JP2014198410A - Transfer sheet for forming cycloolefin resin layer and method of producing cycloolefin resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer sheet for forming a cycloolefin resin layer which is useful for producing a cycloolefin resin laminate, and to provide a method of producing a cycloolefin resin laminate using the transfer sheet.SOLUTION: The transfer sheet for forming a cycloolefin resin layer comprises a transfer support and a polymerizable composition layer formed on the transfer support. The polymerizable composition layer comprises: a polymerizable composition which contains a cycloolefin monomer; a polymerization catalyst having a specific ligand; and an inorganic filler. The method of producing a cycloolefin resin laminate uses the transfer sheet.

Description

  The present invention relates to a transfer sheet for forming a cycloolefin resin layer useful for producing a laminate having a cycloolefin resin layer (cycloolefin resin laminate), and a method for producing a cycloolefin resin laminate using the transfer sheet.

A cycloolefin resin obtained by polymerizing a polymerizable composition containing a cycloolefin monomer generally has excellent heat resistance and electrical characteristics (low dielectric loss tangent and low dielectric constant), and has recently attracted attention as an electronic circuit board material. Has been.
For example, in Patent Document 1, a resin molded body obtained by bulk polymerization of a polymerizable composition containing a cycloolefin monomer, an inorganic filler, and a ruthenium catalyst (metathesis polymerization catalyst) in a mold is used as a prepreg, It has been proposed to use it as a printed wiring board, an insulating sheet or the like. Moreover, in patent document 2, the coating material and impregnation material which were obtained using the polymeric composition containing the same component are heated, and a resin molding etc. are formed, and this thing is used as a high frequency board material etc. It has been proposed to use.

  However, when a cycloolefin resin layer is formed on a substrate by the methods described in Patent Documents 1 and 2, the surface of the cycloolefin resin layer may be oxidized due to heating in a polymerization reaction or the like. In the subsequent steps, when a metal thin film (plating layer) is formed on the surface of the cycloolefin resin layer, the interlayer adhesion between the metal thin film and the cycloolefin resin layer may be lowered. In addition, when a low-boiling cycloolefin monomer is used, there is a case where a cycloolefin resin having a target repeating unit cannot be obtained due to volatilization before the low-boiling cycloolefin monomer is polymerized by heating. .

Conventionally, a method of providing a synthetic resin layer on a surface of a release sheet or the like by previously forming a synthetic resin layer or a material layer thereof, stacking the layer on a predetermined surface, and performing a pressure-bonding treatment or the like. A method of forming a synthetic resin layer on a substrate using (transfer method) is known.
For example, Patent Document 3 discloses a multilayer printed wiring board using a support base film having a release layer and an adhesive film made of a thermosetting resin composition laminated on the surface of the release layer by a transfer method. A method of manufacturing is described. In addition, this document describes that by thermally curing the resin composition with a support base film attached, it is possible to avoid dust and foreign matter from adhering to the resin surface during curing.

  In connection with the present invention, Non-Patent Document 1 describes a ruthenium complex having a carbene ligand and a method for producing the same.

WO2005 / 000579 pamphlet JP 2012-140538 A JP 2001-196743 A

Organometallics 2010, 29, 117-124

  The present invention has been made in view of the above-described prior art, and is useful for the production of a cycloolefin resin laminate, a transfer sheet for forming a cycloolefin resin layer, and a method for producing a cycloolefin resin laminate using this transfer sheet. The purpose is to provide.

  In order to solve the above-mentioned problems, the present inventors use a transfer sheet for forming a cycloolefin resin layer comprising a transfer support and a polymerizable composition layer formed on the transfer support. The earnest examination was repeated about the method of manufacturing a resin laminated body. As a result, a transfer sheet obtained using a polymerizable composition containing a ruthenium metal complex having a specific structure as a cycloolefin monomer, an inorganic filler, and a polymerization catalyst can be stored for a long time near room temperature. I found out. In addition, this polymerizable composition layer has an appropriate viscosity when laminated with a substrate (base material), and a bulk polymerization reaction at a general temperature (around 150 ° C.) used for heating by a hot press or the like. It has been found that a cycloolefin resin laminate having a high-quality cycloolefin resin layer can be obtained sufficiently. The present invention has been completed based on these findings.

  Thus, according to the present invention, there are provided the following [1] to [3] transfer sheet for forming a cycloolefin resin layer and the method for producing the cycloolefin resin laminate of [4]. The transfer sheet for forming a cycloolefin resin layer can form a cycloolefin resin layer as an embodiment of a laminate including the cycloolefin resin layer.

