KR100965018B1 - Processes for producing thermoplastic resins, crosslinked resins and crosslinked resin composite materials - Google Patents

Abstract

The present invention provides a monomer liquid comprising (I) 10% by weight or more of a cyclic olefin (α) having two or more metathesis ring-opening reaction sites in the molecule, or a monomer comprising a norbornene-based monomer and a crosslinking agent. Method for producing postcrosslinkable thermoplastic resin which bulk polymerizes polymerizable composition (A) comprising a liquid, (II) metathesis polymerization catalyst and (III) chain transfer agent, and thermoplastic resin obtainable by this production method, and the thermoplastic It is a manufacturing method of the crosslinked resin and crosslinked resin composite material which laminated | stacked resin as needed with the base material, and bridge | crosslinked the thermoplastic resin (part). According to this invention, the thermoplastic resin which is excellent in storage stability can be obtained efficiently, without the problem of the bad smell by a residual monomer by the simple method of bulk-polymerizing a polymeric composition (A). This manufacturing method is simple and is capable of continuous production, which is industrially advantageous. The crosslinked resin and crosslinked resin composite material obtained according to the present invention are excellent in electrical insulation, mechanical strength, heat resistance, dielectric properties, and the like, and are useful as electrical materials and the like.

Description

PROCESSES FOR PRODUCING THERMOPLASTIC RESINS, CROSSLINKED RESINS AND CROSSLINKED RESIN COMPOSITE MATERIALS}             

The present invention relates to a post-crosslinkable thermoplastic resin, a method for producing the same, and a method for producing a crosslinked resin and a crosslinked resin composite material having a step of heating, melting and crosslinking the thermoplastic resin.

Conventionally, the method of hardening resin obtained by metathesis polymerization of cyclic olefin etc. and obtaining a molded object is known. For example, a method of obtaining a crosslinked molded product by crosslinking a thermoplastic resin such as thermoplastic norbornene-based resin obtained by solution polymerization with a crosslinking agent such as an organic peroxide, or cyclic olefins capable of metathesis polymerization in the presence of a carbene complex such as ruthenium in the absence of a solvent A method of obtaining a copper-clad laminated plate by laminating with copper foil, carrying out heating and pressure, and then obtaining a molded material in a semi-cured state by reacting with a has been proposed.

As a method of obtaining the former crosslinked molded article, Japanese Patent Laid-Open Publication No. 94-248164 discloses a crosslinking aid based on 0.001 to 30 parts by weight of an organic peroxide and 1 part by weight of an organic peroxide, based on 100 parts by weight of a thermoplastic hydrogenated ring-opening norbornene-based resin. Crosslinking formed by adding 0.1 to 10 parts by weight of a norbornene-based resin composition uniformly dispersed into a film or prepreg, laminating with another material (base material), followed by heat-press molding, crosslinking and heat fusion. A method of obtaining a molded article is described. In addition, this document describes that the resulting crosslinked molded article is excellent in heat resistance, solvent resistance, chemical resistance, moisture resistance, water resistance, electrical characteristics, and useful as an interlayer insulating film, a film for forming a moisture barrier layer, and the like.

However, in the method described in this document, the thermoplastic resin composition solution is applied onto a substrate, the solvent is removed to obtain a sheet, and then the sheet is peeled off from the substrate, and overlaid with copper foil or the like. For this reason, the number of processes is large and complicated, and it cannot necessarily be advantageous in manufacturing on an industrial production scale. Moreover, there existed a possibility that a copper foil might peel off or a gas might generate | occur | produce by blister etc. by a residual solvent.

Further, as a method of obtaining a copper-clad laminate by metathesis polymerization of the latter cyclic olefin, Japanese Patent Laid-Open Publication No. 2001-71416 reacts cycloolefins capable of metathesis polymerization in the presence of a ruthenium or osmium carbene complex. After obtaining the curable molded material in a semi-cured state, a method for producing a copper-clad laminate is described, wherein a copper foil is disposed on at least one of the molded materials, and heated and pressed. This method comprises a first step of obtaining a molding material which is curable in a state in which polymerization (metathesis) reaction of raw material cycloolefins is not completed (semi-curing state), and a second step of further heating and completely curing the molding material. By dividing by, it is possible to efficiently manufacture a copper-clad laminate using a press molding machine.

However, in the said method, when obtaining the molding material of the semi-hardened state, there existed a problem that an unreacted monomer remained and the working environment became remarkably deteriorated by this bad smell. Moreover, since the polymerization reaction advances and the hardness of a molding material changes also while storing the molding material of a semi-hardened state, the copper-clad laminated board of a desired shape may not be obtained.

Patent Publication No. 99-507962 discloses a method of metathesis-polymerizing cyclic olefins in the presence of a ruthenium carbene complex and a crosslinking agent to produce a polycyclic olefin, followed by postcure (postcrosslinking).

However, according to the findings of the present inventors, even if the obtained norbornene-based resin and copper foil are stacked and hot pressed, the resin before post-curing does not melt and flow, and only the crosslinking reaction proceeds. For this reason, it was difficult to manufacture the copper-clad laminated board which was excellent in interlayer adhesiveness.

The present invention has been made under such circumstances, and firstly, it is a post-crosslinkable thermoplastic resin obtained by bulk polymerization of cyclic olefins in the presence of a metathesis polymerization catalyst, and has no problem of odor due to residual monomer, and fluidity during heating melting. An object of the present invention is to provide a thermoplastic resin excellent in storage stability with excellent storage stability and a method of producing the same. Secondly, it is an object of the present invention to provide a crosslinked resin obtained by crosslinking the thermoplastic resin, which is excellent in electrical insulation, mechanical strength, heat resistance, dielectric properties, and the like and a method of producing the same. Thirdly, the present invention is a crosslinked resin composite material obtained by laminating the thermoplastic resin of the present invention with a base material and crosslinking the thermoplastic resin portion, and is excellent in adhesion between the crosslinked resin and the base material, and is useful as an electric material. The object of this invention is to provide a manufacturing method.

Summary of the Invention

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, earnestly researched about the method of mass-polymerizing a cyclic olefin or norbornene-type monomer in presence of a metathesis polymerization catalyst, and producing a postcrosslinkable thermoplastic resin efficiently.

As a result, (i) the monomer liquid which contains 10 weight% or more of cyclic olefin ((alpha)) which has two or more metathesis ring-opening reaction site | parts in a molecule | numerator with respect to all monomer amounts, or the monomer liquid which contains norbornene-type monomer and a crosslinking agent When the bulk transfer agent coexists in the presence of a metathesis polymerization catalyst and undergoes bulk polymerization, it is possible to efficiently obtain a post-crosslinkable thermoplastic resin having no problem of odor caused by residual monomer, excellent fluidity during heating and excellent storage stability. Heat-melting and crosslinking the thermoplastic resin to obtain a crosslinked resin having excellent electrical insulation, mechanical strength, heat resistance, dielectric properties, and the like, and (iii) laminating the thermoplastic resin with another material. By crosslinking this thermoplastic resin, the crosslinked resin composite material excellent in adhesiveness is obtained efficiently To find that, thus completing the present invention.

Therefore, firstly, according to the present invention, there is provided a process for producing a postcrosslinkable thermoplastic resin, characterized in that the polymerizable composition (A) comprising the components of the following (I) to (III) is subjected to bulk polymerization.

(I) Monomer liquid which contains 10 weight% or more of cyclic olefin ((alpha)) which has two or more metathesis ring-opening reaction site | parts in a molecule with respect to all monomer amounts, or monomer liquid containing norbornene-type monomer and a crosslinking agent.

(II) metathesis polymerization catalyst

(III) Chain Transfer Agent

That is, the manufacturing method of the thermoplastic resin of this invention,

(1) Polymerizable composition (A) containing monomer liquid, metathesis polymerization catalyst, and chain transfer agent which contain 10 weight% or more of cyclic olefin ((alpha)) which has 2 or more metathesis ring-opening reaction site | part in a molecule with respect to all monomer amounts. Bulk polymerization, or

(2) Mass polymerization of the polymerizable composition (A) containing a norbornene-based monomer, a metathesis polymerization catalyst, a chain transfer agent and a crosslinking agent.

It is preferable that the maximum temperature at the time of the superposition | polymerization superposition | polymerization of the manufacturing method of the thermoplastic resin of this invention is less than 230 degreeC, and it is preferable that polymerization reaction rate is 80% or more.

In the production method of the thermoplastic resin of the present invention, as the chain transfer agent, formula CH ₂ = CH-Q (wherein, Q is a methacryloyl group, acryloyl group, vinyl silyl group, at least one group selected from an epoxy group and an amino group It is preferable to use the compound represented by the following).

In the manufacturing method of the thermoplastic resin of this invention, in the case of said (1), it is preferable to use dicyclopentadiene as said cyclic olefin ((alpha)).

In the method for producing a thermoplastic resin of the present invention, in the case of (2), epoxy is used as the crosslinking agent by using a norbornene monomer mixture containing a norbornene monomer having a carboxyl group or an acid anhydride group as the norbornene monomer. Preference is given to using compounds. Moreover, as another example of said (2), it is preferable to use a radical generator as said crosslinking agent, and to bulk-polymerize a polymerizable composition (A) at reaction temperature below 1 minute half life temperature of the said radical generator, As a polymerizable composition (A), it is more preferable to use what contains a radical crosslinking retarder further.

Secondly, according to the present invention, a postcrosslinkable thermoplastic resin obtained by the production method of the present invention is provided.

It is preferable that the thermoplastic resin of this invention is obtained by shape | molding in said film form by mass-polymerizing the said polymeric composition (A) on a support body, and it is more preferable that the said support body is a metal foil or a resin film.

It is preferable that the thermoplastic resin of this invention is obtained by shape | molding the said polymeric composition (A) in a predetermined shape by mass-polymerizing in a mold.

It is preferable that the thermoplastic resin of this invention is obtained by bulk-polymerizing after impregnating the said polymeric composition (A) in a fiber material.

Third, according to the present invention, there is provided a method for producing a crosslinked resin having a step of crosslinking the thermoplastic resin of the present invention.

Fourthly, according to the present invention, there is provided a method for producing a crosslinked resin composite material having a step of laminating the thermoplastic resin of the present invention with a substrate and crosslinking the thermoplastic resin portion.

In the manufacturing method of the crosslinked resin composite material of this invention, it is more preferable to use metal foil as said base material, As said metal foil, the silane coupling agent represented by following formula (1), or the thiol coupling represented by following formula (2) It is more preferable to use the zero-treated thing.

RSiXYZ

T (SH) n

(Wherein R represents a group having a double bond, a mercapto group or an amino group at the terminal, X and Y each independently represent a hydrolyzable group, a hydroxyl group or an alkyl group, and Z represents a hydrolyzable group or a hydroxyl group. T represents an aromatic ring) , An aliphatic ring, a heterocycle, or an aliphatic chain, and n represents an integer of 2 or more.

