferable because the cross-linking reactivity of the obtained resin molding can be increased and the cross-linking density of the cross-linking resin molding can be increased.

(Polymerization catalyst)
The polymerization catalyst constituting the polymerizable composition of the present invention can be appropriately selected according to the above-mentioned bulk polymerizable monomer and polymerization reaction mode. For example, in the above cycloolefin monomer, a metathesis polymerization catalyst can be selected as a suitable polymerization catalyst. Examples of the metathesis polymerization catalyst include a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds with a transition metal atom as a central atom. 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 which is an atom of 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 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 and 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.

  Among these ruthenium carbene complexes, a ruthenium complex compound having a substituted imidazoline-2-ylidene substituted at the 4-position and 5-position with a halogen atom as a ligand 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.

  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.

  When the polymerizable monomer is an acrylate compound, examples of the polymerization catalyst include a radical generator, a cationic polymerization initiator, and an anionic polymerization initiator, and a radical generator is preferred.

  When the polymerizable monomer is styrene, the polymerization catalyst includes a radical generator, a cationic polymerization initiator, an anionic polymerization initiator, a metallocene catalyst, a phenoxyimine catalyst, and the like. The radical generator, the metallocene catalyst, and the phenoxy An imine catalyst is preferred, and a radical generator is more preferred.

  Known radical generators that are polymerization catalysts for acrylate compounds and styrenes can be used. For example, persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate; hydrogen peroxide; lauroyl peroxide, benzoyl peroxide, di-2-ethylhexyl peroxydicarbonate, t-butyl hydroperoxide, t-butyl Organic peroxides such as peroxypivalate, cyclohexanone peroxide, cumene hydroperoxide, etc., and these may be used alone or in combination, or with reducing agents such as acidic sodium sulfite, sodium thiosulfate, ascorbic acid, etc. Can be used as a combined redox system. 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. Among them, those having a 1 minute half-life temperature of 150 ° C. or lower are preferable, and those having a half-life temperature of 130 ° C. or lower are more preferable. In the present invention, the 1-minute half-life temperature represents a temperature at which the radical generator decomposes and becomes half in one minute.

(Surface-treated solid powder)
The polymerizable composition of the present invention comprises a surface-treated solid powder in addition to the bulk polymerizable monomer and the polymerization catalyst.

  As long as the solid powder used in the present invention is a particle that is insoluble in a block polymerizable monomer and a solvent used as required, various powders can be used regardless of whether they are organic or inorganic. And is appropriately selected according to the use of the finally obtained resin molded body. Further, the shape of the powder is not particularly limited, and may be any shape such as a spherical shape, a granular shape, an indefinite shape, a dendritic shape, a needle shape, a rod shape, or a flat shape.

  The average particle size of the solid powder is not particularly limited, but is usually 0.001 to 70 μm, preferably 0.01 in terms of median diameter containing 50% by volume of all particles measured by a laser scattering diffraction particle size distribution meter. It is -50 micrometers, More preferably, it is 0.05-15 micrometers, Most preferably, it is 0.1-5 micrometers. Even if the particle size is smaller than this range, even if the particle size is larger, molding may be difficult and handling may be difficult.

The solid powder may be an organic substance or an inorganic substance, but is preferably an inorganic substance from the viewpoint that a resin molded body having a higher dielectric constant can be obtained. Examples of inorganic substances include metals such as iron, copper, nickel, gold, silver, aluminum, lead, and tungsten; carbon such as carbon black, graphite, activated carbon, and carbon balloon; non-metal oxides such as glass, silica, and silica balloon; Alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, antimony oxide, beryllium oxide, tungsten oxide, barium ferrite, strontium ferrite, BaTiO ₃ , BaPbO ₃ , MgTiO ₃ , CaTiO ₃ , SrTiO ₃ , NaNbO ₃ , Metal oxides which may be complex oxides such as KNbO ₃ , NaTaO ₃ , KTaO ₃ , LiTaO ₃ , LiNbO ₃ , Rochelle salt, etc .; inorganic hydroxides such as aluminum hydroxide and magnesium hydroxide; calcium carbonate, carbonate magnesium, Inorganic carbonates such as sodium hydrogen carbonate; inorganic sulfates such as calcium sulfate; inorganic silicates such as talc, clay, mica, kaolin, fly ash, montmorillonite, calcium silicate, glass, glass balloon; calcium titanate, titanium Examples thereof include titanates such as lead zirconate acid; aluminum nitride; silicon carbide; whiskers. Among these, a metal oxide is preferable because it is an insulator, and a metal composite oxide is more preferable because a dielectric loss of the obtained resin molded body can be reduced.

As the metal complex oxide, one having a perovskite structure is preferable because it exhibits a high dielectric constant. The metal composite oxide having a perovskite structure generally has a structure represented by the formula ABX ₃ and the cation at the A site and the O ²⁻ which is the anion at the X site have the same size. A cation having a size smaller than that of the A site is located at the B site in a cubic unit cell composed of the A site and the X site. In the above formula, A and B represent different metal ions, and the total valence of A and B is 6. _{Specifically, BaTiO 3, CaTiO 3, SrTiO} 3, PbTiO 3, PbZrO 3, those represented by BaMnO ₃ ^A 2+ ^B 4+ _{O 3,} such _as; KNbO _3, KTaO _3, A, such as NaNbO _3, NaTaO 3 Those represented by ⁺ B ⁵⁺ O ₃ ; those represented by A ³⁺ B ³⁺ O ₃ such as BiFeO ₃ , BiAlO ₃ , YFeO ₃ , GdFeO ₃ , LaAlO ₃ ;