[1] A transfer sheet for forming a cycloolefin resin layer comprising a transfer support and a polymerizable composition layer formed on the transfer support, wherein the polymerizable composition layer is a cycloolefin monomer. A transfer sheet for forming a cycloolefin resin layer comprising a polymerizable composition containing a polymerization catalyst represented by the following formula (1) and an inorganic filler.

(X ¹ and X ² each independently represents an anionic ligand. L represents a heteroatom-containing carbene compound.)
[2] The transfer sheet for forming a cycloolefin resin layer according to [1], wherein the cycloolefin monomer is a compound represented by the following formula (2) or a compound represented by the following formula (3).

Wherein ^(2), R 1 to R ⁴ are each independently a hydrogen atom, or an organic group having 1 to 30 carbon atoms, and ^{R 1} or ^{R 2, R 3} or ^{R 4} is bonded to each other To form a ring structure. p represents 0, 1 or 2. ]

[In Formula (3), A represents a C1-C30 bivalent organic group. q and r each independently represents 0, 1 or 2. ]
[3] The polymerizable composition according to [1] or [2], wherein the polymerizable composition has a viscosity at 25 ° C. and a shear rate of 1000 (1 / s) of more than 1 Pa · s and not more than 3 Pa · s. Olefin resin layer forming transfer sheet.
[4] A method for producing a cycloolefin resin laminate having a substrate and a cycloolefin resin layer laminated on the substrate, wherein the substrate and any one of [1] to [3] A step of forming a composite in which the substrate and the polymerizable composition layer are opposed to each other, and thermocompression-bonding the composite, And a step of obtaining a laminate having a layer structure of material / cycloolefin resin layer / transfer support. A method for producing a cycloolefin resin laminate.

The transfer sheet for forming a cycloolefin resin layer of the present invention is excellent in storage stability and can be stored for a long time near room temperature.
The polymerizable composition layer of the transfer sheet for forming a cycloolefin resin layer of the present invention has an appropriate viscosity when laminated with a substrate (base material), and is a general temperature used for heating by a hot press or the like. At about 150 ° C., the bulk polymerization reaction proceeds sufficiently to give a high-quality cycloolefin resin layer. Therefore, by using the transfer sheet for forming a cycloolefin resin layer of the present invention, a cycloolefin resin laminate having a high-quality cycloolefin resin layer can be efficiently produced.

  Hereinafter, the present invention will be described in detail by dividing it into 1) a transfer sheet for forming a cycloolefin resin layer and 2) a method for producing a cycloolefin resin laminate.

1) Transfer sheet for forming a cycloolefin resin layer The transfer sheet for forming a cycloolefin resin layer of the present invention (hereinafter sometimes referred to as “transfer sheet”) is formed on a transfer support and the transfer support. A transfer sheet comprising the polymerizable composition layer. The polymerizable composition layer is characterized by comprising a polymerizable composition containing a cycloolefin monomer, a polymerization catalyst represented by the formula (1), and an inorganic filler.

[Transfer support]
The transfer support constituting the transfer sheet of the present invention can hold the polymerizable composition layer and can be easily peeled off from the cycloolefin resin layer after the cycloolefin resin layer is formed. If it is, it will not specifically limit.

Examples of the transfer support include a resin sheet, a metal foil, a paper base, and a laminate including these.
Examples of the resin sheet include polyolefin resins such as polyethylene, polypropylene, cyclic polyolefin, and various olefin copolymers; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polystyrene resins; polyvinyl chloride resins; acrylic resins; Examples of the resin sheet include urethane-modified acrylic resins; polycarbonate resins; polyamide resins; fluorine resins such as polytetrafluoroethylene; and mixtures of these resins.
Examples of the metal foil include copper foil and aluminum foil.
Examples of the paper substrate include craft paper, fine paper, imitation paper, art paper, and coated paper.

The transfer support may have a surface that has been subjected to a release treatment with a release agent. Examples of such release agents include alkyd release agents, silicone release agents, fluorine release agents, unsaturated polyester release agents, polyolefin release agents, and wax release agents.
The thickness of the transfer support is not particularly limited. For example, it is 10-100 micrometers.

(Polymerizable composition)
The polymerizable composition used for forming the polymerizable composition layer contains a cycloolefin monomer, a polymerization catalyst represented by the formula (1), and an inorganic filler.

[Cycloolefin monomer]
The cycloolefin monomer used in the present invention is an olefin having an alicyclic structure in the molecule. The alicyclic structure is a non-aromatic ring structure composed of carbon-carbon bonds, and the number of rings includes monocyclic, polycyclic, condensed polycyclic, bridged ring, and combination polycyclic thereof. . The cycloolefin monomer has one or more carbon-carbon double bonds. Although carbon number which comprises an alicyclic structure does not have a special restriction | limiting, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is the range of 5-15 pieces.