Moreover, in the manufacturing method of the crosslinked resin composite material of this invention, it is preferable to use a printed wiring board as said base material,

Hereinafter, the present invention is specifically divided into 1) a method for producing a post-crosslinkable thermoplastic resin, a thermoplastic resin obtained by the method, 2) a method for producing a crosslinked resin, and 3) a method for producing a crosslinked resin composite material. Explain.

1) Manufacturing method and thermoplastic resin of post-crosslinkable thermoplastic resin

The method for producing a post-crosslinkable thermoplastic resin according to the present invention comprises (I) a monomer liquid containing 10% by weight or more of cyclic olefins (α) having two or more metathesis ring-opening reaction sites in the molecule, or novo It is characterized by mass-polymerizing the polymerizable composition (A) containing a monomer liquid containing a Nene monomer and a crosslinking agent, (II) metathesis polymerization catalyst, and (III) chain transfer agent.

(I) monomer liquid

In the present invention, a monomer liquid comprising 10% by weight or more of a cyclic olefin (α) having two or more metathesis ring-opening reaction sites in a molecule as a monomer liquid (hereinafter referred to as "monomer liquid 1"). ) Or a monomer liquid (hereinafter referred to as "monomer liquid 2") containing a norbornene-based monomer and a crosslinking agent.

(Monomer liquid 1)

Monomer liquid 1 consists of 10 weight% or more of cyclic olefin ((alpha)) which has two or more metathesis ring-opening reaction site | parts in a molecule with respect to all monomer amounts.

Cyclic olefin ((alpha)) is an olefin compound which has a ring structure which has two or more metathesis ring-opening reaction site | parts in a molecule | numerator. Here, a "metathesis ring-opening reaction site" means a carbon-carbon double bond, and the site | part which the said double bond cleaves and ring-opens by a metathesis reaction.

As an olefin compound which has a ring structure which has a metathesis ring opening reaction site, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, a cyclododecene ring, a bicyclo [2.2.1] heptene ring etc. Can be mentioned.

As cyclic olefin ((alpha)), the monocyclic compound which consists of 1 type of ring structure which has a metathesis ring-opening reaction site, the condensed cyclic compound which consists of 1 type, or 2 or more types of the said ring structure, 1 or 2 types of the said ring structure, for example The polycyclic compound etc. which the above combine | bonded are mentioned.

Although carbon number in particular of cyclic olefin ((alpha)) is not restrict | limited, Usually, it is 7-30, Preferably it is 7-20. The number of metathesis reaction sites of the cyclic olefin (α) is not particularly limited as long as it is 2 or more, but is usually 2 to 5, preferably 2 to 4.

As cyclic olefin ((alpha)) used for this invention, it is preferable that the ring structure in which the said 2 or more metathesis ring-opening reaction site | part is contained differs. When using such a cyclic olefin ((alpha)), since the reactivity of each ring-opening reaction site | part is different, only one ring-opening reaction site | part participates in a ring-opening polymerization reaction, and the other remains in the thermoplastic resin obtained as it is unreacted. It is involved in metathesis crosslinking reaction during post-crosslinking. Therefore, a post-crosslinkable thermoplastic resin having few residual monomers (high polymerization reaction rate) and excellent storage stability can be efficiently obtained.

As a specific example of cyclic olefin ((alpha)), what is shown to following (a)-(c) etc. are mentioned.

(a) Condensed ring compound which has a condensed ring of the same or different cycloolefin ring.

^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, dicyclopentadiene, tetracyclo [6.2.1.1 ^{3,6 2,7} ] dodeca-4,9-diene, tricyclo [12.2.1.0 ^2,13 ] Heptadeca-5,9,15-triene, tetracyclo [9.2.1.0 ^{2,10 4,8} ] tetradeca-5,12-diene, pentacyclo [9.2.1.1 ^3,9 .0 ^{2 , 10} .0 ^4,8 ] pentadeca-5,12-diene, norbornadiene, bicyclo [6.2.0] deca-4,9-diene, bicyclo [6.3.0] undeca-4, 9-diene, tricyclo [8.2.1.0 ^2,9 ] trideca-5,11-diene.

(b) Polycyclic compounds in which the same or different cycloolefin rings are bonded in a single bond.

9-cyclohexenyl tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodec-4-ene, 9-cyclopentenyl tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodec- 4-en, 5-cyclohexenyl-2-norbornene, 5-cyclopentenyl-2-norbornene, 5,5'-bi- (2-norbornene), 5-cyclooctenyl-2-norbornene , 5-norbornene-2-carboxylic acid-3-cyclopenten-1-yl, 5-norbornene-2-carboxylic acid-5-norbornene-2-yl.

(c) The compound shown to said (a) and (b) WHEREIN: Alkyl groups, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group; Alkylidene groups such as methylidene group, ethylidene group, propylidene group and butylidene group; Aromatic hydrocarbon groups such as phenyl group and naphthyl group; Carboxyl groups; Alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group and butoxycarbonyl group; Acid anhydride groups; And compounds having at least one substituent, such as a cyano group.

These compounds can be used individually by 1 type or in combination of 2 or more types as cyclic olefin ((alpha)).

Among these, it is especially preferable to use dicyclopentadiene as cyclic olefin ((alpha)) from the point which can obtain a thermoplastic resin which is easy to obtain, has a high metathesis polymerization reaction rate, and is excellent in storage stability.

Content of cyclic olefin ((alpha)) is 10 weight% or more with respect to all monomer amounts, Preferably it is 20 weight% or more, More preferably, it is 30 weight% or more. When content of cyclic olefin ((alpha)) is less than 10 weight%, post-crosslinking becomes difficult.

To the monomer liquid 1, in addition to the cyclic olefin (α), a cyclic olefin (β) having one metathesis ring opening reaction site in the molecule can be added.

As a preferable specific example of cyclic olefin ((beta)), Norbornene-type monomer; Monocyclic olefins, such as cyclobutene, a cyclooctene, and 1, 5- cyclooctadiene, etc. are mentioned. These may be substituted by hydrocarbon groups, such as an alkyl group, an alkenyl group, an alkylidene group, and an aryl group, or a polar group.

Specific examples of the norbornene-based monomers include tetracyclo [6.2.1.1 ^{3,6 2,7} ] dodec-4-ene and 9-methyltetracyclo [6.2.1.1 ^{3,6 2,7} ] dodec- 4-ene, 9-ethyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodec-4-ene, 9-cyclohexyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodec -4-ene, 9-cyclopentyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodec-4-ene, 9-methylenetetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dode X-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-propenyltetracyclo [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 ] dodec-9-ene-4-carboxylic acid methyl, 4-methyltetracyclo [6.2.1.1 ^3,6 .0 ^{2 , 7} ] dodec-9-ene-4-carboxylic acid methyl, tetracyclo [6.2.1.1 ^{3,6 2,7} ] dodec-9-ene-4-methanol, tetrasa Eclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodec-9-en-4-ol, tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodec-9-en-4- Carboxylic Acid, Tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic acid, Tetracyclo [6.2.1.1 ^{3,6 2,7} ] dodec-9 -Ene-4,5-dicarboxylic anhydride, tetracyclo [6.2.1.1 ^{3,6 2,7} ] dodec-9-ene-4-carbonitrile, tetracyclo [6.2.1.1 ^3,6 .0 ^{2 , 7} ] dodec-9-ene-4-carbaldehyde, tetracyclo [6.2.1.1 ^{3,6 2,7} ] dodec-9-ene-4-carboxamide, tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic acid imide, 9-chlorotetracyclo [6.2.1.1 ^{3,6 2,7} ] dodec-4-ene, 4-trimethoxysilyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodec-9-ene, 9-acetyltetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodec-4 Tetracyclododecenes such as -ene;

Tricyclo [5.2.1.0 ^2,6 ] deck-8-ene, 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5- Hexyl-2-norbornene, 5-decyl-2-norbornene, 5-cyclohexyl-2-norbornene, 5-cyclopentyl-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl- 2-norbornene, 5-propenyl-2-norbornene, 5-phenyl-2-norbornene, tetracyclo [9.2.1.0 ^{2,10 3,8} ] tetradeca-3,5,7,12- Tetraene (also known as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), tetracyclo [10.2.1.0 ^2,11 .0 ^4,9 ] pentadeca-4,6 , 8,13-tetraene (also known as 1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene), 5-norbornene-2-carboxylic acid methyl, 5-norbornene-2 Ethyl carboxylic acid, 2-methyl-5-norbornene-2-methyl carboxylic acid, 2-methyl-5-norbornene-2-carboxylic acid ethyl, 5-norbornene-2-yl acetate, 2-methyl-5-novo acetate Nen-2-yl, 5-norbornene-2-yl acrylate, 5-norbornene-2-yl methacrylate, 5-norbornene-2-carboxylic acid, 5-norbornene-2,3- Dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid anhydride, 5-norbornene-2-methanol, 5-norbornene-2,3-dimethanol, 5-norbornene-2,2-dimethanol, 5 Norbornene-2-ol, 5-norbornene-2-nitrile, 5-norbornene-2-carbaldehyde, 5-norbornene-2-carboxamide, 2-acetyl-5-norbornene, 3 Norbornenes such as -methoxycarbonyl-5-norbornene-2-carboxylic acid;

7-oxa-2-norbornene, 5-methyl-7-oxa-2-norbornene, 5-ethyl-7-oxa-2-norbornene, 5-butyl-7-oxa-2-norbornene, 5- Hexyl-7-oxa-2-norbornene, 5-cyclohexyl-7-oxa-2-norbornene, 5-ethylidene-7-oxa-2-norbornene, 5-phenyl-7-oxa-2-novo Oxanobornenes such as methylene, 7-oxa-5-norbornene-2-carboxylic acid, acetic acid 7-oxa-5-norbornene-2-yl, and methacrylic acid 7-oxa-5-norbornene-2-yl ; And

Hexahydro cycloalkyl, and the like ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] heptadecyl-4-deca-yen or more 5 hwanche cyclic olefin, such as acids.

These compounds can be used individually by 1 type or in combination of 2 or more types as cyclic olefin ((beta)).

(Monomer liquid 2)

Monomer liquid 2 contains a norbornene-type monomer and a crosslinking agent.

As the norbornene-based monomer, any of the norbornene-based monomers exemplified in the cyclic olefin (β) can be used. Moreover, as long as what was illustrated to cyclic olefin ((alpha)) has a bicyclo [2.2.1] heptene ring, all can be used.

Although norbornene-type monomer can be used individually by 1 type, the norbornene-type monomer mixture which mixed 2 or more types can also be used. By using 2 or more types of monomers together and changing the blend ratio, the glass transition temperature and melting temperature of the obtained thermoplastic resin can be freely controlled.