Among metal complex oxides having a perovskite structure, complex perovskite type compounds are particularly preferable. The compound perovskite type compound is represented by the formula A
And / or B has a plurality of metal atom ions. Specifically, A ²⁺ (B ²⁺ _1/3 B ⁵⁺ _2/3 ) O ₃ , A ²⁺ (B ³⁺ _1/2 B ⁵⁺ _1/2 ) O ₃ , A ²⁺ (B ²⁺ _1/2 B ^{6 +} _{1) / 2} ) O ₃ , A ²⁺ (B ³⁺ _2/3 B ⁶⁺ _1/3 ) O ₃ , A ²⁺ (B ⁺ _1/4 B ⁵⁺ _3/4 ) O ₃ , (A ⁺ _1/2 B ³⁺ _{1 / 2} ) B ⁴⁺ O ₃ , A ³⁺ (B ²⁺ _1/2 B ⁴⁺ _1/2 ) O ₃ , (A ⁺ _1/2 A ³⁺ _1/2 ) (B ²⁺ _1/3 B ⁵⁺ _2/3 ) O ₃ And the like. Here, as A and B, ^{A Li} + as ^{+, Na +, K +,} Ag +; A 2+ as ^{Pb 2+, Ba 2+, Sr 2+} , Ca 2+; A 3+ as ^{Bi 3+, La 3+, Ce 3+} , Nd ³⁺ ; B ⁺ as Li ⁺ , Cu ⁺ ; B ²⁺ as Mg ²⁺ , Ni ²⁺ , Zn ²⁺ , Co ²⁺ , Sn ²⁺ , Fe ²⁺ , Cd ²⁺ , Cu ²⁺ , Cr ²⁺ ; B ³⁺ as Mn ³⁺ , Sb ^{3+ , Al 3+, Yb 3+, In} 3+, Fe 3+, Co 3+, Sc 3+, Y 3+, Sn 3+; B 4+ as ^{Ti 4+,} Zr ^{4+; B 5+} as ^{Nb 5+, Sb 5+, Ta 5+} , Bi 5+; B ^Examples of ⁶⁺ include W ⁶⁺ , Te ⁶⁺ , Re ⁶⁺ ; Specific examples of such composite perovskite compounds include Pb (Ni _1/3 Nb _2/3 ) O ₃ , Ba (Ni _1/3 Nb _2/3 ) O ₃ , Pb (Sc _1/2 Nb _2/3 ). _{O 3, (Li 1/2 Bi 1/2} ) TiO 3, (Na 1/2 Bi 1/2) TiO 3, (K 1/2 Bi 1/2) TiO 3, (Ag 1/2 Bi 1 / ₂ ) TiO ₃ , Bi (Mg _1/2 Ti _1/2 ) O ₃ , Bi (Zn _1/2 Ti _1/2 ) O ₃ , Bi (Ni _1/2 Ti _1/2 ) O ₃ , (Na _{1 / 2} Bi _1/2 ) (Mg _1/3 Nb _2/3 ) O _{3 and the} like. By using the composite perovskite type compound, the obtained resin molded body can have a stable temperature characteristic of dielectric constant and a small dielectric loss tangent.

  Examples of organic substances include wood flour, starch, organic pigments, polystyrene, nylon, polyolefins such as polyethylene and polypropylene, vinyl chloride, various elastomers, and waste plastics.

  In addition to the above, short fiber solid powders such as chopped strands and milled fibers can also be used. The types of fibers include inorganic fibers such as glass fibers, carbon fibers, metal fibers, or aramid fibers, nylon fibers, jute fibers, kenaf fibers, bamboo fibers, polyethylene fibers, drawn polyethylene fibers, polypropylene fibers, drawn polypropylene fibers, etc. Fiber.

  Further, the solid powder may be a solid flame retardant such as a phosphorus compound, an organic halogen-containing compound, and an organic nitrogen-containing compound.

  The relative dielectric constant of the solid powder is usually 5 to 10,000, preferably 10 to 5,000, more preferably 20 to 1,000, still more preferably 50 to 500, and particularly preferably 60 to 300. When the relative dielectric constant of the solid powder is within this range, a high dielectric material having low dielectric loss and excellent moldability, reliability, and heat resistance can be obtained. Moreover, it becomes easy to adjust the relative dielectric constant of the obtained resin molding to about 5-30 suitable as various dielectric materials.

The solid powder used in the present invention is a first surface treatment step in which a surface treatment is performed with a first surface treatment agent selected from tetraalkoxysilane compounds and a silane compound represented by the following formula (I). Surface treatment is performed by a process including a second surface treatment process in which a surface treatment is performed with two surface treatment agents.
SiR ¹ (OR ² ) _n X _3-n (I)
(In the formula, R ¹ and R ² each independently represent a hydrocarbon group, X represents a halogen atom, and n represents an integer of 0 to ^3. )

  Examples of the tetraalkoxysilane compound used as the first surface treating agent include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraphenoxysilane. Since the reactivity of hydrolysis and condensation is excellent, tetraethoxysilane is preferable. preferable.

In the silane compound represented by the formula (I) used as the second surface treating agent, R ¹ represents a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group, and these may further have a substituent composed of a hydrocarbon. Among these, an alkyl group or a hydrocarbon group having a carbon-carbon double bond is preferable.

  The alkyl group generally has 1 to 200 carbon atoms, preferably 5 to 30 carbon atoms, and more preferably 10 to 20 carbon atoms. When the carbon number of the alkyl group is within this range, a polymerizable composition having a low viscosity and excellent dispersibility of the solid powder can be obtained. The alkyl group may be linear or branched, but is preferably linear because it has high wettability and a high effect of reducing the viscosity of the polymerizable composition.

  Examples of the hydrocarbon group having a carbon-carbon double bond include an alkenyl group or a cycloalkyl group, aryl group or aralkyl group having an alkenyl group as a substituent. Among them, an alkenyl group such as vinyl group, allyl group and butenyl group; a group represented by the following formula (II) such as styryl group and vinylbenzyl group; a group having an unsaturated bond at the terminal, such as carbon-carbon, is preferable. Since the double bond is a conjugated double bond, the radical stability is high, and therefore a group represented by the following formula (II) is more preferable.

  In formula (II), m represents an integer of 0-20.

In the silane compound represented by the formula (I), R ² represents a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group, and an alkyl group is preferable.
X represents a halogen atom, and specific examples include a chlorine atom and a bromine atom.

Specific examples of the silane compound represented by the formula (I) include silane compounds in which R ¹ is an alkyl group such as n-octadecyltrimethoxysilane, n-decyltrimethoxysilane, n-hexyltrimethoxysilane; Methoxysilane, 3-butenyltrimethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, allyltrichlorosilane, allylmethyldichlorosilane, styryltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris Silane compounds in which R ¹ is a hydrocarbon group having a carbon-carbon double bond, such as (2-methoxyethoxy) silane and vinyltrichlorosilane.