  Examples of the cycloolefin monomer include norbornene monomers and monocyclic hydrocarbon monomers.

  The norbornene-based monomer is a compound having a norbornene ring structure, and examples thereof include norbornenes, dicyclopentadiene, tetracyclododecenes, and benzoindenes. These include hydrocarbon groups such as alkyl groups, alkenyl groups, alkylidene groups, and aryl groups, hydroxyl groups, carboxyl groups, alkoxyl groups, epoxy groups, glycidyl groups, oxycarbonyl groups, carbonyl groups, amino groups, ester groups, And a polar group such as a carboxylic acid anhydride group, or a hydrocarbon group having these polar groups. Moreover, in addition to the double bond of the norbornene ring, it may have another double bond.

Specific examples of such norbornene-based monomers include bicyclo [2.2.1] hept-2-ene (commonly used norbornene), tricyclo [4.3.0.1 ^2,5 ] deca-3,7- Diene (common name dicyclopentadiene), tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (common name tetracyclododecene), 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (common name ethyltetracyclododecene), tetracyclo [7.4.1 ^10,13 . 0 ^1,9 . 0 ^2,7 ] trideca-2,4,6,11-tetraene (common name methanotetrahydrofluorene; MTF) and the like, and the hydrocarbon group, polar group, and hydrocarbon group having a polar group bonded thereto Things.

The monocyclic hydrocarbon monomer is a cycloolefin monomer having an alicyclic structure, and examples thereof include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, and 2- (2-methylbutyl). Monocyclic cycloalkenes such as -1-cyclohexene, cyclooctene, cycloheptene, and vinylcyclohexene; alicyclic nonconjugated dienes such as 1,4-cyclohexadiene and 1,5-cyclooctadiene; cyclopentadiene, cyclohexadiene, And alicyclic conjugated dienes such as 1,3-cyclooctadiene;
These cycloolefin monomers can be used alone or in combination of two or more.

  Among these cycloolefin monomers, a norbornene-based monomer is preferable because a polymerizable composition having an appropriate viscosity and reactivity is easily obtained, and a norbornene-based monomer having one polymerizable carbon-carbon double bond ( Monofunctional norbornene-based monomers) or norbornene-based monomers having two or more polymerizable carbon-carbon double bonds (polyfunctional norbornene-based monomers) are more preferable, and among them, monofunctional norbornene-based monomers or bifunctional norbornene-based monomers Alternatively, a combination of a monofunctional norbornene monomer and a bifunctional norbornene monomer is more preferable, and among them, a combination of a monofunctional norbornene monomer and a bifunctional norbornene monomer is particularly preferable.

  Examples of the monofunctional norbornene-based monomer include compounds represented by the following formula (2).

In formula (2), R ^{1 to} R ⁴ each independently represent a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R ¹ or R ² and R ³ or R ⁴ are bonded to each other. A ring structure may be formed.
p represents 0, 1 or 2.

The carbon number of the organic group having 1 to 30 carbon atoms R ¹ to R ⁴ is preferably 1 to 20, more preferably 1 to 15.
Examples of the organic group having 1 to 30 carbon atoms of R ^{1 to} R ⁴ include a hydrocarbon group having 1 to 30 carbon atoms, a polar group having 1 to 30 carbon atoms, and a hydrocarbon group having a polar group having 1 to 30 carbon atoms. Etc.

  Examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, and a propyl group; an alkenyl group having 2 to 30 carbon atoms such as a vinyl group, a propenyl group, and a crotyl group; C2-C30 alkynyl groups such as ethynyl group, propargyl group, 3-butynyl group; aryl groups having 6-30 carbon atoms such as phenyl group, 1-naphthyl group, 2-naphthyl group; cyclopropyl group, cyclopentyl group And a cycloalkyl group having 3 to 30 carbon atoms such as a cyclohexyl group; an aralkyl group having 7 to 30 carbon atoms such as a benzyl group and a phenethyl group.

Examples of the polar group having 1 to 30 carbon atoms include a carboxyl group (—COOH), an ester group (—C (═O) —OR ⁵ ), an amide group (—C (═O) —N (R ⁵ ) (R ⁶ ). )), Monovalent polar groups such as alkoxy groups (—OR ⁶ ) (wherein R ⁵ and R ⁶ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 29 carbon atoms); an ether group ( -O-), ester group (-C (= O)-, -O-C (= O)-), amide group (-C (= O) -NH-, -NH-C (= O)-) Divalent groups such as acid anhydride group (—O—C (═O) —O—), carbonyl group (—C (═O) —), ureido group (—NH—C (═O) —NH—), etc. Polar groups of
Moreover, as a C1-C30 hydrocarbon group which has a polar group, a C1-C30 hydrocarbon group which has a monovalent polar group at the terminal of a bivalent coupling group; And a hydrocarbon group having a divalent polar group.