In the present invention, norbornene-based monomers in which monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclooctene, cyclododecene and 1,5-cyclooctadiene and their derivatives having substituents are added to the norbornene-based monomers. The mixture can also be used as the monomer liquid 2. The amount of the monocyclic cycloolefins and their derivatives added is preferably 40% by weight or less, more preferably 20% by weight or less based on the total amount of the norbornene-based monomer mixture. When the addition amount exceeds 40% by weight, the polymer obtained by the bulk polymerization may be an elastomer instead of a resin, which is not preferable.

Among these, when using an epoxy compound as a crosslinking agent mentioned later, since a crosslinked resin is obtained efficiently, it is preferable to use the norbornene-type monomer mixture containing the norbornene-type monomer which has a carboxyl group or an acid anhydride group as a norbornene-type monomer. Content of the norbornene-type monomer which has a carboxyl group or an acid anhydride group in the said norbornene-type monomer mixture becomes like this. Preferably it is 1 mol% or more, More preferably, it is 5 mol% or more.

The crosslinking agent used for this invention crosslinks-reacts with the functional group of the thermoplastic resin by which the norbornene-type monomer is bulk-polymerized, and produces a crosslinked resin. As a functional group, a carbon-carbon double bond, a carboxylic acid group, an acid anhydride group, a hydroxyl group, an amino group, an active halogen atom, an epoxy group is mentioned, for example.

As a crosslinking agent, a radical generator, an epoxy compound, an isocyanate group containing compound, a carboxyl group containing compound, an acid anhydride group containing compound, an amino group containing compound, a Lewis acid, etc. are mentioned. These crosslinking agents can be used individually by 1 type or in combination of 2 or more type. Among these, use of a radical generating agent, an epoxy compound, an isocyanate group containing compound, a carboxyl group containing compound, and an acid anhydride group containing compound is preferable, and a use of a radical generating agent, an epoxy compound, and an isocyanate group containing compound is more preferable, The use of, radical generators or epoxy compounds is particularly preferred.

Examples of the radical generator include organic peroxides and diazo compounds. Although it does not specifically limit as an organic peroxide, For example, hydroperoxides, such as t-butyl hydroperoxide, p-mentane hydroperoxide, cumene hydroperoxide; Dicumyl peroxide, t-butyl cumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, di-t-butylperoxide, 2,5-dimethyl-2,5 Dialkyl peroxides such as -di (t-butylperoxy) -3-hexyne and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane; Diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexine-3,1,3-di ( peroxy ketals such as t-butyl peroxy isopropyl) benzene; peroxy esters such as t-butylperoxy acetate and t-butylperoxy benzoate; peroxy carbonates such as t-butyl peroxy isopropyl carbonate and di (isopropyl peroxy) dicarbonate; Ketone peroxides; Alkyl silyl peroxides, such as t-butyl trimethylsilyl peroxide, are mentioned. Especially, dialkyl peroxide is preferable at the point which has few obstacles to metathesis polymerization reaction.

Examples of the diazo compound include 4,4'-bisazidobenzal (4-methyl) cyclohexanone, 4,4'-diazidochalcone, and 2,6-bis (4'-azidobenzal) cyclohexane. On, 2,6-bis (4'-azidobenzal) -4-methylcyclohexanone, 4,4'-diazidodiphenylsulfone, 4,4'-diazidodiphenylmethane, 2,2'- Diamond road steben etc. are mentioned.

As an epoxy compound, a phenol novolak-type epoxy compound, a cresol novolak-type epoxy compound, a cresol-type epoxy compound, a bisphenol A-type epoxy compound, a bisphenol F-type epoxy compound, a brominated bisphenol A-type epoxy compound, a brominated bisphenol F-type epoxy compound, hydrogen Glycidyl ether epoxy compounds such as added bisphenol A epoxy compounds; Polyvalent epoxy compounds such as alicyclic epoxy compounds, glycidyl ester epoxy compounds, glycidyl amine epoxy compounds, and isocyanurate epoxy compounds; The compound etc. which have two or more epoxy groups in molecules, such as these, are mentioned.

As an isocyanate group containing compound, the compound etc. which have two or more isocyanate groups in molecules, such as p-phenylene diisocyanate, 2, 6-toluene diisocyanate, and hexamethylene diisocyanate, are mentioned.

Examples of the carboxyl group-containing compound include compounds having two or more carboxyl groups in molecules such as fumaric acid, phthalic acid, maleic acid, trimellitic acid, himic acid, terephthalic acid, isophthalic acid, adipic acid, and sebacic acid. .

Examples of the acid anhydride group-containing compound include maleic anhydride, phthalic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, nad anhydride, 1,2-cyclohexane dicarboxylic anhydride, maleic anhydride modified polypropylene, and the like. have.

Examples of the Lewis acid include silicon tetrachloride, hydrochloric acid, sulfuric acid, ferric chloride, aluminum chloride, tin tin chloride, titanium tetrachloride, and the like.                 

As an amino-group containing compound, Aliphatic diamines, such as trimethyl hexamethylenediamine, ethylenediamine, 1, 4- diamino butane; Aliphatic polyamines such as triethylene tetramine, pentaethylene hexamine and aminoethylethanol amine; And compounds having two or more amino groups in the molecule, such as aromatic amines such as phenylenediamine, 4,4'-methylenedianiline, toluenediamine, and diaminoditolyl sulfone.

In this invention, the crosslinking agent to be used can be selected and used according to the site (crosslinking site) of the thermoplastic resin to be crosslinked. For example, a radical generator may be used when crosslinking at a carbon-carbon double bond moiety. Moreover, when crosslinking the thermoplastic resin which has a carboxyl group or an acid anhydride group, an epoxy compound can be used, When crosslinking the thermoplastic resin which has a hydroxyl group, the compound containing an isocyanate group can be used, The thermoplastic resin containing an epoxy group When crosslinking, a carboxyl group-containing compound or an acid anhydride group-containing compound can be used. In addition, when it wants to crosslink cationicly, Lewis acid can also be used as a crosslinking agent.

The usage-amount of a crosslinking agent is not specifically limited, It can set suitably according to the kind of crosslinking agent to be used. For example, when using a radical generator as a crosslinking agent, the usage-amount of a crosslinking agent is 0.1-10 weight part normally with respect to 100 weight part of norbornene-type monomers, Preferably it is 0.5-5 weight part. Moreover, when using an epoxy compound as a crosslinking agent, it is 1-100 weight part normally with respect to 100 weight part of norbornene-type monomers, Preferably it is 5-50 weight part. If the addition amount of the crosslinking agent is too small, crosslinking will be insufficient, and there is a fear that a crosslinking resin having a high crosslinking density cannot be obtained. When the amount of use is excessively large, the crosslinking effect is saturated, and there is a fear that a thermoplastic resin and a crosslinked resin having desired physical properties cannot be obtained.

In addition, in this invention, in order to improve crosslinking efficiency, a crosslinking adjuvant can be used together with a crosslinking agent. As a crosslinking adjuvant, a well-known crosslinking adjuvant can be used without a restriction | limiting in particular. For example, dioxime compounds, such as p-quinone dioxime; Methacrylate compounds such as lauryl methacrylate and trimethylpropane methacrylate; Fumaric acid compounds such as diallyl fumarate: phthalic acid compounds such as diallyl phthalate, cyanuric acid compounds such as triallyl cyanurate; Imide compounds, such as maleimide, etc. are mentioned. Although the usage-amount of a crosslinking adjuvant is not restrict | limited, Usually, 0-100 weight part with respect to 100 weight part of norbornene-type monomers, Preferably it is 0-50 weight part.

In this invention, when using a radical generator as a crosslinking agent, it is preferable to contain a radical crosslinking delay agent in a polymeric composition (A). A radical crosslinking delay agent is generally a compound which has a radical trapping function, and has the effect of slowing down the radical crosslinking reaction by a radical generator. By adding a radical crosslinking delay agent to a polymerizable composition (A), the fluidity | liquidity and the storage stability of a thermoplastic resin when laminating | stacking a thermoplastic resin can be improved.

As a radical crosslinking delay agent to be used, 4-methoxy phenol, 4-ethoxy phenol, 3-t- butyl- 4-hydroxy anisole, 2-t- butyl- 4-hydroxy anisole, 3, 5- di alkoxy phenols such as -t-butyl-4-hydroxyanisole; Hydroquinone, 2-methylhydroquinone, 2,5-dimethyl hydroquinone, 2-t-butyl hydroquinone, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone Hydroquinones such as 2,5-bis (1,1-dimethylbutyl) hydroquinone and 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone; Catechols such as catechol, 4-t-butyl catechol, 3,5-di-t-butyl catechol; Benzoquinones such as benzoquinone, naphthoquinone and methyl benzoquinone; Etc. can be mentioned. Among these, alkoxy phenols, catechols and benzoquinones are preferable, and alkoxy phenols are particularly preferable.

The content of the radical crosslinking retardant is usually 0.001 to 1 mol, preferably 0.01 to 1 mol with respect to 1 mol of the radical generator.

(II) metathesis polymerization catalyst

The metathesis polymerization catalyst used in the present invention is not particularly limited as long as the metathesis polymerization ring-opening polymerization of the cyclic olefin (α) and the norbornene-based monomer is carried out. As a metathesis polymerization catalyst to be used, a complex in which a plurality of ions, atoms, polyatomic ions and / or compounds are bonded using a transition metal atom as a center atom is mentioned. As the transition metal atom, atoms of groups 5, 6 and 8 (long-period periodic table, hereinafter identical) are used. The atoms of each group are not particularly limited, but examples of the Group 5 atoms include tantalum, and Group 6 atoms include molybdenum or tungsten, and Group 8 atoms include ruthenium or osmium. Can be.

Among these, it is preferable to use the group 8 ruthenium or osmium complex as a metathesis polymerization catalyst, and a ruthenium carbene complex is particularly preferable. Since the ruthenium carbene complex has excellent catalyst activity during bulk polymerization, the ruthenium carbene complex has excellent productivity of the postcrosslinkable thermoplastic resin, less odor of the thermoplastic resin obtained (condensed with unreacted monomer), and excellent productivity. In addition, since it is relatively stable with respect to oxygen and moisture in the air and hardly loses activity, production is possible even in the atmosphere.

The ruthenium carbene complex is represented by the following general formula (3) or (4).

Wherein R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a C ₁ to C ₂₀ hydrocarbon group which may include a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom . X ¹ and X ² each independently represent any anionic ligand. L ¹ and L ² each independently represent a heteroatom containing carbene compound or a neutral electron donating compound. In addition, R ¹ , R ² , X ¹ , X ² , L ¹ and L ² may combine with each other in any combination to form a multidentate chelating ligand.

A hetero atom means the atom of group 15 or 16 of a periodic table, and a N, O, P, S, As, Se atom etc. are mentioned specifically ,. Among these, since a stable carbene compound can be obtained, N, O, P, S atoms, etc. are preferable, and N atom is especially preferable.

The heteroatom-containing carbene compound preferably has heteroatoms adjacent to and bonded to both sides of the carbene carbon, and more preferably a heterocycle including a carbene carbon atom and heteroatoms on both sides thereof. Moreover, it is preferable to have a bulky substituent in the hetero atom adjacent to carbene carbon.