The silane compounds represented by the formula (I) can be used singly or in combination of two or more. In particular, a silane compound in which R ¹ is an alkyl group of from 5 to 200 carbon atoms, R ¹ is a carbon - viscosity when used in combination with the silane compound is a hydrocarbon group having a carbon-carbon double bond, the polymerizable composition Is low, and it is preferable because the obtained resin molded body can have high crosslinkability, heat resistance, and electrical reliability. The ratio of the amount used, (R ¹ is a silane compound is an alkyl group of 5 to 200 carbon atoms) :( R ¹ is carbon - an amount of the silane compound is a hydrocarbon group having a carbon-carbon double bond), Preferably it is 1: 9-9: 1, More preferably, it is 4: 6-6: 4.
Moreover, you may use together silane compounds other than the silane compound represented by Formula (I) in the range which does not impair the effect of this invention.

  In the present invention, first, a first surface treatment step is performed in which the surface of the solid powder is treated with a first surface treatment agent selected from tetraalkoxysilane compounds. The surface treatment is performed by bringing the first surface treatment agent into contact with the solid powder surface. The treatment conditions of the first surface treatment step are not particularly limited, and a condition that allows the first surface treatment agent to contact the surface of the solid powder may be selected. Specifically, there are a dry method in which the first surface treatment agent is directly brought into contact with the surface of the solid powder, and a wet method in which the solid powder is added to and mixed with a solution obtained by dissolving the first surface treatment agent in a solvent. However, the dry method is preferable because the process is simple and the productivity is excellent.

  The amount of the first surface treatment agent used in the first surface treatment step is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the solid powder before the surface treatment. About a part. Further, the treatment temperature is preferably 40 to 200 ° C., and the mixture of the first surface treatment agent and the solid powder may be stirred in an inert atmosphere in order to prevent the surface treatment agent from being altered. The treatment time is not particularly limited, and is usually 5 minutes to 100 minutes, preferably 15 to 60 minutes. Moreover, it is preferable to perform a drying process before and after the 1st and 2nd surface treatment process as needed. Usually, it is 20-200 degreeC, Preferably it is 60-160 degreeC, More preferably, it is 80-120 degreeC. The drying time is usually 10 to 60 minutes, preferably 20 minutes to 4 hours, more preferably 30 minutes to 2 hours.

  Next, the solid powder subjected to the first surface treatment process is further subjected to a second surface treatment process in which a surface treatment is performed with a second surface treatment agent selected from silane compounds represented by the formula (I).

  In the second surface treatment step, the solid powder 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 solid powder surface. The contact method is the same as the first surface treatment step, and a dry method is preferable. The amount of the second surface treatment agent used in the second surface treatment step is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the solid powder before the surface treatment. Part. The treatment temperature is preferably 40 to 200 ° C., and the mixture of the second surface treatment agent and the solid powder may be stirred in an inert atmosphere in order to prevent the surface treatment agent from being altered. The treatment time is not particularly limited, and may be about 10 minutes to 60 minutes.

  Next, it is preferable to dry the surface-treated solid powder. 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 amount of the surface-treated solid powder is usually 50 to 600 parts by weight, preferably 100 to 500 parts by weight, more preferably 150 to 450 parts by weight, particularly preferably 100 parts by weight of the block polymerizable monomer. 200 to 400 parts by mass. If it is more or less than this, defects are likely to occur during processing or lamination with other materials.

  Here, the total volume and the total mass of the polymerizable composition refer to a composition comprising all these components in the case of including a bulk polymerizable monomer, a polymerization catalyst and a solid powder, and optional components described later. It means the volume and mass of an object. If the amount of the solid powder is less than the above range, the effect of blending the solid powder may not be obtained, and if it is more than this range, the moldability may be deteriorated.

As described above, by using the solid powder surface-treated in two steps, a polymerizable composition having a low viscosity and easy handling can be obtained even when the amount of the solid powder is large. In addition, a resin molded body formed by bulk polymerization of such a polymerizable composition and a crosslinked resin molded body formed by further crosslinking the resin composition are excellent in adhesion between the resin and the solid powder. The reason why such an effect is obtained is not clear, but since the tetraalkoxysilane compound easily forms SiO ₂ by condensation, a SiO ₂ film is formed on the surface of the solid powder by the first surface treatment step. It is estimated to be. In particular, when the solid powder is a metal oxide, the surface often has a hydroxyl group and is basic, and the silane compound represented by the formula (I) is difficult to bond. By forming the SiO ₂ film on the surface of the solid powder, the efficiency of the surface treatment with the silane compound represented by the formula (I) as the second surface treatment agent can be increased. In addition, since the efficiency of the second surface treatment process is increased, the surface of the solid powder can be made hydrophobic. Therefore, when the block polymerizable monomer is a nonpolar monomer, it is considered that the compatibility with the monomer is increased, and a uniformly dispersed polymerizable composition is obtained with less aggregation of the solid powder.

(Polymerizable composition)
In the polymerizable composition of the present invention, various additives such as a chain transfer agent, a crosslinking agent, a crosslinking aid, a radical crosslinking retarder, a polymerization reaction retarder, a dispersant, a solvent, a reinforcing material, a modifier, Antioxidants, colorants, light stabilizers and the like can be included. These can be used by dissolving or dispersing in a monomer solution or a catalyst solution described later in advance.

It is preferable that the polymerizable composition further contains a chain transfer agent for bulk polymerization reaction. By including the chain transfer agent, the progress of the polymerization reaction at room temperature or lower can be suppressed. Moreover, since it can suppress that a polymerization reaction and a crosslinking reaction advance simultaneously, the manufacturing conditions of a crosslinked resin molding can be adjusted by selecting the kind and quantity suitably.
A chain transfer agent can be suitably selected according to the monomer to be used. When a cycloolefin monomer is used, a compound having a vinyl group can be usually 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, a compound represented by the formula (C): CH ₂ ═CH—QY is preferable. 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 a chain transfer agent having this structure, it is possible to obtain a crosslinked resin molded product 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.

  When an acrylate compound or styrene is used as the polymerizable monomer, lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-propion mercapto acid, α-methylstyrene dimer, or the like is used as the chain transfer agent. be able to.

  The amount of the chain transfer agent is usually 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the total amount of the block polymerizable monomers. When the amount of the chain transfer agent is within this range, a resin molded product having a high polymerization reaction rate and capable of post-crosslinking can be obtained efficiently.