  Examples of the monofunctional norbornene-based monomer represented by the formula (2) include compounds represented by the following formulas (2a) to (2d). In addition, p represents the same thing as the above.

In formula (2), R ⁷ represents an organic group having 1 to 30 carbon atoms, and R ⁸ represents an organic group having 1 to 29 carbon atoms. Specific examples thereof are the same as those listed as the organic group having 1 to 30 carbon atoms of R ^{1 to} R ⁴ .
Examples of the bifunctional norbornene monomer include a compound represented by the following formula (3).

  In formula (3), A represents a C1-C30 bivalent organic group. q and r each independently represents 0, 1 or 2.

Carbon number of the C1-C30 divalent organic group of A becomes like this. Preferably it is 1-20, More preferably, it is 1-15.
Examples of the divalent organic group having 1 to 30 carbon atoms of A include an alkylene group having 1 to 30 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, and a propylene group; 1,4-phenylene group, 1,3- Arylene groups having 6 to 30 carbon atoms such as phenylene group, 1,2-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group; ether group (—O—), ester Groups (—C (═O) —, —O—C (═O) —), amide groups (—C (═O) —NH—, —NH—C (═O) —), acid anhydride groups ( Divalent polar groups such as —O—C (═O) —O—), carbonyl group (—C (═O) —), ureido group (—NH—C (═O) —NH—); A group consisting of a combination; and the like.
Among these, as the compound represented by the formula (3), a compound represented by the following formula (3a) is preferable.

In Formula (3a), A ′ is an alkylene group having 1 to 28 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, or a propylene group; 1,4-phenylene group, 1,3-phenylene group, 1, And arylene groups having 6 to 28 carbon atoms such as 2-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group and 2,6-naphthylene group; and groups composed of combinations thereof.
Specific examples of the compound represented by the formula (3a) include compounds represented by the following formulas (3a1) and (3a2). q and r each represents the same thing as the above.

In addition, as long as expression of the effect of this invention is not inhibited, the polymerizable composition of this invention may contain the arbitrary monomers copolymerizable with the above cycloolefin monomer.
Such monomers include α-olefins, dienes, (meth) acrylates and the like.

[Polymerization catalyst]
The polymerization catalyst used in the present invention is a ruthenium carbene complex represented by the following formula (1) (hereinafter sometimes referred to as “polymerization catalyst (α)”).

In formula (1), X ¹ and X ² each independently represents an anionic ligand. Anionic ligands are ligands that have a negative charge when pulled away from a central atom. X ¹ and X ² may be bonded to each other to form a bidentate ligand.

  Examples of the anionic ligand include halogen atoms such as fluorine atom (F), chlorine atom (Cl), bromine atom (Br), and iodine atom (I); diketonate group; substituted cyclopentadienyl group; alkoxy Group; aryloxy group; carboxyl group; and the like. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

  In formula (1), L represents a hetero atom-containing carbene compound. Examples of the heteroatom-containing carbene compound include compounds represented by the following formula (4) or formula (5).

R ^{9 to} R ¹² are each independently a hydrogen atom; a halogen atom; or a cyclic or chain-like carbon that may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. This represents a hydrocarbon group having a number of 1 to 20. R ^{9 to} R ¹² may be bonded together in any combination to form an aliphatic ring or an aromatic ring.

  Examples of the compound represented by the formula (4) or (5) include 1,3-dimesitylimidazolidin-2-ylidene, 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1, 3-dicyclohexylimidazolidine-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-di (1-phenylethyl) ) -4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene, and the like.

A polymerization catalyst ((alpha)) can be used individually by 1 type or in combination of 2 or more types.
Specific examples of the polymerization catalyst (α) include those represented by the following formula (6). In the following formula (6), “Mes” represents a mesityl group (2,4,6-trimethylphenyl group).

  The polymerization catalyst (α) can be produced by a method described in Organometallics 2010, 29, 117-124 and the like.

  The content of the polymerization catalyst (α) in the polymerizable composition is usually from 1: 2,000 to 1: 2,000,000 in a molar ratio (metal atom in the polymerization catalyst (α): cycloolefin monomer). The range is preferably 1: 5,000 to 1: 1,000,000, more preferably 1: 10,000 to 1: 500,000.