As an example of a hetero atom containing carbene compound, the compound represented by following formula (5) or formula (6) is mentioned.

(Wherein, R ³ to R ⁶ each independently represent a hydrogen atom, a halogen atom, or a C ₁ to C ₂₀ hydrocarbon group which may include a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom In addition, R ³ to R ⁶ may combine with each other in any combination to form a ring.

Specific examples of the compounds represented by the formulas (5) and (6) include 1,3-dimesitylimidazolidine-2-ylidene and 1,3-di (1-adamantyl) imidazolidine-2-yl Den, 1-cyclohexyl-3-methytylimidazolidine-2-ylidene, 1,3-dimethyloctahydrobenzimidazole-2-ylidene, 1,3-diisopropyl-4-imide Dazoline-2-ylidene, 1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene, 1,3-dimethyl-2,3-dihydrobenzimidazole-2 -Ylidene etc. are mentioned.

In addition, in addition to the compounds represented by Formula 5 and Formula 6, 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5-ylidene, 1,3-dicyclohexylhexahydropyrimidin-2-ylidene, N, N, N ', N'-tetraisopropylformalidinylidene, 1,3,4-triphenyl-4,5-di Heteroatom-containing carbenes such as hydro-1H-1,2,4-triazole-5-ylidene and 3- (2,6-diisopropylphenyl) -2,3-dihydrothiazole-2-ylidene Compounds can also be used.

In the above formulas (3) and (4), the anionic ligands X ¹ and X ² are ligands having a negative charge away from the center metal, and for example, halogen atoms such as F, Cl, Br, I, diketonate A group, a substituted cyclopentadienyl group, an alkoxy group, an aryl oxy group, a carboxyl group, etc. are mentioned. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

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

As a complex compound represented by the said Formula (3), for example, benzylidene (1, 3- dimesitylimidazolidine-2- lylidene) (tricyclohexyl phosphine) ruthenium dichloride, (1, 3- dimesh Thilimidazolidine-2-ylidene) (3-methyl-2-butene-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimethyloctahydrobenzimimi Dazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine Ruthenium dichloride, benzylidene (1,3-dimethyl-2,3-dihydrobenzimidazole-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) ) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5-ylidene) ruthenium dichloride, (1,3-dia Isopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimethylimidazolidine-2-ylidene) pyridineruthenium Dichloride, (1,3-dimethylimimidazole lidin2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimethyl-4- Ruthenium complex compounds in which a heteroatom-containing carbene compound such as imidazoline-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride and a neutral electron donating compound are bonded;

Ruthenium bonded by two neutral electron donating compounds such as benzylidene bis (tricyclohexylphosphine) ruthenium dichloride and (3-methyl-2-butene-1-ylidene) bis (tricyclopentylphosphine) ruthenium dichloride compound;

Benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride, benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium di Ruthenium complex compound etc. which two hetero atom containing carbene compounds, such as chloride, couple | bonded are mentioned.

In addition, in said Formula (3), the compound represented by following formula (7) is mentioned as a complex compound which R <^1> and L <^1> couple | bond.

Examples of the complex compound represented by the above formula (4) include (1,3-dimesitylimidazolidine-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butyl Vinylidene) (1,3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline- 2-ylidene) phenyl vinylidene ruthenium dichloride, etc. are mentioned.

These ruthenium complex catalysts are described, for example, in Org. Lett. , 1999, Vol. 1, p. 953 and Tetrahedron. Lett., 1999, Vol. 40, p. 2247].

The amount of metathesis polymerization catalyst to be used is usually 1: 2,000 to 1: 2,000,000, preferably 1: 5,000 to 1: 1,000,000, more preferably 1: 10,000 to 1 in a molar ratio of (metal atom in the catalyst: cyclic olefin). The range is 500,000.

The metathesis polymerization catalyst can be used after being dissolved or suspended in a small amount of inert solvent, if necessary. As such a solvent, For example, Chain aliphatic hydrocarbons, such as n-pentane, n-hexane, n-heptane, a liquid paraffin, mineral spirit; Cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene cyclohexane, cyclooctane Alicyclic hydrocarbons such as these; Aromatic hydrocarbons such as benzene, toluene and xylene; Nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; Oxygen hydrocarbons, such as diethyl ether and tetrahydrofuran, etc. are mentioned. Among these, use of industrially general-purpose aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons is preferable. In addition, as long as the activity as a metathesis polymerization catalyst is not lowered, a liquid antioxidant, a plasticizer or an elastomer can be used as the solvent.

The metathesis polymerization catalyst may be used in combination with an activator (cocatalyst) for the purpose of controlling the polymerization activity or improving the polymerization reaction rate. Examples of the active agent include alkylates, halides, alkoxides and aryloxylides of aluminum, scandium, tin, titanium and zirconium.                 

Specific examples of the activator include trialkoxy aluminum, tripenoxy aluminum, dialkoxyalkyl aluminum, alkoxydialkyl aluminum, trialkyl aluminum, dialkoxy aluminum chloride, alkoxyalkyl aluminum chloride, dialkyl aluminum chloride, trialkoxy scandium, tetraalkoxy titanium , Tetraalkoxy tin, tetraalkoxy zirconium and the like.

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

In the case of using complexes of transition metal atoms of Groups 5 and 6 as metathesis polymerization catalysts, it is preferable to dissolve both metathesis polymerization catalysts and active agents in monomers, but they do not inherently impair the properties of the product. If it is a range, it can use it, suspending or dissolving in a small amount of solvents.

(III) Chain Transfer Agent

In the manufacturing method of this invention, a chain transfer agent is used as a structural component of a polymeric composition (A). A thermoplastic resin can be obtained by polymerizing in the presence of a chain transfer agent.

As the chain transfer agent, for example, chain olefins which may have a substituent can be used. As an example, Aliphatic olefins, such as 1-hexene and 2-hexene; Olefins having aromatic groups such as styrene, divinylbenzene and stilbene; Olefins having an alicyclic hydrocarbon group such as vinylcyclohexane; 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; Formula CH ₂ = CH-Q compounds represented by there may be mentioned (wherein, Q is a methacryloyl group, acryloyl group which can be selected from a group, vinyl silyl group, epoxy group and amino group having at least one shown). Among these compounds, the use of the compound represented by the formula CH ₂ = CH-Q is preferred because Q is introduced into the polymer-terminus and the crosslinking density can be increased by contributing to crosslinking of the terminal Q during postcrosslinking.

Specific examples of the compound represented by the formula CH ₂ = CH-Q include vinyl methacrylate, allyl methacrylate, 3-buten-1-yl methacrylate, 3-buten-2-yl methacrylate, and methacrylic acid Compounds in which Q has a methacryloyl group, such as styryl; Q such as allyl acrylate, 3-buten-1-yl acrylate, 3-buten-2-yl acrylate, 1-methyl-3-buten-2-yl acrylate, styryl acrylate and ethylene glycol diacrylate A compound having acryloyl group; Compounds in which Q has a vinylsilyl group, such as allyltrivinyl silane, allylmethyldivinyl silane, and allyldimethylvinyl silane; Compounds in which Q has an epoxy group, such as glycidyl acrylate and allyl glycidyl ether; And a compound in which Q has an amino group, such as allylamine, 2- (diethylamino) ethanol vinyl ether, 2- (diethylamino) ethyl acrylate, and 4-vinylaniline.

The amount of the chain transfer agent added is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight based on the whole monomer liquid. When the amount of the chain transfer agent added is within the above range, the polymerization reaction rate is high, and further, a post-crosslinkable thermoplastic resin can be efficiently obtained. When the addition amount of a chain transfer agent is too small, it may not become a thermoplastic resin. On the contrary, when there is too much addition amount, post-crosslinking may become difficult.

A polymerizable composition (A) comprising a monomer liquid 1 or a monomer liquid 2 (hereinafter also referred to as "monomer liquid" collectively), a metathesis polymerization catalyst and a chain transfer agent is prepared to prepare the composition (A). A thermoplastic resin can be manufactured by block polymerization.

Although there is no restriction | limiting in particular in the method of preparing a polymeric composition (A), For example, the monomer liquid and the solution (catalyst liquid) which melt | dissolved or disperse | distributed a metathesis polymerization catalyst separately were prepared separately, and mixed just before making it react. The method of preparation is mentioned. In this case, the chain transfer agent may be added to the monomer liquid, may be added to the catalyst liquid, or may be added after mixing the monomer liquid and the catalyst liquid. In addition, a crosslinking agent may be added to a catalyst liquid, without including it in a monomer liquid, and may be added after mixing a norbornene-type monomer and a catalyst liquid.

The polymerizable composition (A) may contain various additives such as reinforcing agents, modifiers, antioxidants, flame retardants, fillers, colorants, light stabilizers and the like. These additives can be dissolved or dispersed in the monomer liquid or the catalyst liquid in advance.

As a reinforcing material, glass fiber, a glass cloth, a paper base material, a glass nonwoven fabric, etc. are mentioned, for example. As the modifier, for example, natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene polymer (SIS) And elastomers such as ethylene-propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), and hydrides thereof. Examples of the antioxidants include various plastic and rubber antioxidants such as hindered phenols, phosphorus and amines. Although these antioxidants can be used independently, it is preferable to use in combination of 2 or more type.

Examples of the flame retardant include phosphorus flame retardants, nitrogen flame retardants, halogen flame retardants, and metal hydroxide flame retardants such as aluminum hydroxide. Although a flame retardant can be used individually, it is preferable to use in combination of 2 or more type.

Examples of the filler include inorganic fillers such as glass powder, carbon black, silica, talc, calcium carbonate, mica, alumina, titanium dioxide, zirconia, mullite, cordierite, magnesia, clay and barium sulfate. And organic fillers such as wood flour and polyethylene powder can be used. In addition, the use of graphite powder, charcoal powder, bamboo charcoal powder, metal powder or the like can improve the conductivity or electromagnetic shielding properties. The use of powders such as barium titanate, strontium titanate, lead titanate, magnesium titanate, bismuth titanate and lead zirconate can increase the dielectric constant. Ferromagnetic metal powders such as ferrites such as Mn-Mg-Zn, Ni-Zn and Mn-Zn, carbonyl iron, iron-silicon alloys, iron-aluminum-silicon alloys, and iron-nickel alloys Use to give ferromagneticity. Moreover, the thing surface-treated with the silane coupling agent etc. can also be used for a filler.

As a coloring agent, dye, a pigment, etc. are used. There are various types of dyes, and it is preferable to use a known one appropriately. As the pigment, for example, carbon black, graphite, sulfur lead, iron oxide yellow, titanium dioxide, zinc oxide, trioxide, trioxide, standan, chromium oxide, bluish blue, titanium black and the like can be mentioned. As a light stabilizer, a benzotriazole type ultraviolet absorber, a benzophenone type ultraviolet absorber, a salicylate type ultraviolet absorber, a cyanoacrylate type ultraviolet absorber, an oxalinide type ultraviolet absorber, an obstacle amine type ultraviolet absorber, a benzoate type, UV absorbers, etc. are mentioned.