  The polymerizable composition of the present invention preferably further contains a cross-linking agent so that a cross-linking reaction can be performed after the bulk polymerization reaction. The crosslinkable resin molded article of the present invention can be obtained by bulk polymerization of the polymerizable composition containing the crosslinker.

  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 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 a generator is particularly preferred.

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; 2,2-di (t-butylperoxy) butane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -2-methyl Peroxyketals such as cyclohexane and 1,1-di (t-butylperoxy) cyclohexane; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropylcarbonate, di (isopropylperoxy) Peroxycarbonates such as dicarbonate; alkylsilyl peroxides such as t-butyltrimethylsilyl peroxide; and the like. Of these, dialkyl peroxides and peroxyketals are preferred in that they have few obstacles to the metathesis polymerization reaction.

  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.

  Examples of the nonpolar radical generator used in the present invention include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diphenylbutane, 1,4-diphenylbutane, and 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 1,1,2-triphenylethane, triphenylmethane, 1,1,1-triphenylethane, 1,1,1-triphenylpropane, 1,1,1-triphenylbutane, 1,1,1-triphenyl Examples include phenylpentane, 1,1,1-triphenyl-2-propene, 1,1,1-triphenyl-4-pentene, 1,1,1-triphenyl-2-phenylethane, and the like.

  These radical generators can be used alone or in combination of two or more. By using two or more kinds of radical generators in combination and adjusting the amount ratio, it is possible to freely control the glass transition temperature and the molten state of the resulting crosslinkable resin molded article and the crosslinked resin molded article. The cross-linking agent preferably has a 1 minute half-life temperature of 150 to 300 ° C, more preferably 180 to 250 ° C.

  These radical generators include those that act as the polymerization catalyst. When an acrylate compound or styrene is used as the bulk polymerizable monomer, two or more radical generators having different half-life temperatures for 1 minute are used, and a temperature at which only some radical generators are selectively decomposed. It is preferable to carry out bulk polymerization in order to decompose the remaining radical generator at a temperature higher than that to perform crosslinking. In addition, when only one kind of radical generator is used, a part of the radical generator remains in the resulting crosslinkable resin molded article by stopping the polymerization reaction in the middle, and this may be used as a crosslinking agent. it can.

  The amount of the crosslinking agent is usually 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the block polymerizable monomer. If the amount of the crosslinking agent is too small, crosslinking may be insufficient, and a crosslinked resin molded product having a high crosslinking density may not be obtained. When the amount of the cross-linking agent is too large, the cross-linking effect is saturated, while the polymer and the cross-linked resin molded product having desired physical properties may not be obtained.

In the present invention, when a radical generator is used as the crosslinking agent, a crosslinking aid can be used to promote 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.

When the bulk polymerizable monomer is a cycloolefin monomer and a metathesis catalyst is used as a polymerization catalyst, the polymerization reaction retarder is triphenylphosphine, tributylphosphine, trimethylphosphine, triethylphosphine, dicyclohexylphosphine, vinyldiphenylphosphine, allyl. Phosphine compounds such as diphenylphosphine, triallylphosphine, and styryldiphenylphosphine; Lewis bases such as aniline and pyridine; and the like can be used.
Of the cyclic olefin monomers copolymerizable with the norbornene monomer, the cyclic olefin having a 1,5-diene structure or a 1,3,5-triene structure in the molecule also functions as a polymerization reaction retarder. Examples of such a compound 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.

  Furthermore, the polymerizable composition of the present invention may contain a dispersant as long as the effects of the present invention are not impaired. Examples of the dispersant include a cationic dispersant, an anionic dispersant, a betaine dispersant, and a nonionic dispersant. These may be used alone or in combination of two or more.

  The solvent is used in a small amount to dissolve or disperse the polymerization catalyst and the crosslinking agent as required. Such a solvent is not particularly limited as long as it does not decrease the activity of the polymerization catalyst, and examples thereof include chain aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; cyclopentane, cyclohexane, and methylcyclohexane. Alicyclic hydrocarbons such as dimethylcyclohexane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene, indene and tetrahydronaphthalene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; diethyl ether, Oxygen-containing hydrocarbons such as tetrahydrofuran; and the like. Among these, aromatic hydrocarbons, chain aliphatic hydrocarbons, and alicyclic hydrocarbons that are excellent in solubility of the polymerization catalyst and are widely used industrially 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 polymerization catalyst. You may use these individually by 1 type or in combination of 2 or more types.

  Examples of the antioxidant include various hindered phenol-based, phosphorus-based and amine-based antioxidants for plastics and rubbers. These antioxidants may be used alone or in combination of two or more.

  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. Examples of the modifier include natural rubber, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), ethylene-propylene-dienter. Examples include polymers (EPDM), ethylene-vinyl acetate copolymers (EVA), and elastomers such as hydrides thereof.

It is particularly desirable to adjust the viscosity of the polymerizable composition of the present invention so that the upper limit is usually 5 Pa · s, preferably 3 Pa · s, more preferably 2 Pa · s, particularly preferably 1 Pa · s. The lower limit is usually 0.01 Pa · s, preferably 0.1 Pa · s. If the viscosity is too high or too low than this range, molding may be difficult. For example, the viscosity of the polymerizable composition tends to increase as the amount of the solid powder increases, and tends to decrease as the amount of the surface treatment agent used or the amount of the dispersant increases. Since the treated solid powder has a markedly increased affinity with the block polymerizable monomer, the polymerizable composition of the present invention has a low viscosity even when a large amount of the solid powder is used. it can.
Here, as described later, the viscosity of the polymerizable composition is a value measured at 20 rpm using a high shear rate viscometer immediately after adding the polymerization catalyst to the monomer liquid.

  The polymerizable composition is not particularly limited by the method for preparing the polymerizable composition. The polymerizable composition is prepared, for example, 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 solid-polymerizing a monomer capable of bulk polymerization, and Prepared by preparing a liquid (hereinafter sometimes referred to as “monomer liquid”) containing additives such as a chain transfer agent and a crosslinking agent as required, adding the catalyst liquid to the monomer liquid, and stirring. it can. The catalyst solution is preferably added immediately before the polymerization described below. The solid powder is preferably added to the monomer solution.