  The polymerization catalyst (α) is stable around room temperature (25 ° C.). For this reason, the polymerization composition containing the polymerization catalyst (α) as the polymerization catalyst hardly undergoes the polymerization reaction near room temperature, and the viscosity hardly increases after the preparation or in the polymerizable composition layer. Therefore, by using the polymerizable catalyst (α), a polymerizable composition excellent in workability and a transfer sheet for forming a cycloolefin resin layer excellent in storage stability can be obtained.

[Inorganic filler]
The inorganic filler used in the present invention is generally added as a functional additive such as a colorant; a modifier having a modification effect such as an increase in strength, an improvement in flame retardancy, and a suppression of an increase in linear expansion coefficient. Is. The inorganic filler located on the surface of the cycloolefin resin layer has a function of roughening the surface of the cycloolefin resin layer by dissolving or decomposing with a chemical etching agent, or exposing or desorbing, etc. The inorganic filler located in the position exhibits the intended function and improves the performance of the cycloolefin resin.

  As an inorganic filler, since the adhesion between the cycloolefin resin and the plating layer is excellent, the inorganic filler can be dissolved in a chemical etching agent (acid, alkali, oxidizing agent, etc.) used for chemical etching which is a pretreatment for plating or Inorganic and metal particles that are decomposed are preferred.

As inorganic particles, aluminum hydroxide, magnesium hydroxide, sodium hydroxide, calcium hydroxide, ferrous hydroxide, ferric hydroxide, cuprous hydroxide, cupric hydroxide, stannous hydroxide , And metal hydroxides such as stannic hydroxide; silicon oxide (silica), aluminum oxide, zirconia oxide, zinc oxide, magnesium oxide, titanium oxide, sodium oxide, calcium oxide, ferrous oxide, ferric oxide , Cuprous oxide, cupric oxide, tin oxide, cordierite (2MgO · 2Al ₂ O ₃ · 5SiO ₂ ), and metal oxides such as antimony oxide; sodium chloride, sodium bromide, calcium chloride, aluminum chloride, Ferrous chloride, ferric chloride, cuprous chloride, cupric chloride, stannous chloride, stannic chloride, chlorosilane, ammonium chloride, and trisalt Metal chlorides such as antimony; metal sulfates such as sodium hydrogen sulfate, sodium sulfate, calcium sulfate, and ammonium sulfate; nitrates such as sodium nitrate and calcium nitrate; sodium dihydrogen phosphate, sodium hydrogen phosphate, sodium phosphate, phosphorus Phosphate such as ammonium phosphate and sodium polyphosphate; hydrated magnesium silicate (talc) and silicate (mineral) such as mica; antimonate such as sodium antimonate; sodium bicarbonate, sodium carbonate, and carbonate Carbonates such as calcium; sulfites such as sodium hydrogen sulfite and sodium sulfite; hypophosphites such as sodium hypophosphite and ammonium hypophosphite; phosphites such as sodium phosphite; Sodium chlorate, calcium hypochlorite And hypohalates such as sodium hypobromite; thiosulfates such as sodium thiosulfite and thiosulfates such as sodium thiosulfate; halogen acids such as sodium chlorate, calcium chlorate, and sodium bromate Salts; Halogenates such as sodium chlorite, calcium chlorite, and sodium bromate; Perhalogenates such as sodium perchlorate, calcium perchlorate, and sodium perbromate; Silicon carbide and carbonized Examples thereof include carbides such as boron; nitrides such as aluminum nitride, boron nitride, and silicon nitride; glass materials such as glass powder, glass cloth, glass fiber, and glass nonwoven; carbon black; and the like.

  Examples of the metal particles include metal particles such as aluminum, nickel, magnesium, copper, zinc, and iron.

  Among these, metal hydroxides and metal oxides are preferable, aluminum hydroxide and magnesium hydroxide are preferable in the former, silicon oxide (silica) is more preferable in the latter, and silicon oxide (silica) is preferable from the viewpoint of excellent electrical characteristics. Particularly preferred.

  The inorganic filler used in the present invention is preferably particulate. When the inorganic filler is in the form of particles, the number average particle diameter of the particles calculated from the average of the values obtained by measuring the major axis of 1000 inorganic filler particles by observing with a scanning electron microscope is The thickness is 0.001 to 100 μm, preferably 0.01 to 50 μm, more preferably 0.1 to 20 μm, and particularly preferably 0.5 to 10 μm. This is because the adhesion between the molded body and the plating layer is stable and good.

  The amount of the inorganic filler used is usually 1 to 500 parts by weight, preferably 5 to 400 parts by weight, more preferably 10 to 300 parts by weight, and particularly preferably 20 to 200 parts by weight with respect to 100 parts by weight of the cycloolefin monomer. It is. If the amount is too small, the adhesion between the molded body and the plating layer is not sufficiently good, and if it is too large, the strength of the resulting laminate is reduced, and therefore, neither is preferable.