Although the usage-amount of these additives is not specifically limited, Usually, it is the range used as 0.001-500 weight part with respect to 100 weight part of said thermoplastic resins.

As a method of bulk-polymerizing a polymeric composition (A), for example, (a) the method of bulk-polymerizing by pouring or apply | coating a polymeric composition (A) on a support body, (b) polymeric composition (A) in a mold A method of bulk polymerization and (c) a method of bulk polymerization after impregnating a polymerizable composition (A) with a fiber material is mentioned.

According to the method of (a), a thermoplastic resin film is obtained. As a support body used here, resin, such as polyethylene terephthalate, polypropylene, polyethylene, a polycarbonate, polyethylene naphthalate, polyallylate, nylon; Metal materials, such as iron, stainless steel, copper, aluminum, nickel, chromium, gold, silver, etc. are mentioned. Although the shape is not specifically limited, 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, and more preferably 3 to 75 µm from the viewpoint of workability and the like.

The method of applying the polymerizable composition (A) to the support surface is not particularly limited. For example, the spray coating method, the dip coating method, the roll coating method, the curtain coating method, the die Known coating methods, such as a coating method and a slit coating method, are mentioned.

There is no restriction | limiting in particular as a method of heating a polymeric composition (A) to predetermined temperature, The method of heating a support body on a heating plate, The method of heating (heat press), pressurizing using a press machine, and the pressurizing with the heated roller The method, the method of using a heating furnace, etc. are mentioned.

The thickness of the thermoplastic resin film obtained as mentioned above is 15 mm or less normally, Preferably it is 10 mm or less, More preferably, it is 5 mm or less.

According to the method of (b), the thermoplastic resin molded object of arbitrary shape can be obtained. As the shape, a sheet shape, a film shape, columnar shape, columnar shape, polygonal columnar shape, etc. are mentioned.

As the shaping mold used here, a conventionally known shaping mold, for example, a shaping mold having a split structure, that is, a core mold and a cavity mold, can be used. The reaction solution is injected into these voids (cavities) and subjected to bulk polymerization. . The core mold and the cavity mold are manufactured so as to form voids that coincide with the shape of the target molded article. The shape, material, size, etc. of the molding die are not particularly limited. In addition, a sheet-like or film-like thermoplastic resin molded body can be obtained by preparing a plate-shaped mold such as a glass plate or a metal plate and a spacer having a predetermined thickness, and injecting the reaction liquid into a space formed by sandwiching the spacer into two plate-shaped molds. .

The filling pressure (injection pressure) when filling the reaction liquid into the mold cavity is usually 0.01 to 10 MPa, preferably 0.02 to 5 MPa. If the filling pressure is too low, the transfer of the transfer surface formed on the inner circumferential surface of the cavity tends not to be performed satisfactorily. If the charge voltage is too high, the rigidity of the molding die must be increased and it is not economical. The mold clamping pressure is usually in the range of 0.01 to 10 MPa.

According to the method of (c), a thermoplastic resin impregnation prepreg can be obtained. The material of the fiber material used here is organic and / or inorganic fiber, for example, well-known, such as glass fiber, carbon fiber, aramid fiber, polyethylene terephthalate fiber, vinylon fiber, polyester fiber, amide fiber, metal fiber, ceramic fiber, etc. It can be mentioned. These can be used individually by 1 type or in combination of 2 or more type. Examples of the shape of the fiber material include mats, cloths, and nonwoven fabrics.

In order to impregnate the polymerizable composition (A) with the fiber material, for example, a predetermined amount of the polymerizable composition (A) is spray coated, dip coated, roll coated, curtain coated, die coated, or slit coated. It can apply | coat to a fiber material by well-known methods, such as these, and can superimpose a protective film on it as needed, and can press by a roller etc. from the upper side. After the polymerizable composition (A) is impregnated with the fiber material, the impregnated fiber material (impregnated material) of the obtained polymerizable composition (A) is subjected to bulk polymerization by heating to a predetermined temperature to obtain a thermoplastic resin impregnated prepreg.

The heating method of the impregnated material is not particularly limited, and a method similar to the method of the above (a) can be employed, and the impregnated material can be installed on a support and heated. Moreover, it is also possible to bulk-polymerize according to the method of said (b) after providing a fiber material in mold beforehand, and impregnating a polymeric composition (A).

Since the polymerizable composition (A) has a lower viscosity than the conventional resin varnish and is excellent in impregnation with respect to the fiber material, the obtained prepreg is obtained by uniformly impregnating a thermoplastic resin in the fiber material. In addition, since this prepreg is obtained by impregnating a polymeric composition (A) and heating to predetermined temperature, and mass-polymerizing, it does not require the process of removing a solvent after impregnating a resin varnish like conventionally. Therefore, productivity is excellent and the problem, such as bad smell and blister by a residual solvent, also does not arise. Moreover, since the thermoplastic resin of this invention is excellent in storage stability, the obtained prepreg is also excellent in storage stability.

Also in any of said (a), (b) and (c), the heating temperature for superposing | polymerizing a polymeric composition (A) is 50-200 degreeC normally, Preferably it is 100-200 degreeC. It is preferable to select a polymerization time suitably, Usually, it is 20 minutes from 10 second, Preferably it is within 5 minutes.

The polymerization reaction is started by heating the polymerizable composition (A) to a predetermined temperature. This polymerization reaction is an exothermic reaction. Once the bulk polymerization starts, the temperature of the reaction solution rises rapidly, and reaches the peak temperature in a short time (for example, about 1 second to about 5 minutes). If the maximum temperature at the time of a polymerization reaction becomes high too much, not only a polymerization reaction but a crosslinking reaction may advance and there exists a possibility that a postcrosslinkable thermoplastic resin may not be obtained. Therefore, only the polymerization reaction proceeds completely, so that the crosslinking reaction does not proceed. Specifically, the peak temperature of the bulk polymerization is usually controlled below 230 ° C, preferably below 200 ° C.

When using a radical generator as said crosslinking agent, it is preferable to make the peak temperature at the time of block polymerization into below 1 minute half life temperature of the said radical generator. Here, the half-life temperature for one minute is the temperature at which half of the radical generator decomposes in one minute. For example, the 1-minute half-life temperature of di-t-butylperoxide is 186 ° C, and the 1-minute half-life temperature of 2,5-dimethyl-2,5-bis (t-butyl peroxy) -3-hexine is 194 ° C. .

Moreover, in order to prevent overheating by the heat of polymerization reaction, it can also make it react slowly by adding a reaction retardant to a polymeric composition (A).

Examples of the reaction delay agent that can be used include 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, (cis, cis) -2,6-octadiene, (cis, Chain 1,5-diene compounds such as trans) -2,6-octadiene and (trans, trans) -2,6-octadiene; (Trans) -1,3,5-hexatriene, (cis) -1,3,5-hexatriene, (trans) -2,5-dimethyl-1,3,5-hexatriene, ( Chain 1,3,5-triene compounds such as cis) -2,5-dimethyl-1,3,5-hexatriene; Phosphines such as triphenylphosphine, tri-n-butylphosphine and methyldiphenylphosphine; Lewis bases, such as aniline, etc. are mentioned.

Moreover, in the said cyclic olefin type monomer, the cyclic olefin which has a 1, 5- diene structure and a 1, 3, 5- triene structure in a molecule | numerator also acts as a reaction delay agent. For example, 1,5-cyclooctadiene, 1,5-dimethyl-1,5-cyclooctadiene, 1,3,5-cycloheptatriene, (cis, trans, trans) -1,5, Monocyclic compounds such as 9-cyclododecatriene, 4-vinylcyclohexene and dipentene; Polycyclic compounds such as 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, and 5- (1-propenyl) -2-norbornene; Etc. can be mentioned.

The addition ratio of the reaction delay agent is in the range of 0.001 to 5% by weight, preferably 0.002 to 2% by weight based on the monomer liquid. If the addition rate of the reaction delay agent is less than 0.001% by weight, the reaction delay effect is not exerted. On the contrary, when it exceeds 5 weight%, there exists a possibility that a physical property may fall, or a polymerization reaction may not fully advance with the reaction delay agent which remain | survives in a polymer.

The thermoplastic resin of this invention is obtained by the manufacturing method of this invention, and is resin which can be postcrosslinked. Here, "post-crosslinkable" specifically means that a thermoplastic resin is heated and melted, and further heating is continued, and a crosslinking reaction advances and it becomes a crosslinked resin.

Since the bulk polymerization has progressed almost completely, the thermoplastic resin of this invention has few residual monomers. That is, since the polymerization reaction rate is high, the working environment does not deteriorate due to the odor derived from the monomers. The polymerization reaction rate of the thermoplastic resin of the present invention is usually 80% or more, preferably 90% or more, and more preferably 95% or more. The polymerization reaction rate of the thermoplastic resin can be determined by, for example, analyzing the solution obtained by dissolving the thermoplastic resin in a solvent by gas chromatography.

Resin obtained by block polymerization dissolves in a solvent, and it can confirm that this resin is a thermoplastic resin. That is, if the obtained resin is melt | dissolved in a solvent, it is a thermoplastic resin, and if it is not melt | dissolved, it is a crosslinked resin. As said solvent, Aromatic hydrocarbons, such as benzene and toluene; Ethers such as diethyl ether and tetrahydrofuran; Halogenated hydrocarbons, such as dichloromethane and chloroform, are mentioned.

In addition, the thermoplastic resin of this invention may not be the whole thermoplastic resin which can be post-crosslinked, and may be a part made into a crosslinked resin. That is, in the case of bulk polymerization of the thermoplastic resin of the present invention to obtain a resin molded article having a constant thickness, since the heat of polymerization is difficult to dissipate in the central portion of the molded article, the polymerization reaction temperature may be partially increased. Also in this case, at least the surface portion may be a post-crosslinkable thermoplastic resin.

In the thermoplastic resin of the present invention, since the bulk polymerization proceeds almost completely, the bulk polymerization (metathesis ring-opening polymerization) does not proceed during the storage of the thermoplastic resin. In addition, even if it contains a crosslinking agent in a polymeric composition (A), unless it heat-melts, a crosslinking reaction does not advance. Therefore, the surface hardness of the thermoplastic resin hardly changes during storage, and is excellent in storage stability. In particular, what is obtained by the bulk polymerization of the polymerizable composition (A) containing a radical generator and a radical crosslinking delay agent as a crosslinking agent is excellent in storage stability.

2) Manufacturing Method of Crosslinked Resin

The manufacturing method of the crosslinked resin of this invention has the process of bridge | crosslinking the thermoplastic resin of this invention, It is characterized by the above-mentioned. That is, a crosslinking reaction can advance and a crosslinked resin can be obtained by carrying out heat melting of the thermoplastic resin of this invention, and continuing heating further. It is preferable that the temperature at the time of crosslinking a thermoplastic resin is 20 degreeC or more higher than the peak temperature at the time of the said mass polymerization, and is usually 170-250 degreeC, Preferably it is 180-220 degreeC. In addition, the crosslinking time is not particularly limited, but is usually several minutes to several hours.

The method of crosslinking the thermoplastic resin is not particularly limited as long as the thermoplastic resin melts and crosslinks. In the case where the thermoplastic resin is a sheet-like or film-like molded article, a method of laminating and hot pressing the molded articles as necessary is preferable. The pressure at the time of hot pressing is usually 0.5 to 20 MPa, preferably 3 to 10 MPa. The method of hot pressing can be performed using a press machine, such as a well-known press which has a press frame type for flat plate forming, sheet mold compounding (SMC), or bulk mold compounding (BMC), and productivity is high. great.

3) Manufacturing method of crosslinked resin composite material

The manufacturing method of the crosslinked resin composite material of this invention has the process of laminating | stacking the thermoplastic resin part by laminating | stacking the thermoplastic resin of this invention with a base material.

As a base material to be used, Metal foil, such as copper foil, aluminum foil, nickel foil, chromium foil, gold foil, silver foil; Printed wiring boards; Films, such as a conductive polymer film and another resin film, etc. are mentioned. Moreover, when a thermoplastic resin is manufactured by the method of said (a), a support body can be used as it is as a base material.

Although it does not restrict | limit especially as a method of crosslinking the said thermoplastic resin part, In order to manufacture a crosslinked resin composite material with favorable productivity, the method of heat-pressing what laminated | stacked the thermoplastic resin with the base material is preferable. The conditions of hot press are the same as the case of manufacturing the said crosslinked resin.

Since the thermoplastic resin of this invention to be used has excellent fluidity | liquidity and adhesiveness, it is laminated | stacked and bridge | crosslinked with a base material, excellent in flatness, the base material and crosslinked resin adhere firmly, and the crosslinked resin composite material which has favorable adhesiveness can be obtained. .

The manufacturing method of the crosslinked resin composite material of this invention is suitable for manufacturing a metal foil-clad laminated board using metal foil and preferably copper foil as said base material. The thickness and the surface roughness state of the metal foil used here are not particularly limited and can be appropriately selected according to the purpose of use. In addition, the surface of the metal foil may be treated with a silane coupling agent, a thiol coupling agent, a titanate coupling agent, various adhesives, or the like, and a silane coupling agent represented by the following general formula (1) or a thiol-based couple represented by the general formula (2). It is preferable that it is processed with the ring agent.

Formula 1

RSiXYZ

Formula 2

T (SH) n

In the silane coupling agent represented by the formula (1), R represents a group having a double bond, a mercapto group or an amino group at its terminal, and X and Y each independently represent a hydrolyzable group, a hydroxyl group or an alkyl group. Z represents a hydrolyzable group or a hydroxyl group.

Specific examples of the silane coupling agent represented by the formula (1) include allyl trimethoxy silane, 3-butenyl trimethoxy silane, styryl trimethoxy silane, and N-β- (N- (vinylbenzyl) amino Ethyl)-[gamma] -aminopropyltrimethoxysilane and salts thereof, allyltrichlorosilane, allylmethyldichlorosilane, styryltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Triacetoxysilane, vinyl tris (2-methoxyethoxy) silane, vinyltrichlorosilane, β-methacryloxyethyltrimethoxysilane, β-methacryloxyethyltriethoxysilane, γ -Methacryloxypropyltrimethoxysilane, δ-methacryloxybutyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyl Methyldimethoxysilane, γ-amino Field and the like trimethoxy silane, N- phenyl -γ- aminopropyl trimethoxy silane, N-β- (aminoethyl) -γ- aminopropyl trimethoxy silane.

In the thiol coupling agent represented by the formula (2), T represents an aromatic ring, an aliphatic ring, a heterocycle, or an aliphatic chain, and n represents an integer of 2 or more.

As the thiol coupling agent represented by the formula (2), for example, 2,4,6-trimercapto-1,3,5-triazole, 2,4-dimercapto-6-dibutylamino-1,3,5 -Triazine, 2,4-dimercapto-6-anilino-1,3,5-triazine, etc. are mentioned.

When the thermoplastic resin of this invention is laminated | stacked with metal foil and heat-pressed, a thermoplastic resin part melt | dissolves once, adhering to metal foil, and a crosslinking reaction advances to become a crosslinked resin after that. According to the manufacturing method of this invention, the crosslinked resin-metal foil-clad laminated board formed by firmly bonding a crosslinked resin and metal foil can be obtained. The peeling strength of the metal foil of the obtained crosslinked resin-metal foil-clad laminate is, for example, when copper foil is used as the metal foil, a value measured according to JIS C6481, preferably 0.8 kN / m or more, more preferably 1.2 kN / m That's it.

The manufacturing method of the crosslinked resin composite material of this invention is suitable also for manufacturing a multilayer printed wiring board using a printed wiring board as said base material. As a printed wiring board used here, if it is a normal printed wiring board for a circuit, it will not specifically limit, A well-known thing can be used. For example, a multilayer printed wiring board can be manufactured by stacking an outer layer material (single-side copper-clad laminated board etc.) and an inner layer material (double-sided printed wiring board etc.) through the said prepreg, and pressurizing heating.

The crosslinked resin composite material obtained by the present invention is suitable as an electrical material because the crosslinked resin excellent in electrical insulation, mechanical strength, heat resistance, dielectric properties, and the like adheres firmly to the substrate and has good adhesion.

Moreover, according to this invention, the printed wiring board in which the crosslinked resin excellent in electrical insulation, mechanical strength, and adhesiveness was firmly adhere | attached with a printed wiring board can be manufactured efficiently.

Next, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to the following Example. In addition, in the following examples and comparative examples, "part" and "%" are basis of weight unless there is particular notice.

The steel foil peeling strength of the copper-clad laminated board, the bending strength after copper foil removal, and the bending elastic modulus were measured according to JIS C6481.

Reference Example 1

Preparation of Catalyst Liquid

In a glass flask, 51 parts of benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, 79 parts of triphenylphosphines, 952 parts of toluene It melt | dissolved and prepared the catalyst liquid.

Example 1

A monomer comprising 2800 parts of tetracyclo [6.2.1.1 ^{3,6.0 2,7} ] dodec-4-ene, 1200 parts of 5-ethylidene-2-norbornene, and 6,000 parts of dicyclopentadiene in a glass flask To the liquid, 909 parts of styrene was added as a chain transfer agent, and 39 parts of the catalyst solution were added while stirring to prepare a polymerizable composition a.

When this composition a was sprayed on the iron plate heated at 150 degreeC, it hardened instantly. The cured product was immediately removed from the iron plate to obtain an odorless film-like polymer. Since this film was 0.1 mm in thickness and soluble in toluene, it was found that it was uncrosslinked. Moreover, it was 98.9% when the residual monomer in the toluene solution of this film was measured by gas chromatography, and the polymerization reaction rate was calculated | required.

After the film was stored in air for one week at room temperature, the polymerization reaction rate was similarly determined and found to be 98.9%, indicating that the reaction did not proceed as compared with immediately after the production of the film.

Example 2

The film obtained in Example 1 was placed on a faceplate heater heated to 200 ° C., and once melted, it did not flow by crosslinking. The obtained crosslinked polymer was one that did not dissolve in toluene, and it was found that a crosslinked resin was obtained.

Comparative Example 1

It operated like Example 1 except not adding styrene. The obtained film did not dissolve in toluene.

From Example 1 and Comparative Example 1, it was found that a chain transfer agent such as styrene is required in order to obtain a postcrosslinkable thermoplastic resin.

Comparative Example 2

The iron plate was made 60 ° C and operated in the same manner as in Comparative Example 1 except that the iron plate was cured for 20 minutes on the iron plate. The film obtained had a monomer odor. In addition, as in Example 1, the polymerization reaction rates after the preparation of the film and after storage for one week were measured, and it was found that the reaction proceeded during storage at 76% and 85%, respectively.

Comparative Example 3

The polymerizable composition a prepared in the same manner as in Example 1 was placed in a glass flask. This glass flask was solidified by soaking in a 50 degreeC water bath. At this time, the internal temperature of the flask rose to 235 ° C due to polymerization exotherm. The obtained polymer was insoluble in toluene. In addition, even if this polymer was placed on a faceplate heater heated to 200 ° C, it did not melt.

As mentioned above, when superheating at the time of superposition | polymerization, it also turned out that a crosslinking reaction advances and a thermoplastic resin cannot be obtained.

Example 3

45 parts of dicyclopentadiene, 5 parts of norbornene, 0.45 part of styrene, and 0.197 part of catalyst liquid obtained by the reference example 1 were added to the bottle made of polyethylene, stirring, and the synthetic composition b was obtained.

Subsequently, this composition b was conveyed in the metal mold | die. Here, the metal mold | die used what put the "co" shaped spacer on the chrome plated iron plate with a heater for 2.2 mm x 120 mm x 120 mm flat plate shaping | molding. The die temperature was set at 68 ° C. on one side and 50 ° C. on the other side.

Two minutes after the polymeric composition b was conveyed in the metal mold | die, it demolded and the flat plate was picked out. The flat plate was cut into a disk shape having a diameter of 10 mm and immersed in toluene for one day. The surface part was dissolved, but the central part of the flat plate remained without melting. From this, it was found that the central portion of the obtained plate was undergoing crosslinking while the surface portion remained uncrosslinked.

Further, the obtained flat plate was cut into a square of 87 mm x 87 mm, and using a 'lo' shaped press frame for flat plate forming of 2 mm x 90 mm x 90 mm, and one side (mold temperature at the time of polymerization was 68 Electrolytic copper foil (Type GTS, thickness 0.018mm, product made from Furukawa Sakihoil Co., Ltd.) was laminated | stacked on the surface of the side of (degreeC) and heat-pressed, and the single-sided copper-clad board of board thickness 2mm was obtained. The conditions of the hot press were press temperature 200 degreeC * 15 minutes, and press pressure 5 Mpa.

The copper foil peeling strength of the obtained copper clad laminated board was 1.6 kN / m.

After measuring copper foil peeling strength, only the resin part from which copper foil was peeled off was cut out in the disk shape of diameter 10mm, and immersed in toluene for one day, and when melt | dissolution of the surface like the test before a press did not occur, it swelled whole.

As mentioned above, it turned out that the surface part of resin melt | dissolves once, adhere | attaches with copper foil by heat press, and crosslinks after that.                 

Comparative Example 4

A flat plate was obtained in the same manner as in Example 3 except that no styrene was added. The obtained flat plate was cut out into a disk shape having a diameter of 10 mm and immersed in toluene for one day. As a result, dissolution of the surface as shown in Example 3 did not occur, but only swelled as a whole.

Further, using this flat plate, a single-sided copper-clad laminate having a plate thickness of 2 mm was obtained in the same manner as in Example 3. It was 0.2 kN / m when the copper foil peeling strength of this copper-clad laminated board was measured.

In Example 3, the crosslinked resin copper-clad laminated board which copper foil and crosslinked resin adhered firmly was obtained. On the other hand, in Comparative Example 4, in which the chain transfer agent was not added, no thermoplasticity was observed in the surface portion. Moreover, even if the obtained resin and copper foil were piled up and heat-pressed, the obtained crosslinked resin copper-clad laminated board was weak in adhesiveness of copper foil and crosslinked resin.

Example 4

Styrene as a monomer liquid and a chain transfer agent which consist of 38.5 parts of tetracyclo [6.2.1.1 ^{3,6.0 2,7} ] dodec-4-ene and 18.5 parts of 5-ethylidene- 2-norbornene in the bottle made from polyethylene. 0.31 part, 0.51 part of di-t-butyl peroxides (186 minute half life temperature 186 degreeC), and 0.197 part of said catalyst liquids were added as a crosslinking agent, and the polymeric composition c was prepared.

Subsequently, the flat plate was produced similarly to Example 3 using this composition c. The obtained flat plate was cut out into a disk shape having a diameter of 10 mm and immersed in toluene for one day. The surface portion dissolved, but the plate thickness center portion remained without melting. From this, it was found that crosslinking was progressing in the central portion of the obtained plate while the surface portion remained uncrosslinked.

It was 95% when the surface part was scraped off only thickness of 0.2 mm on both sides, the samples cut together were melt | dissolved in toluene, the residual monomer was quantified by gas chromatography, and the polymerization reaction rate was 95%.

Further, using the obtained flat plate, a single-sided copper-clad laminate having a plate thickness of 2 mm was obtained in the same manner as in Example 3. The copper foil peeling strength of the obtained copper-clad laminate was 1.2 kN / m.

After measuring the copper foil peeling strength, the resin part from which the steel foil was peeled off was cut into a disk shape having a diameter of 10 mm and immersed in toluene for one day. As a result, dissolution of the surface as shown in the test before pressing did not occur, but only swelled as a whole. Moreover, even if the resin part in which the copper foil peeled off after copper foil peeling strength measurement was floated in 260 degreeC solder bath for 20 second, generation | occurrence | production of a gas and deformation | transformation were not seen.

As mentioned above, it turned out that the surface part of resin melt | dissolves once by hot press, and adhere | attaches with copper foil, and then crosslinks and the crosslinked resin which has high heat resistance is obtained.

Comparative Example 5

Except not adding the di-t- butyl peroxide, it was molded in the same manner as in Example 4 to obtain a 2.2 mm thick flat plate. Using the obtained flat plate, a single-sided copper-clad laminate with a plate thickness of 2 mm was obtained in the same manner as in Example 4. The peeling strength of the copper foil of this single-sided copper-clad laminated sheet was 1.1 kN / m.

After measuring copper foil peeling strength, the resin part from which copper foil was peeled off was cut into the disk shape of diameter 10mm, and it immersed in toluene for one day, and completely melt | dissolved. Moreover, when the resin part from which copper foil peeled after copper foil peeling strength measurement was suspended for 20 second in the solder bath at 260 degreeC, it melted and deformed and generation | occurrence | production of gas was seen on the surface. In view of the above, when a cyclic olefin having two or more metathesis ring opening reaction sites is not used and a crosslinking agent such as di-t-butylperoxide is not added, the crosslinking reaction proceeds even if the thermoplastic resin is heated and melted. It was found that the obtained copper-clad laminate was inferior in heat resistance because a crosslinked resin could not be obtained.

Comparative Example 6

Except not adding styrene, it shape | molded like Example 4 and the flat plate of 2.2 mm thickness was obtained. The obtained flat plate was cut out into a disk shape having a diameter of 10 mm and immersed in toluene for one day. As a result, dissolution of the surface as shown in Example 4 did not occur but only swelled as a whole.

Further, using this flat plate, a single-sided copper-clad laminate having a plate thickness of 2 mm was obtained in the same manner as in Example 4. The peeling strength of the copper foil of this single-sided copper-clad laminated board was 0.2 kN / m.

As mentioned above, when chain transfer agents, such as styrene, were not added, it turned out that a thermoplastic resin cannot be obtained and it does not melt and adhere with copper foil.

Example 5

In a vial, tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] dodecane-4 25 parts of a greater ene, tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] dodec-9-yen 8 parts of 4-carboxylic acid, 8.2 parts of brominated bisphenol A epoxy resin (Epoxy equivalent 420-480 g / eq, Ciba Specialty Chemicals Co. product, brand name: AER8049), hydrogenated bisphenol 4.9 parts of an A-type epoxy resin (epoxy equivalent 210 g / eq, manufactured by Dainippon Ink and Chemicals, Inc., trade name: EXA-7015) and 0.2 parts of styrene as a chain transfer agent The mixture was heated and stirred in an oil bath at 80 ° C to obtain a monomer mixture 1.

A stirrer was put into a glass bottle, and 0.013 part and triphenylphosphine 0.00062 were added benzylidene (1, 3- dimesitylimidazolidin-2- lydene) (tricyclohexyl phosphine) ruthenium dichloride. 0.013 parts of toluene was added and dissolved, and then 3 parts of the monomer mixture 1 obtained above was added to the polymerizable composition d with vigorous stirring, and heated in a 60 ° C. water bath. The formation of (mist) was observed and the polymerization was complete.

The obtained polymer was found to be uncrosslinked because it was dissolved in tetrahydrofuran. A portion of the polymer was dissolved in tetrahydrofuran, the residual monomer was quantified by gas chromatography, and the polymerization reaction rate was 91%. When the polymer was gradually heated by the face plate heater 1, it melted and flowed at 210 ° C, but when the temperature was raised, the fluidity disappeared at 250 ° C to give a rubbery material.

Example 6

In a branched flask, 26 parts of 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene, 4.2 parts of 5-norbornene-2,3-dicarboxylic anhydride and brominated bisphenol A 5.2 parts of type epoxy resins (AER8049), 3.1 parts of hydrogenated bisphenol A type epoxy resins (EXA-7015), and 0.18 parts of styrene as a chain transfer agent were added and heated and stirred in an 80 ° C oil bath to prepare a monomer mixture. 2 was obtained.

A stirrer was put into the glass bottle, 0.024 part of benzylidene (1, 3- dimesitylimidazolidin-2- lydene) (tricyclohexyl phosphine) ruthenium dichloride, and 0.0037 part of triphenylphosphine were added. 0.013 parts of toluene was added to make a homogeneous solution, and 3 parts of the monomer mixture 2 obtained above was added to the polymerizable composition e while stirring vigorously, and heated in a 70 ° C. water bath. The production | generation of mist by was observed, and the polymerization reaction was completed.

The obtained polymer was dissolved in chloroform and found to be thermoplastic (uncrosslinked). As a result of quantifying the residual monomers by gas chromatography of the polymer solution, all of the norbornene-based monomers (1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene and 5-norbornene-2, 3-dicarboxylic acid anhydride) was 98%. When the polymer was slowly heated with a face plate heater, it melted and flowed at 170 ° C, but when the temperature was raised, the fluidity disappeared at 230 ° C, resulting in a rubbery product.

Example 7

A bottle of polyethylene, 3,5-di -t- butyl-hydroxy anisole, 0.2089 parts of tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] dodec 22.5 parts of 4-ene, 2-norbornene 7.5 parts of linen, 0.69 parts of allyl methacrylate, 0.443 parts of di-t-butyl peroxide (1 minute half-life temperature 186 DEG C) were added, and 0.11 parts of the catalyst solution of Reference Example 1 was added to the mixture, followed by stirring. Prepared.

On top of a glass fiber reinforced polytetrafluoroethylene resin (PTFE resin) film (cut to 300 mm x 300 mm, thickness 0.08 mm. Product number: 5310, manufactured by Saint-Gobain KK). Glass fiber fabric (cut to 200 mm × 200 mm, thickness 0.092 mm.) Item name: 2116/350 / AS891AW, manufactured by Asahi-Schwebel Co., Ltd. The polymerizable composition f was poured onto about half the glass fiber fabric, covered from above and one more glass fiber reinforced PTFE resin film, and impregnated by pressing with a roller.

Each glass fiber reinforced PTFE resin film was stuck to an aluminum plate heated at 145 ° C. for 1 minute and polymerized. Thereafter, both glass fiber reinforced PTFE resin films were peeled off to obtain a prepreg.

A portion of the obtained prepreg was placed in a platinum crucible, and the resin portion was burned with an electric furnace to determine the glass content from the remaining glass weight, which was 58%. Moreover, it was 97% when a part of this prepreg was immersed in toluene, the resin part was melt | dissolved, the residual monomer was quantified by gas chromatography of the solution, and the polymerization reaction rate was calculated from this and glass content rate.                 

0.05 part of acetic acid was added to 60 parts of distilled water, and 0.18 part of vinyl tris (2-methoxyethoxy) silane (trade name: A-172, manufactured by Nippon Unicar Co., Ltd.) was added thereto. The mixture was stirred for 10 minutes to hydrolyze and dissolve to prepare a silane coupling agent solution. This silane coupling agent solution was contained in the cotton wool, and it was applied to the rough surface of the electrolytic copper foil (roughening GTS processed product, thickness 0.018mm, made by Furukawa Circuit Foil Co., Ltd.) under nitrogen atmosphere. It dried at 130 degreeC for 1 hour.

Three pieces of the prepreg (87 mm x 87 mm) obtained above were put into a 'ro' shaped frame (thickness 1 mm) having an inner dimension of 90 mm x 90 mm, and the silane coupler from both sides. The prepreg side was sandwiched with a ring-treated copper foil (cut to 115 mm × 115 mm) so as to be a rough surface, and was hot pressed at 200 ° C. for 15 minutes at a press pressure of 4.1 MPa. Then, the sample was obtained by cooling with the press pressure applied, cooling to 100 degrees C or less, and obtaining a double-sided copper clad laminated board.

It was 1.6 kN / m when the peeling strength of the copper foil of this double-sided copper-clad laminated board was measured. Moreover, when the lead heat test was done for 20 second in the 260 degreeC lead bath, swelling was not seen.

When the bending test of the fiber reinforced resin part (thickness 1.5mm) after copper foil removal was carried out, the bending elastic modulus was 12 GPa and the bending strength was 385 MPa. In addition, the dielectric constant and dielectric loss tangent were measured by an impedance analyzer (type: E4991, manufactured by Agilent Technologies), at 3.5 MHz and 0.0013 at 100 MHz, respectively, at 13.1 GHz. 3.5 and 0.0022.

Example 8

0.4 parts of fumed silica (brand name: AEROSIL 200, product made by AEROSIL Japan Inc.) in polyethylene bottle, tetracyclo [6.2.1.1 ^3,6 .0] ^2,7 ] dodec-4-ene 22.5 parts, 2-norbornene 7.5 parts, methacrylic acid styryl 1.0 parts, 2,5-dimethyl-2,5-bis (t-butylperoxy) 0.36 part of -3-hexine (1 minute half life temperature 194 degreeC) was put, 0.11 part of catalyst liquid of the reference example 1 was added, and it stirred, and the polymeric composition g was prepared.

0.05 part of acetic acid was added to 60 parts of distilled water, and 0.18 part of styryl trimethoxysilane (trade name: KEM-1403, manufactured by Shin-Etsu Chemical Co., Ltd.) was added for 1 hour. It stirred, hydrolyzed and dissolved, and prepared the silane coupling agent solution. This silane coupling agent solution was contained in cotton wool, it apply | coated to the rough surface of electrolytic copper foil (used in Example 7), and it dried at 130 degreeC under nitrogen atmosphere for 1 hour.

Using a coating roller, the polymerizable composition g was applied to the rough surface of the electrolytic steel foil (cut to a size of 220 mm x 220 mm), and then the glass fiber reinforced PTFE resin film (used in Example 7) was used from above. The copper foil side was covered with an aluminum plate heated at 145 ° C. for 1 minute and polymerized. Then, the glass fiber reinforced PTFE resin film was peeled off, and the copper foil with resin was obtained.

A part of this copper foil with resin was immersed in toluene, the resin part was dissolved, the residual monomer was quantified by gas chromatography of the solution, and the polymerization reaction rate was calculated from this and the remaining copper foil weight, and it was 97%.

Glass epoxy double-sided copper-clad laminated board (thickness cut into 1 mm, 80 mm x 80 mm) which microetched the copper foil surface using the surface roughening agent CZ-8100 (made by Mack Corporation) with the said resin It sandwiched so that resin side might become inner side with copper foil, and it hot-pressed at 200 degreeC for 15 minutes at the press pressure of 5.2 MPa. Thereafter, the resultant was cooled with the press pressure applied, cooled to 100 ° C. or lower, and then a sample was obtained to obtain a multilayer copper-clad laminate.

It was 1.6 kN / m when the peeling strength of the copper foil on the back surface of this multilayer copper-clad laminated board was measured. Moreover, when the adhesiveness with the inner side copper foil was confirmed with the peeling adhesive test (JIS K5400) with respect to the surface resin layer after peeling copper foil, there was no peeling.

Moreover, the copper with resin mentioned above about the board (cut | disconnected to thickness 1.4mm and 80mm x 80mm) which removed the copper by etching with aqueous ammonium persulfate solution from the double-sided copper-clad laminated board manufactured like Example 7 The resin side was sandwiched with foil so as to be inward, and hot pressed at 200 ° C. for 15 minutes at a press pressure of 5.2 MPa. Then, the sample was obtained by cooling with the press pressure applied, cooling to 100 degrees C or less, and obtaining a double-sided copper clad laminated board.

It was 1.6 kN / m when the peeling strength of the copper foil of the surface of this double-sided copper-clad laminated board was measured. Moreover, when adhesiveness with the inner side resin layer was confirmed with the peeling adhesive test (JISK5400) with respect to the surface resin layer after peeling copper foil, it was not peeled off.

Example 9

In a polyethylene bottle, 0.6 parts of fumed silica (aerosil 200), 12 parts of tetracyclo [6.2.1.1 ^{3,6.0 2,7} ] dodec-4-ene, 5.4 of 2-norbornene 12 parts of dicyclopentadiene, 0.36 part of styrene and 0.34 part of di-t-butyl peroxide were added, and 0.11 part of catalyst solution of Reference Example 1 was added and stirred to prepare a polymerizable composition h.

Using a painting roller, the polymerizable composition h was applied to the surface of the glass fiber reinforced PTFE resin film (used in Example 7), covered with another glass fiber fabric reinforced PTFE resin film from above, and 145 ° C. It stuck to the aluminum plate heated by 1 minute, and superposed | polymerized. Thereafter, the glass fiber fabric reinforced PTFE resin film was peeled off to obtain a resin film.

It was 98% when a part of this film was immersed in toluene, the resin part was dissolved, the residual monomer was quantified from the gas chromatography of the solution, and the polymerization reaction rate was calculated.

Except having used the resin film obtained above, it carried out similarly to Example 8, and obtained the double-sided copper clad laminated board by which the crosslinked resin adhered to the surface. When the adhesiveness with the copper foil of the inside was confirmed with respect to the surface resin layer by the peel adhesion test (JIS K5400), there was no peeling.

Examples 10-15

It operated like Example 7 except having used the thing shown in Table 1 as a silane coupling agent. Table 1 shows the results of measuring the copper foil peeling strength of the obtained double-sided copper-clad laminate. However, in Examples 12 and 15, the silane coupling agent solution prepared without using acetic acid was used.

Example 16

The same procedure as in Example 7 was repeated except that a 0.3% tetrahydrofuran solution of 2,4,6-trimercapto-1,3,5-triazine was used instead of the silane coupling agent solution. Table 1 shows the results of measuring the copper foil peeling strength of the obtained double-sided copper-clad laminate.

Examples 17-19

Operation was carried out in the same manner as in Example 11, except that styryl methacrylate (Example 17), 1-octene (Example 18) or styrene (Example 19) was used instead of allyl methacrylate as the chain transfer agent. Examples 17, 18 and 19 were carried out. Copper foil peeling strength became 1.5 kN / m, 1.1 kN / m, and 1.1 kN / m, respectively.

From this, when the chain transfer agent which has a methacryloyl group is used, it turns out that adhesion | attachment of copper foil and resin becomes more firm.

According to the present invention, a polymerizable composition (A) containing (I) a cyclic olefin (α) or a monomer liquid containing a norbornene-based monomer and a crosslinking agent, (II) a metathesis polymerization catalyst, and (III) a chain transfer agent is bulky. By the simple method of superposition | polymerization, the thermoplastic resin which does not have a problem of the odor by a residual monomer and is excellent in storage stability can be obtained efficiently. Since the manufacturing method of the crosslinked resin and crosslinked resin composite material of this invention is simple, and continuous production is possible, it is an industrially advantageous manufacturing method. The crosslinked resin obtained by the present invention is excellent in electrical insulation, mechanical strength, heat resistance, dielectric properties, and the like. According to the present invention, a crosslinked resin composite material obtained by laminating a thermoplastic resin of the present invention with a base material and crosslinking the thermoplastic resin portion has excellent adhesion between the crosslinked resin and the base material, and is useful as an electrical material. Is provided.

Claims (20)

A bulk polymerization of the polymerizable composition (A) comprising the components of the following (I) to (III), characterized in that the method for producing a post-crosslinkable thermoplastic resin. (I) Monomer liquid which contains 10 weight% or more of cyclic olefin ((alpha)) which has two or more metathesis ring-opening reaction site | parts in a molecule with respect to all monomer amounts, or monomer liquid containing norbornene-type monomer and a crosslinking agent. (II) Metathesis Polymerization Catalyst (III) Chain Transfer Agent Bulk polymerization of the polymerizable composition (A) comprising a monomer liquid, a metathesis polymerization catalyst and a chain transfer agent, each containing 10% by weight or more of a cyclic olefin (α) having two or more metathesis ring-opening reaction sites in the molecule. Method for producing a post-crosslinkable thermoplastic resin, characterized in that. A method for producing a postcrosslinkable thermoplastic resin, characterized in that the polymerizable composition (A) comprising a norbornene-based monomer, a metathesis polymerization catalyst, a chain transfer agent and a crosslinking agent. 4. The method according to any one of claims 1 to 3, A method for producing a postcrosslinkable thermoplastic resin, characterized in that the maximum temperature at the time of polymerization of the bulk polymerization is less than 230 ° C. 4. The method according to any one of claims 1 to 3, A process for producing a postcrosslinkable thermoplastic resin, characterized in that the polymerization reaction rate is 80% or more. 4. The method according to any one of claims 1 to 3, As the chain transfer agent, a compound represented by the formula CH ₂ = CH-Q (wherein Q represents a group having at least one group selected from methacryloyl group, acryloyl group, vinyl silyl group, epoxy group and amino group) is used. A method of producing a postcrosslinkable thermoplastic resin. The method according to claim 1 or 2, A dicyclopentadiene is used as said cyclic olefin ((alpha)), The manufacturing method of the postcrosslinkable thermoplastic resin characterized by the above-mentioned. The method according to claim 1 or 3, The norbornene-based monomer mixture comprising a norbornene-based monomer having a carboxyl group or an acid anhydride group as the norbornene-based monomer, and using an epoxy compound as the crosslinking agent. The method according to claim 1 or 3, A method for producing a post-crosslinkable thermoplastic resin, characterized in that the polymerizable composition (A) is bulk polymerized using a radical generator as the crosslinking agent, at a reaction temperature of 1 minute or less of the half-life temperature of the radical generator. The method of claim 9, A method for producing a post-crosslinkable thermoplastic resin, characterized by further comprising a radical crosslinking retardant as the polymerizable composition (A). delete 4. The method according to any one of claims 1 to 3, A method for producing a postcrosslinkable thermoplastic resin, characterized in that the polymerizable composition (A) is molded into a film by mass polymerization on a support. 13. The method of claim 12, A metal foil or a resin film is used as the support, wherein the post-crosslinkable thermoplastic resin is produced. 4. The method according to any one of claims 1 to 3, A method for producing a post-crosslinkable thermoplastic resin, characterized in that the polymerizable composition (A) is molded into a predetermined shape by bulk polymerization in a mold. 4. The method according to any one of claims 1 to 3, The polymerizable composition (A) is impregnated with a fibrous material and then bulk polymerized. A method for producing a crosslinked resin having a step of crosslinking a postcrosslinkable thermoplastic resin obtained by the method according to any one of claims 1 to 3. The manufacturing method of the crosslinked resin composite material which has the process of laminating | stacking a postcrosslinkable thermoplastic resin obtained by the manufacturing method of any one of Claims 1-3 with a base material, and crosslinking a thermoplastic resin part. The method of claim 17, Metal foil is used as said base material, The manufacturing method of the crosslinked resin composite material characterized by the above-mentioned. The method of claim 18, A method for producing a crosslinked resin composite material using the metal foil, which is treated with a silane coupling agent represented by the following formula (1) or a thiol-based coupling agent represented by the following formula (2). Formula 1 RSiXYZ Formula 2 T (SH) n (Wherein R represents a group having a double bond, a mercapto group or an amino group at the terminal, X and Y each independently represent a hydrolyzable group, a hydroxyl group or an alkyl group, and Z represents a hydrolyzable group or a hydroxyl group. T represents an aromatic ring) , An aliphatic ring, a heterocycle, or an aliphatic chain, and n represents an integer of 2 or more. The method of claim 17, The manufacturing method of the crosslinked resin composite material which uses a printed wiring board as said base material.