  In the present invention, the temperature of the monomer liquid when adding the polymerization catalyst is usually -10 ° C to 25 ° C, preferably -5 ° C to 20 ° C, more preferably -5 ° C to 15 ° C, and particularly preferably -5 ° C to 10 ° C. It is preferable to set it as ° C. If it is higher than this temperature, the polymerization proceeds abruptly at the moment when the polymerization catalyst is added, and the viscosity of the polymerizable composition may increase and the molding may become impossible.

  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 molding 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.

  When preparing the monomer liquid, the order in which the solid powder and other additives are added to the bulk polymerizable monomer is not particularly limited. Further, since the dispersibility of the solid powder may be improved by adding the dispersant before adding the solid powder, it is particularly preferable to add the solid powder after the addition of the dispersant.

  The mixing apparatus used for the preparation of the monomer liquid is not particularly limited, and may be appropriately selected depending on the viscosity of the monomer liquid. 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.

(Resin molding)
The resin molded body of the present invention can be obtained by bulk polymerization of the polymerizable composition substantially without using a solvent. There is no limitation on the method for obtaining a molded product by bulk polymerization of the polymerizable composition of the present invention. For example, (a) a method in which a polymerizable composition is applied on a support and then bulk polymerization is performed, and (b) polymerization. And a method of injecting the polymerizable composition into the space of the mold and then performing bulk polymerization, and (c) impregnating the polymerizable composition into a fibrous reinforcing material and then performing a bulk 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 5 mm or less, more preferably 0.5 mm or less, and most preferably 0.1 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 bulk polymerized. The polymerizable composition is heated for bulk 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.

  Bulk 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 product obtained by the method (c) include a prepreg formed by filling a bulk polymer with a gap between fibrous reinforcing materials. As the fibrous reinforcing material, inorganic and / or organic fibers can be used, such as glass fibers, metal fibers, ceramic fibers, carbon fibers, aramid fibers, polyethylene terephthalate fibers, vinylon fibers, polyester fibers, amide fibers, Examples include known liquid crystal fibers such as polyarylate. 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 cloth, mat, etc. It can be performed by stacking a protective film on top and pressing with a roller or the like from above. A prepreg impregnated with a resin can be obtained by impregnating the fibrous composition with the polymerizable composition and then heating to a predetermined temperature to bulk polymerize the impregnated material. 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 above methods (a), (b) and (c), the heating temperature for bulk polymerization of the polymerizable composition (the mold temperature in the method (b)) is usually 30 to 250 ° C. The temperature is 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.

  The bulk polymerization reaction is started by heating the polymerizable composition to a predetermined temperature. 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 molded product 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 molded object obtained from the polymeric composition which mix | blended the chain transfer agent, the polymerization reaction rate of a polymer is 80% or more normally, Preferably it is 90% or more, More preferably, it is 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.

  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 the crosslinking reaction may progress all at once. Therefore, it is preferable to control the peak temperature of the polymerizable composition in the bulk polymerization to less than 200 ° C. so that only the bulk polymerization reaction proceeds completely and the crosslinking reaction does not proceed. However, from the viewpoint of productivity and the like, the bulk polymerization reaction and the crosslinking reaction may proceed simultaneously. When using a polymerizable composition containing a radical generator as a crosslinking agent, it is preferable that the peak temperature in bulk polymerization is not more than the 1 minute half-life temperature of the radical generator.

(Crosslinked resin molding)
The crosslinked resin molded product of the present invention is obtained by heating and crosslinking the crosslinkable resin molded product of the present invention obtained using a polymerizable composition containing a crosslinking agent. The temperature at which the crosslinkable resin molded body 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.

  The method for heating and crosslinking the crosslinkable resin molded product is not particularly limited. When the crosslinkable resin molded product is in the form of a film, a method of laminating a plurality of sheets as necessary and applying pressure simultaneously with heating by hot pressing is preferable. The pressure at the time of hot pressing is usually 0.5 to 20 MPa, preferably 3 to 10 MPa.

  In addition, as above-mentioned, from a viewpoint of productivity etc., a block polymerization reaction and a crosslinking reaction may be advanced simultaneously to obtain a crosslinked molded body 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.

  The resin molded body or the crosslinked resin molded body may be used as a laminate. The laminate has a constituent layer composed of the resin molded body or the bridge resin bridge molded body, more specifically, has at least two or more layers, and at least one of the layers is the resin molded body or crosslinked It is formed of a resin molded body. 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 molded body or the crosslinked resin molded body 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 molded body or a crosslinked resin molded body are alternately laminated like a multilayer laminated substrate. Here, when a plurality of resin layers made of a resin molded body or a crosslinked resin molded body 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 of obtaining the laminate, and when obtaining a laminate comprising the resin molded product of the present invention in the constituent layers, for example, a resin molded product obtained using the polymerizable composition of the present invention is suitable. A laminate may be obtained by superimposing on a base material, or a laminate may be obtained by superimposing resin molded bodies on each other. Furthermore, a polymerizable composition can be coated on a suitable base material or resin molded body, 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 molding of this invention, for example, (1) The crosslinking | crosslinked resin molding obtained using the polymeric composition containing a crosslinking agent is used as a base | substrate. Superposed on the material and then crosslinked by heating; (2) laminating the polymerizable composition on the substrate material and proceeding bulk polymerization and crosslinking reaction; (3) using a polymerizable composition containing a crosslinking agent. A method in which two or more crosslinkable resin moldings obtained in this manner are superposed and then heated for crosslinking.

  In order to obtain a laminate by the above method (1), for example, a crosslinkable resin molded body 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 0.2 KN / m using F0 copper foil. Greater than, preferably greater than 0.4 kN / m, more preferably greater than 0.6 kN / m.

  In order to obtain a laminate by the method (2), the bulk polymerization temperature of the polymerizable composition is set high, and heating is performed at a temperature at which a crosslinking reaction occurs. However, as in the method (1), the peel strength at the interface increases once the cross-linked resin molded article is passed through.

  A plurality of such laminates may be further laminated. For example, when a laminate in which a metal foil, a crosslinked resin molded body, and a crosslinkable resin molded body are laminated in this order is used, a multilayer circuit board can be easily obtained. As a specific method, first, a conductive circuit is formed by patterning the metal foil layer of the laminate. The method for patterning the metal foil is not particularly limited, and examples thereof include a photolithography method and a laser processing method.