[Other ingredients]
The polymerizable composition may contain other components in addition to the cycloolefin monomer, the polymerization catalyst, and the inorganic filler.
Other components include chain transfer agents, radical generators (crosslinking agents), crosslinking aids, flame retardants, polymerization regulators, polymerization reaction retarders, reactive fluidizers, flame retardants, antioxidants, colorants, etc. Is mentioned.
As these compounds, generally used compounds, for example, compounds described in JP2009-242568A, compounds described in JP2010-10000683, and the like can be used.

(Polymerizable composition)
The polymerizable composition can be obtained by mixing the above components. What is necessary is just to follow a conventional method as a mixing method. For example, a solution (catalyst solution) in which a polymerization catalyst (α) is dissolved or dispersed in an appropriate solvent is added to a solution (monomer solution) containing a cycloolefin monomer, an inorganic filler or other components, and stirred. A polymerizable composition can be prepared.

  As a solvent used when preparing a catalyst liquid, an inert solvent is preferable. Examples of such solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, decahydronaphthalene, and bicycloheptane. Alicyclic hydrocarbons such as tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as indene, benzene, toluene and xylene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; diethyl ether, tetrahydrofuran and the like Of ethers; and the like. Among these, it is preferable to use industrially general-purpose aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons. Moreover, as long as the activity as a polymerization catalyst is not lowered, a liquid anti-aging agent, a plasticizer or an elastomer may be used as a solvent.

  As described above, the polymerizable composition used in the present invention hardly causes a polymerization reaction near room temperature, maintains a low viscosity, and is excellent in coatability. The viscosity of the polymerizable composition at 25 ° C. and a shear rate of 1000 (1 / s) is preferably more than 1 Pa · s and not more than 3 Pa · s, and more preferably more than 1 Pa · s and not more than 2 Pa · s.

2. Formation method of polymeric composition layer The formation method of polymeric composition layer is not specifically limited. For example, the polymerizable composition layer can be formed by applying the polymerizable composition described above on a transfer support and drying the obtained coating film as necessary.

  When coating the polymerizable composition on the transfer support, use a known coating method such as spray coating, dip coating, roll coating, curtain coating, die coating, and slit coating. Can do.

  In addition, a fibrous reinforcing material is placed on a transfer support, and the polymerizable composition is applied to impregnate the fibrous reinforcing material to form an impregnated material, or the polymerizable composition is applied to the fibrous reinforcing material. The impregnated material obtained by impregnating the material may be placed on a transfer support, and the impregnated material on the transfer support may be used in place of the coating film to form a polymerizable composition layer. Good.

Examples of the fibrous reinforcing material used when forming the impregnated material include woven or non-woven fabrics of inorganic and / or organic fibers.
Examples of inorganic fibers include glass fibers, carbon fibers, alumina fibers, tungsten fibers, molybdenum fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, and silica fibers.
Examples of the organic fiber include PET (polyethylene terephthalate) fiber, aramid fiber, ultra-high molecular weight polyethylene fiber, polyamide (nylon) fiber, and liquid crystal polyester fiber.
These fibers may be used by opening a fiber bundle.

[Transfer sheet for forming cycloolefin resin layer]
The transfer sheet of the present invention comprises a transfer support and a polymerizable composition layer formed on the transfer support, and the polymerizable composition layer comprises the polymerizable composition. Is.

The transfer sheet of the present invention is excellent in storage stability and is less likely to deteriorate in performance over time. Further, the polymerizable composition in the polymerizable composition layer is, for example, a substrate (base material). ), The bulk polymerization reaction proceeds sufficiently at a general temperature (around 150 ° C.) used for heating by a hot press or the like.
Therefore, the transfer sheet of the present invention is useful for the production of a cycloolefin resin laminate.

2) Manufacturing method of cycloolefin resin laminated body The manufacturing method of the cycloolefin resin laminated body of this invention is a manufacturing method of the cycloolefin resin laminated body which has a base material and the cycloolefin resin layer laminated | stacked on the said base material. A step of forming a composite in which the base material and the transfer sheet of the present invention are superposed so that the base material and the polymerizable composition layer of the transfer sheet face each other; And a step of obtaining a laminate having a layer structure of base material / cycloolefin resin layer / transfer support by thermocompression bonding.

  The apparatus and pressure bonding conditions used in the thermocompression bonding in the step of obtaining the laminate are the cycloolefin resin layer formed by this polymerization reaction as the polymerization reaction of the polymerizable composition constituting the polymerizable composition layer proceeds. Is not particularly limited as long as it can be pressure-bonded to the substrate.

Examples of the apparatus used for thermocompression bonding include pressure laminators, presses, vacuum laminators, vacuum presses, roll laminators and the like.
A cycloolefin resin laminate having excellent interlayer adhesion can be obtained by thermocompression bonding using these pressurizers.

The temperature at the time of thermocompression bonding is usually 30 to 250 ° C., preferably 70 to 200 ° C., the applied pressure is usually 10 kPa to 20 MPa, preferably 100 kPa to 10 MPa, and the time is usually 30 seconds to 5 seconds. Time, preferably 1 minute to 3 hours.
The thermocompression bonding is preferably performed under reduced pressure in order to suppress the generation of bubbles in the cycloolefin resin layer. The pressure under reduced pressure at which thermocompression bonding is performed is usually 100 kPa to 1 Pa, preferably 40 kPa to 10 Pa. Moreover, you may further heat with a heating furnace etc. after thermocompression bonding as needed. The heating temperature in that case is 100-250 degreeC, Preferably it is 150-200 degreeC. Moreover, the heating time in that case is 20 second-3 hours, Preferably they are 1 minute-1 hour.

  The thermocompression bonding is performed in a state where the transfer support is present as the outermost layer. By performing thermocompression bonding in this way, contact between the surface of the polymerizable composition layer (cycloolefin resin layer) and air can be prevented, and oxidation of the surface of the cycloolefin resin layer can be suppressed. Furthermore, even when a low boiling point cycloolefin monomer is contained in the polymerizable composition layer, volatilization of the monomer can be suppressed.

  The transfer support is peeled off after the cycloolefin resin layer is formed. If it is after formation of a cycloolefin resin layer, the time in particular which peels the support for transfer will not be restricted. For example, the peeling treatment may be performed immediately after the formation of the cycloolefin resin layer, or may be performed after another process (for example, a drilling process using a laser or a drill).

After peeling off the transfer support, for example, a metal layer (corresponding to the aforementioned plating layer) may be formed on the exposed cycloolefin resin layer. The formation method of a metal layer is not specifically limited, For example, the electroless-plating method is mentioned.
The cycloolefin resin laminate obtained by the production method of the present invention is one in which oxidation of the cycloolefin resin layer surface is suppressed, and efficiently forms a metal layer having excellent interlayer adhesion on the cycloolefin resin layer. It is something that can be done.

  Thus, according to the method for producing a cycloolefin resin laminate of the present invention, a cycloolefin resin laminate useful as a circuit board material can be efficiently produced.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples. In the following Examples and Comparative Examples, “parts” and “%” are based on weight unless otherwise specified.

The compounds used in Examples and Comparative Examples are shown below.
Cycloolefin monomer (1): monofunctional norbornene monomer represented by the following formula

Cycloolefin monomer (2): bifunctional norbornene monomer represented by the following formula

Polymerization catalyst (1): complex represented by formula (6) (manufactured by Umicore)
Polymerization catalyst (2): (1,3-Dimesityl-4-imidazoline-2-ylidene) (2-pyrrolidone-1-ylmethylene) (tricyclohexylphosphine) ruthenium dichloride filler (1): fused silica (average particle size 0) .5um, surface treatment with silane coupling agent)

[Example 1]
The polymerization catalyst (1) was dissolved in cyclohexanone to prepare a catalyst solution having a concentration of 2%.
On the other hand, 90 parts of cycloolefin monomer (1), 10 parts of cycloolefin monomer (2) and 210 parts of filler (1) were placed in a glass container, and these were uniformly mixed to prepare a monomer solution.
1 part of the catalyst solution was added to the monomer solution and stirred to obtain a polymerizable composition (A).

  Using a polyethylene terephthalate film as a transfer support, the polymerizable composition (A) is coated on the polyethylene terephthalate film so as to have a thickness of 40 μm using an automatic coating apparatus to form a cycloolefin resin layer. A transfer sheet (A) was obtained.

[Comparative Example 1]
In Example 1, a polymerizable composition (B) was prepared in the same manner as in Example 1, except that 1 part of the catalyst solution containing the polymerization catalyst (2) was used instead of the polymerization catalyst (1). Using the polymerizable composition (B), an attempt was made to produce a transfer sheet for forming a cycloolefin resin layer by the same method as in Example 1, but the viscosity was too high to be applied, and the target cyclohexane was not coated. A transfer sheet for forming an olefin resin layer was not obtained.

[Example 2]
The cycloolefin resin laminate (A) was obtained by superposing the transfer sheet (A) for forming the cycloolefin resin layer on a polyethylene terephthalate film as a transfer support and heating at 160 ° C. for 1 hour.