  Next, a via hole through which the conductor circuit is exposed is formed at the bottom while penetrating the layer of the crosslinked resin molded body and the layer of the crosslinkable resin molded body. Then, a conductor is provided to the via hole and a wiring electrically connected from the conductor circuit to the crosslinkable resin molded body layer side is provided to obtain a single-sided circuit board for a multilayer circuit board. A method for forming the via hole is not particularly limited, and examples thereof include a laser drilling method and a paste printing method. After forming the via hole, a permanganate desmear method can be performed in order to remove laser smear generated by the laser drilling method.

  Moreover, the method in particular of providing a conductor to a via hole is not restrict | limited, The method of filling a conductive paste into a via hole by the screen printing method is mentioned. When the protective film used in the screen printing method is removed, a conductive bump in which the conductive paste protrudes from the surface of the crosslinkable resin molded body layer can be formed. The height of the conductive bump is usually 5 to 100 μm. Further, instead of filling the conductive paste, a conductor may be applied to the via hole by plating.

  Two or more single-sided circuit boards for the multilayer circuit board are superposed or superposed on another circuit board and laminated by hot pressing to obtain a multi-layer circuit board having an inner layer wiring and a surface wiring. By the hot press, the crosslinkable resin molded body layer is melted and deformed according to the unevenness of the circuit board. In the crosslinkable resin molded body layer, when it is further heated, the crosslinking reaction proceeds and the adhesion is improved.

  The resin molded body and cross-linked resin molded body of the present invention can be produced by bulk polymerization and have an advantage that they can be produced very easily because a step of evaporating a large amount of solvent as in the conventional casting method is unnecessary.

  The resin molded body and cross-linked resin molded body of the present invention have excellent electrical characteristics such as low dielectric loss tangent, and have a low linear expansion coefficient compared to conventional molded bodies, and the molded body has high strength, such as metal foil. The adhesion to other substrates is also high.

  The resin molded body and cross-linked resin molded body 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 Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified.

Each characteristic in an Example and a comparative example was measured in accordance with the following method.
(1) Viscosity of polymerizable composition Using a high shear rate viscometer (model CAP2000 + L: manufactured by Brookfield), the viscosity of the polymerizable composition was measured at a rotation speed of 10 rpm / 25 ° C. It was evaluated with.
A: Over 0.01 and 1 Pa · s or less B: Over 1 Pa · s and 2 Pa · s or less C: Over 2 Pa · s and 3 Pa · s or less D: Over 3 Pa · s and 5 Pa · s or less 5 Pa · s If it exceeds s, it becomes a sandy state that cannot be measured, so it was marked as x.

(2) Surface shape The thickness of the laminate A having a two-layer structure of copper foil / crosslinkable resin molding was measured with a micrometer at 10 points, and the thickness at each point was determined by subtracting the thickness of the copper foil. . However, in Examples 9 and 10, the thickness of the crosslinkable resin molded article impregnated with glass cloth was measured in the same manner. The maximum variation from the average thickness was determined as a percentage (%), and evaluated according to the following index. It represents that the moldability of a polymeric composition is excellent, so that this value is small.
A: 5% or less B: Over 5% to 10% or less C: Over 10% to 20% or less D: Over 20%

(3) Peel strength The strength when the copper foil was peeled off from the laminate B was measured based on JIS C6481. The following indices were used for evaluation according to the peel strength value.
A: More than 0.6 kN / m B: More than 0.4 kN / m and 0.6 kN / m or less C: More than 0.2 kN / m and 0.4 kN / m or less D: 0.2 kN / m or less

(4) Electrical properties The laminate B was cut into a 20 mm square, and this was immersed in a ferric chloride solution (manufactured by Sanhayato) at 40 ° C to remove the copper foil on the surface, thereby obtaining a test piece. About this test piece, the dielectric constant (εr) and dielectric loss (tan δ) at a frequency of 1 GHz were measured by a capacitance method using an impedance analyzer (manufactured by Agilent Technologies, model number E4991).
The dielectric loss was evaluated according to the following index according to the value.
A: 0.0015 or less B: Over 0.0015 and 0.0020 or less C: Over 0.0020 and 0.0025 or less D: Over 0.0025

Example 1
(Preparation of surface-treated solid powder)
In a Henschel mixer, 500 parts of CaTiO ₃ (average particle size 1.5 μm, dielectric constant 180) was added as a solid powder, and 2 parts of tetraethoxysilane (TEOS) was added as a first surface treatment agent. The first surface treatment step was performed by stirring this at 120 ° C. for 30 minutes. Next, a mixture of 1 part of triethoxyoctadecylsilane and 1 part of trimethoxystyrylsilane was added as a second surface treatment agent and stirred at 120 ° C. for 30 minutes to perform a second surface treatment step.

(Preparation of catalyst solution)
(1,3-Dimesitylimidolin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride 0.1 part as a polymerization catalyst and 0.2 part of triphenylphosphine as a polymerization reaction retarder are placed in a flask, and a nitrogen atmosphere Below, 2.4 parts of toluene was added to dissolve the polymerization catalyst to prepare a catalyst solution.

(Preparation of polymerizable composition)
As a cycloolefin monomer, 20 parts of 2-norbornene (NB) and tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] 80 parts of dodec-4-ene (TCD) was put into a glass container, and 200 parts of the surface-treated CaTiO ₃ was added thereto and mixed uniformly. Here, 1.8 parts of hexenyl methacrylate (Economer ML C5 type, Shin-Nakamura Chemical Co., Ltd.) as a chain transfer agent and di-t-butyl peroxide (product of Kayaku Akzo Co., Ltd., product) as a crosslinking agent for organic peroxide A monomer solution was obtained by adding 1 part of name Kayabutyl D, 1 minute half-life temperature 192 ° C). To the monomer solution, 0.35 part of the catalyst solution was added and mixed to obtain a polymerizable composition. The results of measuring the viscosity of this polymerizable composition are shown in Table 1.

(Crosslinkable resin molding)
The obtained polymerizable composition was cast on an electrolytic copper foil (Type F0, thickness 0.012 mm, manufactured by Furukawa Circuit Foil) as a support so as to have a thickness of 100 μm. A phthalate (PEN) film (manufactured by Teijin DuPont Films, Inc., thickness 75 μm) was stacked. This was heated in an inert oven at 130 ° C. for 1 minute to bulk polymerize the polymerizable composition to obtain a laminate having a three-layer structure of copper foil / crosslinkable resin molded body / PEN film. The PEN film was peeled off from this laminate to obtain a laminate A having a two-layer structure of copper foil / crosslinkable resin molded product. The surface shape of the laminate A was measured. The results are shown in Table 1.

(Crosslinked resin molding)
What peeled off the copper foil from the laminated body A was created, and six this was piled up. Next, the both sides were sandwiched between two laminates A so that the copper foil side was the outer surface. This was hot-pressed at a pressure of 3 MPa and a temperature of 200 ° C. for 30 minutes to obtain a laminate B having a three-layer structure of copper foil / crosslinked resin molded body / copper foil. Using this laminate B, peel strength and electrical characteristics were measured. The results are shown in Table 1.

Example 2
The solid powder was replaced with 500 parts of CaTiO ₃ and 400 parts of dielectric particles mainly composed of BaTiO ₃ (HF90, manufactured by Kyoritsu Materials Co., Ltd., average particle size 1.2 μm, dielectric constant 90) were used. The surface treatment was performed in the same manner as in Example 1 to obtain a surface-treated HF90. Next, the experiment was carried out in the same manner as in Example 1 except that 200 parts of the surface-treated CaTiO ₃ was used and 400 parts of the surface-treated HF90 was used, and each characteristic was measured. The results are shown in Table 1.

Example 3
Example 2 except that instead of a mixture of 1 part of triethoxyoctadecylsilane and 1 part of trimethoxystyrylsilane, a mixture of 1 part of triethoxydecylsilane and 1 part of trimethoxystyrylsilane was used as the second surface treatment agent. Experiments were performed in the same manner as described above to measure each characteristic. The results are shown in Table 1.

Example 4
The experiment was conducted in the same manner as in Example 2 except that 2 parts of triethoxyoctadecylsilane was used instead of a mixture of 1 part of triethoxyoctadecylsilane and 1 part of trimethoxystyrylsilane as the second surface treatment agent. Characteristics were measured. The results are shown in Table 1.

Example 5
Experiments were conducted in the same manner as in Example 4 except that 2 parts of trimethoxyoctylylsilane was used instead of 2 parts of triethoxyoctadecylsilane as the second surface treatment agent, and each characteristic was measured. The results are shown in Table 1.

Example 6
Each characteristic was measured in the same manner as in Example 4 except that 2 parts of trimethoxyoctadecylsilane was used instead of 2 parts of triethoxyoctadecylsilane as the second surface treatment agent. The results are shown in Table 1.

Example 7
(Preparation of surface-treated solid powder)
As the second surface treatment agent, in place of the mixture of 1 part of triethoxyoctadecylsilane and 1 part of trimethoxystyrylsilane, surface treatment was performed in the same manner as in Example 2, except that 2 parts of trimethoxydecylsilane was used. A surface-treated HF90 was obtained.

(Preparation of polymerizable composition)
As styrenes, 80 parts of styrene and 20 parts of p-divinylbenzene were placed in a glass container purged with nitrogen, and 400 parts of the above-treated HF90 was added thereto and mixed uniformly. Here, 1 part of 3-methyl-2-butene-1-thiol as a chain transfer agent and di-t-butyl peroxide (product name: Kayabutyl D, manufactured by Kayaku Akzo Co., Ltd., 1 minute half-life temperature: 192 ° C.) ) 1 part was added to obtain a monomer solution. To this monomer solution, 0.02 part of benzoyl peroxide (manufactured by NOF Corporation, product name Nypar FF, 1 minute half-life temperature 130 ° C.) was added and mixed as a polymerization initiator to obtain a polymerizable composition.

(Crosslinkable resin molding)
Using the obtained polymerizable composition, the polymerizable composition was bulk polymerized in the same manner as in Example 1 except that the heating condition was 60 ° C. for 1 minute, and copper foil / crosslinkable resin molded article / PEN. A laminate having a three-layer structure of the film was obtained. The PEN film was peeled off from this laminate to obtain a laminate A having a two-layer structure of copper foil / crosslinkable resin molded product. The surface shape of the laminate A was measured. The results are shown in Table 1. When the laminate A was cut out by 1 cm square and the PEN film and the copper foil were peeled and dissolved in toluene, all of them were dissolved.

(Crosslinked resin molding)
Three layers of copper foil / crosslinked resin molded body / copper foil were used in the same manner as in Example 1 except that the laminate A obtained above was used, and the conditions of hot pressing were set to a pressure of 3 MPa and a temperature of 200 ° C. for 60 minutes. A laminate B having a structure was obtained. Using this laminate B, peel strength and electrical characteristics were measured. The results are shown in Table 1.

Example 8
Surface treatment was performed in the same manner as in Example 1 except that 400 parts of BaTiO ₃ was used instead of 500 parts of CaTiO ₃ as a solid powder, to obtain surface-treated BaTiO ₃ . Next, the experiment was carried out in the same manner as in Example 1 except that 200 parts of the surface-treated CaTiO ₃ was used and 400 parts of the surface-treated BaTiO ₃ was used, and each characteristic was measured. The results are shown in Table 1.

Example 9
A polymerizable composition was obtained in the same manner as in Example 1 except that the amount of the surface-treated CaTiO ₃ was 250 parts. As a support, a glass yarn cloth (product name: GC2116, manufactured by Asahi Sebel, Inc.) cut into a 40 cm square is placed on a polyethylene naphthalate (PEN) film (manufactured by Teijin DuPont Films Co., Ltd., thickness 75 μm). 70 parts of the polymerizable composition was cast. Further, a polyethylene naphthalate film was covered thereon, and the entire glass cloth was impregnated with the polymerizable composition using a roller. Subsequently, this was heated for 1 minute in the heating furnace heated at 130 degreeC, and the polymerizable composition was bulk-polymerized. Next, the PEN film was peeled off to obtain a crosslinkable resin molded article impregnated with glass cloth having an average thickness of 100 μm. The surface shape of the crosslinkable resin molded product impregnated with the glass cloth was measured. The results are shown in Table 1.

  Next, eight crosslinkable resin molded articles impregnated with the glass cloth are stacked, and both sides thereof are sandwiched by two electrolytic copper foils (Type F0, thickness 0.012 mm, manufactured by Furukawa Circuit Foil Co., Ltd.). While maintaining the flat plate shape, heat pressing was performed to obtain a laminate B having a three-layer structure of copper foil / crosslinked resin molded body / copper foil. The conditions for hot pressing were a pressure of 3 MPa, a temperature of 200 ° C., and a time of 30 minutes. Using this laminate B, peel strength and electrical characteristics were measured. The results are shown in Table 1.

Example 10
Surface treatment was performed by mixing 320 parts of the surface-treated CaTiO ₃ obtained in the same manner as in Example 1 and 80 parts of the surface-treated BaTiO ₃ obtained in the same manner as in Example 8. 400 parts of solid powder was obtained. Each characteristic was measured in the same manner as in Example 1 except that 400 parts of the surface-treated solid powder was used instead of 250 parts of the surface-treated CaTiO ₃ . The results are shown in Table 1.

Comparative Example 1
Each characteristic was measured by conducting an experiment in the same manner as in Example 4 except that the first surface treatment step was not performed. The results are shown in Table 1.

Comparative Example 2
Each characteristic was measured by conducting an experiment in the same manner as in Example 5 except that the first surface treatment step was not performed. The results are shown in Table 1.

Comparative Example 3
Each characteristic was measured by conducting an experiment in the same manner as in Example 6 except that the first surface treatment step was not performed. The results are shown in Table 1.

Comparative Example 4
An experiment was conducted in the same manner as in Example 2 except that the second surface treatment step was not performed. However, the resin molded product could not be produced because the viscosity of the polymerizable composition was too high. The results are shown in Table 1.

Comparative Example 5
As the first surface treatment agent, 2 parts of triethoxyoctadecylsilane was used instead of 2 parts of tetraethoxysilane, and as the second surface treatment agent, 2 parts of tetraethoxysilane were used instead of 2 parts of triethoxyoctadecylsilane. Otherwise, the experiment was performed in the same manner as in Example 4 to measure each characteristic. The results are shown in Table 1.

Comparative Example 6
In a Henschel mixer, 400 parts of HF90 was added as a solid powder, and 2 parts of tetraethoxysilane (TEOS) and 2 parts of triethoxyoctadecylsilane were added. This was stirred at 120 ° C. for 30 minutes to obtain surface-treated HF90. Next, the experiment was carried out in the same manner as in Example 1 except that 200 parts of the surface-treated CaTiO ₃ was used and 400 parts of the surface-treated HF90 was used, and each characteristic was measured. The results are shown in Table 1.

Comparative Example 7
Comparative Example, except that the amount of HF90 was 100 parts and instead of 2 parts of trimethoxyvinylsilane, a mixture of 1 part of trimethoxyvinylsilane and 2 parts of sorbidan trioleate (dispersant, SPO30V, manufactured by Kao Corporation) was used. Experiments were conducted in the same manner as in Example 3 to measure each characteristic. The results are shown in Table 1.

As is clear from the above, the polymerizable composition of the present invention using the solid powder subjected to the specific surface treatment according to the present invention has a low viscosity and is easy to handle. And the surface shape of the crosslinkable resin molding obtained using this polymeric composition was uniform. The cross-linked resin molded product obtained by using the cross-linkable resin molded product was excellent in adhesiveness with the copper foil, and had excellent electrical characteristics with high dielectric constant and low dielectric loss (Examples 1 to 7). , 9, 10). When BaTiO ₃ having a high dielectric constant was used as the solid powder, a crosslinked resin molded article having a high dielectric constant of 20 could be obtained although the dielectric loss was slightly increased (Example 8).

On the other hand, when the first surface treatment step is not performed, the viscosity of the polymerizable composition is increased, the surface shape of the resulting crosslinkable resin molded product becomes uneven, or the crosslinkable resin molded product is used. In some cases, the adhesiveness of the crosslinked resin molded body obtained with the copper foil was lowered (Comparative Examples 1 to 3). Therefore, when a dispersant was added to the second surface treatment agent, the viscosity of the polymerizable composition was lowered, but the resulting crosslinked resin molded article had a large dielectric loss (Comparative Example 7).
On the other hand, when the second surface treatment step was not performed, the resin composition could not be produced because the viscosity of the polymerizable composition was too high (Comparative Example 4). Also, when the order of the first surface treatment step and the second surface treatment step is changed (Comparative Example 5), or when the first surface treatment agent and the second surface treatment agent are mixed and the surface treatment is performed collectively. In (Comparative Example 6), the polymerizable composition has a high viscosity, the surface shape of the crosslinkable resin molding becomes non-uniform, the adhesion of the crosslinkable resin molding to the copper foil is low, and the dielectric of the crosslinkable resin molding The loss was also great.

Claims (8)

A polymerizable composition comprising a cycloolefin monomer, a metathesis polymerization catalyst, and a surface-treated solid powder,
The first surface treatment step in which the surface treatment is performed with a first surface treatment agent selected from tetraalkoxysilane compounds, and the second surface treatment agent selected from silane compounds represented by the following formula (I) A second surface treatment step for surface treatment;
The all SANYO included in this order,
Amount of the solid powder, 50 to 600 parts by mass der Ru polymerizable composition with respect to 100 parts by weight of the cycloolefin monomer.
SiR ¹ (OR ² ) _n X _3-n (I)
(In the formula, R ¹ and R ² each independently represent a hydrocarbon group, X represents a halogen atom, and n represents 3.) The polymerizable composition according to claim 1, wherein the second surface treatment agent includes a silane compound in which R ¹ in the formula (I) is an alkyl group having 5 to 200 carbon atoms. The polymerizable composition according to claim 1 or 2, wherein the second surface treatment agent includes a silane compound in which R ¹ in the formula (I) is a hydrocarbon group having a carbon-carbon double bond. The polymerizable composition according to claim 1, wherein the solid powder is a metal oxide. Furthermore, the polymeric composition in any one of Claims 1-4 containing a crosslinking agent. The resin molding formed by carrying out block polymerization of the polymeric composition in any one of Claims 1-4 . A crosslinkable resin molded article obtained by bulk polymerization of the polymerizable composition according to claim 5 . A crosslinked resin molded article obtained by crosslinking the crosslinkable resin molded article according to claim 7 .