[Comparative Example 2]
The cycloolefin resin laminate (B) was obtained by heating the transfer sheet for forming a cycloolefin resin layer (A) at 160 ° C. for 1 hour without using the transfer support.

The respective characteristics of the polymerizable compositions (A) and (B) used in Example 1 and Comparative Example 1 and the cycloolefin resin laminates (A) and (B) formed in Example 2 and Comparative Example 2, respectively. Evaluation was performed according to the following method.
(1) Coating workability The viscosity of the polymerizable compositions (A) and (B) is measured at 25 ° C. and a shear rate of 1000 (1 / s) using a rheometer (HAAKE RS6000, manufactured by EKO Instruments). The coating workability was evaluated using the following indices. The evaluation results are shown in Table 1.
○: Over 1 Pa · s, 2 Pa · s or less Δ: Over 2 Pa · s, 3 Pa · s or less X: Range other than the above ○ and Δ

(2) Polymerization reaction rate The transfer support was peeled off from the cycloolefin resin laminate to obtain a cycloolefin resin layer, and this cycloolefin resin layer was dissolved in toluene to obtain a sample solution. Using this, the residual monomer amount was determined by gas chromatography, and the polymerization reaction rate was calculated from this value. The calculation results are shown in Table 2.

(3) Dielectric loss tangent The transfer support is peeled off from the cycloolefin resin laminate to obtain a cycloolefin resin layer, and this cycloolefin resin layer is cut out to obtain a test piece having a width of 2.6 mm, a length of 80 mm, and a thickness of 40 μm. Got.
Using a cavity resonator perturbation method dielectric constant measuring apparatus (manufactured by Kanto Electronics Application Development Co., Ltd.), the dielectric loss tangent of this test piece at 10 GHz was measured and evaluated according to the following criteria. The evaluation results are shown in Table 2.
○: Less than 0.002 ×: 0.002 or more

Table 1 shows the following.
The polymerizable composition (A) used in Example 1 has a viscosity suitable for coating work, and is excellent in coating workability. Further, the polymerizable composition (A) has a viscosity that hardly changes over a long period of time around 25 ° C. As described above, by using the polymerizable composition (A), a transfer sheet for forming a cycloolefin resin layer having excellent long-term storage stability can be obtained.
On the other hand, the polymerizable composition used in Comparative Example 1 has a viscosity that increases after its preparation and is inferior in coating workability, and it is difficult to obtain a transfer sheet for forming a cycloolefin resin layer.

Table 2 shows the following.
In Example 2, the cycloolefin resin layer was formed by heating in the presence of the transfer support, and the dielectric loss tangent was low and the electrical characteristics were excellent.
On the other hand, in Comparative Example 1, the cycloolefin resin layer was formed by heating in the absence of the transfer support, and since the dielectric loss tangent was high, it is considered that the surface was oxidized.

Claims (4)

A cycloolefin resin layer forming transfer sheet comprising a transfer support and a polymerizable composition layer formed on the transfer support,
The transfer sheet for forming a cycloolefin resin layer, wherein the polymerizable composition layer comprises a polymerizable composition containing a cycloolefin monomer, a polymerization catalyst represented by the following formula (1), and an inorganic filler.

(X ¹ and X ² each independently represents an anionic ligand. L represents a heteroatom-containing carbene compound.) The transfer sheet for forming a cycloolefin resin layer according to claim 1, wherein the cycloolefin monomer is a compound represented by the following formula (2) or a compound represented by the following formula (3).

Wherein ^(2), R 1 to R ⁴ are each independently a hydrogen atom, or an organic group having 1 to 30 carbon atoms, and ^{R 1} or ^{R 2, R 3} or ^{R 4} is bonded to each other To form a ring structure. p represents 0, 1 or 2. ]

[In Formula (3), A represents a C1-C30 bivalent organic group. q and r each independently represents 0, 1 or 2. ]   3. The cycloolefin resin layer formation according to claim 1, wherein the polymerizable composition has a viscosity at 25 ° C. and a shear rate of 1000 (1 / s) of more than 1 Pa · s and not more than 3 Pa · s. Transfer sheet. A process for producing a cycloolefin resin laminate having a substrate and a cycloolefin resin layer laminated on the substrate,
A composite in which the base material and the transfer sheet for forming a cycloolefin resin layer according to any one of claims 1 to 3 are overlapped so that the base material and the polymerizable composition layer face each other is formed. And a process of
A step of thermocompression bonding the composite to obtain a laminate having a layer structure of substrate / cycloolefin resin layer / transfer support;
A process for producing a cycloolefin resin laminate, comprising: