JP5298883B2 - COMPOSITE MATERIAL AND METHOD FOR PRODUCING COMPOSITE MATERIAL - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate having excellent adhesiveness to resin, and heat resistance. <P>SOLUTION: The adhesiveness of the substrate to the resin is improved by treating the substrate using two kinds of coupling agents of specific structural formulas äin a ratio of the coupling agent B to the coupling agent A (the coupling agent B/coupling agent A) of 0.001-2.0 in terms of weight ratio}. The heat resistance of the substrate is improved by the treatment. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a substrate and a composite material using the same, and more particularly to a substrate excellent in adhesion and heat resistance to a resin, and a composite material including the substrate and the resin.

  In recent years, with the miniaturization, weight reduction, and multifunctionalization of electronic devices, high-speed transmission of large-capacity signals in information communication devices has become an urgent issue. In order to achieve high-speed transmission of large-capacity signals, it is important to make fine wiring that shortens the transmission distance and low loss in high-frequency transmission in a circuit board composed of an insulating layer and a conductor layer.

  The circuit board is formed by laminating a copper foil serving as a conductor layer and a resin layer serving as an insulating layer, and thermocompression bonding to obtain a copper-clad laminate, and then etching the copper foil to form a circuit. It is manufactured. As the polymer for forming the insulating layer (resin layer), an epoxy resin is generally used, but as a polymer having a lower dielectric constant and lower loss, polyphenylene ether, polyphenylene oxide, polybutadiene, and cycloolefin polymer can be used. It has been proposed to use a polymer having a low polarity such as. However, when these polymers are used, the adhesion between the resin layer and the copper foil may be insufficient. In addition, for the purpose of increasing the strength of the resin layer or reducing the dielectric constant, it may be used by impregnating a polymer with a fiber material such as glass cloth or by adding a filler such as silica to the resin layer. However, the adhesion between the polymer and the fiber material or filler may be insufficient.

As a method for improving the adhesion between a polymer such as a copper foil, a fiber material, and a filler and a polymer, it has been proposed to treat the surface of the substrate with a silane coupling agent. For example, Patent Document 1 discloses a silane coupling agent-containing aqueous solution having a silane coupling agent content of 0.01% by weight or more and a total light transmittance of 50% or more when the optical path length is 50 mm. A composite comprising a base material obtained by surface treatment and a resin layer is disclosed. In Patent Document 2, a post-crosslinkable thermoplastic resin is laminated on a copper foil treated with a silane coupling agent having a double bond, a mercapto group or an amino group at the end, and the thermoplastic resin portion is crosslinked. It is disclosed that a copper-clad laminate is manufactured. Furthermore, Patent Document 3 discloses a silane coupling formed using a bifunctional silane coupling agent having functional groups of —Si (OCH ₃ ) at both ends of the chemical structural formula on the adhesive surface to the resin base material layer. A surface-treated copper foil provided with an agent-treated layer is disclosed.

International Publication No. 2008/123253 Japanese Patent Laid-Open No. 2004-244609 JP 2007-98732 A

  However, when the present inventors examined, in any of the composite material described in Patent Document 1, the copper-clad laminate described in Patent Document 2, and the copper-clad laminate described in Patent Document 3, an insulating layer is formed. As a crosslinkable resin before cross-linking to form, a low molecular weight, high adhesion when using a high fluidity, the problem that such a high fluidity crosslinkable resin can not be used Furthermore, since heat resistance is not always sufficient, a problem that adhesion after soldering is poor is recognized.

  The objective of this invention is providing the composite material obtained using the base material excellent in the adhesiveness and heat resistance with respect to resin, and such a base material.

  As a result of intensive studies in view of the above problems, the present inventors processed the base material using a treatment agent containing two types of coupling agents having a specific structure, whereby the base material was adhered to a resin ( In particular, it has been found that the adhesiveness when using a resin with high fluidity) and heat resistance (especially the adhesiveness to the resin after soldering) can be made excellent, and based on this finding, the present invention It came to complete.

（上記一般式（１）中、Ｍ^１は、Ｔｉ，Ｓｉ，ＡｌまたはＺｒを表し、Ｒ^１は、末端に二重結合、メルカプト基またはアミノ基を有する炭化水素基を表し、Ｘ^１，Ｘ^２はそれぞれ独立して加水分解性基、水酸基またはアルキル基を表し、Ｘ^３は加水分解性基または水酸基を表す。上記一般式（２）中、Ｍ^２は、Ｔｉ，Ｓｉ，ＡｌまたはＺｒを表し、Ｘ^４，Ｘ^５はそれぞれ独立して加水分解性基、水酸基またはアルキル基を表し、Ｘ^６は加水分解性基または水酸基を表し、Ｙは、窒素原子、酸素原子もしくは硫黄原子を含む置換基を有していても良い炭素数１〜３０の直鎖、分岐もしくは環状の脂肪族炭化水素基、または窒素原子、酸素原子もしくは硫黄原子を含む置換基を有していても良い芳香族炭化水素基を表す。）
また、本発明によれば、基材と、シクロオレフィンモノマーおよびメタセシス重合触媒を含む重合性組成物を塊状重合してなる脂環式構造含有重合体からなる樹脂層とを含む複合材料の製造方法であって、前記基材を、上記一般式（１）で表されるカップリング剤（Ａ）、および上記一般式（２）で表されるカップリング剤（Ｂ）を含む処理剤で処理する工程と、前記基材の表面のうち、前記処理剤により処理が施された部分と、前記重合性組成物とを接触させた状態で前記重合性組成物を塊状重合させることにより前記樹脂層を形成する工程とを備え、前記カップリング剤（Ａ）と、前記カップリング剤（Ｂ）との比率が、重量比で、カップリング剤（Ｂ）／カップリング剤（Ａ）＝０．００１〜２．０である複合材料の製造方法が提供される。
That is, according to the present invention, a composite material comprising a base material and a resin layer comprising an alicyclic structure-containing polymer obtained by bulk polymerization of a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst, The base material is treated with a treatment agent containing a coupling agent (A) represented by the following general formula (1) and a coupling agent (B) represented by the following general formula (2), The ratio of the coupling agent (A) to the coupling agent (B) is, by weight, coupling agent (B) / coupling agent (A) = 0.001 to 2.0, The resin layer is provided by a composite material that is formed by performing bulk polymerization in a state where a portion of the surface of the base material that has been treated with the treatment agent and the polymerizable composition are in contact with each other. Is done.

(In the above general formula (1), M ¹ represents Ti, Si, Al or Zr, R ¹ represents a hydrocarbon group having a double bond, a mercapto group or an amino group at the end, and X ¹ , X ² independently represents a hydrolyzable group, a hydroxyl group or an alkyl group, and X ³ represents a hydrolyzable group or a hydroxyl group, wherein M ² represents Ti, Si, Al or Zr in the general formula (2). X ⁴ and X ⁵ each independently represents a hydrolyzable group, a hydroxyl group or an alkyl group, X ⁶ represents a hydrolyzable group or a hydroxyl group, and Y represents a substituent containing a nitrogen atom, an oxygen atom or a sulfur atom. A linear, branched or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a group, or an aromatic carbon which may have a substituent containing a nitrogen atom, an oxygen atom or a sulfur atom Represents a hydrogen group.)
Further, according to the present invention, a method for producing a composite material comprising a substrate and a resin layer comprising an alicyclic structure-containing polymer obtained by bulk polymerization of a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst. And the said base material is processed with the processing agent containing the coupling agent (A) represented by the said General formula (1), and the coupling agent (B) represented by the said General formula (2). The resin layer is formed by bulk polymerization of the polymerizable composition in a state where the polymerizable composition is brought into contact with a portion of the surface of the base material that has been treated with the treatment agent in the process. And the ratio of the coupling agent (A) and the coupling agent (B) is a weight ratio of coupling agent (B) / coupling agent (A) = 0.001. Provided is a method of manufacturing a composite material that is 2.0 That.

  ADVANTAGE OF THE INVENTION According to this invention, the base material excellent in the adhesiveness and heat resistance with respect to resin, and the composite material obtained using this are provided. The composite material of the present invention has adhesion between the substrate and the resin (particularly adhesion when a resin having high fluidity is used) and heat resistance (particularly, after the solder treatment, the substrate and the resin It can be suitably used for high-frequency circuit boards such as microwaves or millimeter waves for communication equipment applications.

The base material of the present invention is obtained by treating the base material body with a treatment agent containing a coupling agent (A) and a coupling agent (B) described later.
The composite material of the present invention comprises such a base material of the present invention and a resin.

(Base material body)
The substrate body constituting the substrate of the present invention is not particularly limited as long as it has a regular shape, but is preferably made of a metal or an inorganic compound.

  Such metals or inorganic compounds include simple elements or alloys of metal elements such as iron, copper, nickel, silver, gold, platinum, and aluminum; simple elements of non-metallic elements such as phosphorus and sulfur; magnesium, calcium, titanium, Oxides, nitrides, borides, hydroxides, inorganic acid salts and hydrates of metal elements such as zirconium, vanadium, chromium, manganese, iron, copper, nickel, zinc, silver, aluminum, tin and antimony And oxides, nitrides and hydrates of nonmetallic elements such as boron, silicon, and phosphorus; and mixtures thereof. Among these, a simple substance or an alloy of a metal element and an inorganic compound containing silicon dioxide are preferable. As a metal element in the simple substance or alloy of a metal element, copper, aluminum, and nickel are preferable, and copper is particularly preferable. Moreover, as an inorganic compound containing silicon dioxide, glass and silica are preferable, and glass is particularly preferable.

  The shape of the substrate body is not particularly limited, and examples thereof include a plate shape, a sheet shape, a fiber shape, and a particle shape. Among these, a single element or alloy of a metal element in a sheet form, that is, a metal foil, and glass in a fiber form, that is, a glass fiber are preferable.

  The thickness of metal foil becomes like this. Preferably it is 1-250 micrometers, More preferably, it is 2-100 micrometers, More preferably, it is 3-75 micrometers. In addition, in terms of electrical characteristics, the metal foil has a 10-point average roughness (Rz) defined by JIS B0601, and preferably has a surface roughness of 3.0 μm or less, more preferably 2 on the surface in contact with the resin. 0.0 μm or less, more preferably 1.0 μm or less.

  Furthermore, it is preferable that the rust prevention process is performed about the metal foil. The rust prevention treatment is performed by forming a thin film of another metal different from the metal constituting the metal foil on the metal foil by sputtering, electroplating or electroless plating. Among these, electroplating is preferable because the process is simple and the productivity is excellent. Examples of other metals used for the rust prevention treatment include nickel, tin, zinc, chromium, molybdenum, cobalt, and alloys thereof, and among these, zinc or chromium is preferable. In addition, it is preferable that a chromate treatment layer is formed on the rust-proof treatment because adhesion to the resin can be improved.

  Examples of the shape of the glass fiber include short fibers such as chips, milled fibers, and chopped strands; Among these, cloth (glass cloth) is preferable because of its excellent strength and heat resistance. Specific examples of the form of the cloth include woven or non-woven cloth such as roving cloth, cloth, chopped mat, and surfacing mat. Among these forms, a woven fabric and a non-woven fabric are preferable from the viewpoint of dimensional stability. In addition, those obtained by compressing these woven or non-woven fabrics with a hot roll or the like are preferable, and the woven and non-woven fabrics may be laminated and used. A prepreg as a composite material can be obtained by impregnating a glass cloth as a base body with a crosslinkable resin.

  As the glass cloth, as the warp and weft used for weaving, those obtained by using about 100 to 800 monofilaments with a filament diameter of preferably about 5 to 10 μm are preferred. Examples of the weaving structure include plain weaving, satin weaving, Nanako weaving, twill weaving, etc., and plain weaving is preferred. As glass types, in addition to E glass (non-alkali), which is generally used as a substrate for printed wiring boards, NE glass (New Glass manufactured by Nitto Boseki Co., Ltd.), D glass (low dielectric), T glass (high Strength), C glass (alkali lime), S glass and H glass (high dielectric), Q glass and the like. More specifically, EP03C, EP06, EP08A, EP11C, EP10A, EP18B, etc. specified in JIS R3414 may be mentioned.

  Moreover, as glass cloth, what combined the glass fiber which consists of a different glass composition may be sufficient. Further, a cloth or a microfibril such as a liquid crystalline polymer, aramid, polybenzoxazole and natural cellulosic fibers may be mixed with glass cloth.

The weight per unit area of the glass cloth used in the present invention is preferably 1 to 250 g / m ² , more preferably 5 to 180 g / m ² , still more preferably 5 to 120 g / m ² , and particularly preferably 5 to 80 g / m ² . a m ^2. By setting the weight per unit area of the glass cloth within the above range, the strength and adhesion when combined with various resins to form a composite material can be made sufficient. If the weight per unit area is too small, the strength of the resulting composite material may be insufficient. On the other hand, if the size is too large, there are few voids between the fibers and it is difficult to impregnate the resin, so that the resulting composite material may have insufficient adhesion.

  The thickness of the glass cloth used in the present invention is preferably 5 to 300 μm, more preferably 10 to 200 μm, and still more preferably 10 to 100 μm. If the thickness is too thin, the strength of the resulting composite material may be insufficient when combined with various resins to form a composite material. On the other hand, if it is too thick, it may be difficult to control the thickness when a plurality of composite materials are used.

(Processing agent)
The treating agent used in the present invention contains a coupling agent (A) represented by the following general formula (1) and a coupling agent (B) represented by the following general formula (2). .

In the general formula (1), M ¹ is Ti, Si, Al or Zr, preferably Si. R ¹ is a hydrocarbon group having a double bond, a mercapto group or an amino group at the terminal, more preferably a hydrocarbon group having a double bond at the terminal, and more preferably a styryl group. X ¹ and X ² are each independently a hydrolyzable group, a hydroxyl group or an alkyl group, X ³ is a hydrolyzable group or a hydroxyl group, and these X ¹ , X ² and X ³ are A decomposable group is preferred, and an alkoxyl group is more preferred. In addition, the coupling agent (A) represented by the general formula (1) acts as a coupling agent having radical reactivity.

In the general formula (2), M ² is Ti, Si, Al or Zr, preferably Si. X ⁴ and X ⁵ are each independently a hydrolyzable group, a hydroxyl group or an alkyl group, X ⁶ is a hydrolyzable group or a hydroxyl group, and these X ⁴ , X ⁵ and X ⁶ are hydrolyzable. It is preferably a group, more preferably an alkoxyl group. Y is a linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 30 carbon atoms, and a linear aliphatic hydrocarbon group or aromatic carbon group having 2 to 15 carbon atoms. A hydrogen group is preferred. In addition, these aliphatic hydrocarbon groups or aromatic hydrocarbon groups may have a substituent containing a nitrogen atom, an oxygen atom, or a sulfur atom. Further, when Y is an aromatic hydrocarbon group, the aromatic hydrocarbon group may be directly bonded to M ² or via an alkylene group having 1 to 10 carbon atoms. , M ² may be bonded. In addition, the coupling agent (B) represented by the general formula (2) mainly acts as a hydrolyzable coupling agent.

  Specific examples of the coupling agent (A) represented by the general formula (1) include allyltrimethoxysilane, 3-butenyltrimethoxysilane, styryltrimethoxysilane, N-β- (N- (vinylbenzyl) ) Aminoethyl) -γ-aminopropyltrimethoxysilane and salts thereof, allyltrichlorosilane, allylmethyldichlorosilane, styryltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) ) Silane, vinyltrichlorosilane, β-methacryloxyethyltrimethoxysilane, β-methacryloxyethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, δ-methacryloxybutyltrimethoxysilane, γ-acryloxyp Pyrtrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (aminoethyl)- Examples include γ-aminopropyltrimethoxysilane. These may be used alone or in combination of two or more.

  Specific examples of the coupling agent (B) represented by the general formula (2) include bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (tripropoxysilyl) ethane, bis ( Trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tripropoxysilyl) methane, bis (trimethoxysilyl) hexane, bis (trimethoxysilyl) octane, bis (triethoxysilyl) octane, bis (triethoxy Silyl) nonane, bis (triethoxysilyl) octadiene, 1,2-bis (trimethoxysilyl) decane, 1,3-bis (triethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1, 4-bis (triethoxysilyl) benzene, 1,4-bis (triethoxysilyl) Til) benzene, 1,4-bis (triethoxysilylethyl) benzene, bis [(3-methyldimethoxysilyl) propyl] polypropylene oxide, bis [3- (triethoxysilyl) propyl] disulfide, bis [m- (2 -Trimethoxysilylethyl) tolyl] polysulfide, bis [3- (triethoxysilyl) propyl] thiourea, bis (triethoxysilylethyl) vinylmethylsilane, bis (triethoxysilyl) ethylene, 1,3- [bis (3 -Triethoxysilylpropyl) polyethyleneoxy] -2-methylenepropane, bis (4-triethoxysilylpropyl-3-methoxyphenyl) -1,6-heptane and the like. These may be used alone or in combination of two or more.

  The ratio of the coupling agent (A) to the coupling agent (B) in the treating agent is preferably a weight ratio of coupling agent (B) / coupling agent (A), preferably 0.001 to 2.0. More preferably, it is 0.01-1.0, More preferably, it is 0.05-0.5, Most preferably, it is 0.1-0.3. Even if the value of the coupling agent (B) / coupling agent (A) is too low or too high, the adhesion to the resin and the heat resistance tend to decrease.

(Base material)
The base material of this invention processes the said base-material main body using the processing agent containing the said coupling agent (A) and a coupling agent (B).
In this invention, when processing a base-material main body using the processing agent containing the said coupling agent (A) and a coupling agent (B), a coupling agent (A) and a coupling agent (B It is preferable to prepare a treating agent-containing aqueous solution by dispersing or dissolving a treating agent containing) in water, and to treat the substrate body using the prepared treating agent-containing aqueous solution. In addition, as a specific method when processing the substrate body using the treatment agent-containing aqueous solution, for example, (a) the substrate body is immersed in the treatment agent-containing aqueous solution, and then this is pulled up and dried. (B) a roll coater, a die coater. Examples include a method of applying a treatment agent-containing aqueous solution using a coating apparatus such as a gravure coater and then drying, and (c) a method of spraying the treatment agent-containing aqueous solution on the surface of the substrate body using a spraying device. . In addition, the process of the base body using the treatment agent may be performed on the entire surface of the base body, or may be performed on a part of the surface.

  The concentration of the treatment agent in the treatment agent-containing aqueous solution used in the present invention (that is, the total concentration of the coupling agent (A) and the coupling agent (B)) is preferably 0.001% by weight or more, more preferably. Is 0.005 to 10% by weight, more preferably 0.01 to 1% by weight. If the concentration of the treating agent in the treating agent-containing aqueous solution is too low, the surface treatment of the substrate body becomes insufficient, and the adhesion of the resulting substrate to the resin and the heat resistance may be insufficient. On the other hand, when the concentration of the treating agent is too high, a condensation reaction due to hydrolysis of the treating agent tends to occur, and the storage stability of the treating agent may be lowered.

  Moreover, pH of the processing agent containing aqueous solution used for this invention becomes like this. Preferably it is 3-10, More preferably, it is 3-7, More preferably, it is 3.5-6. When the pH is within this range, the condensation reaction due to hydrolysis of the treatment agent is suppressed, and the storage stability of the treatment agent can be increased. The pH of the treatment agent-containing aqueous solution may be adjusted using an organic acid such as acetic acid, formic acid, oxalic acid, citric acid, or butyric acid, or a pH adjusting agent such as aqueous ammonia.

  In the present invention, a surfactant containing a coupling agent (A) and a coupling agent (B) is dispersed or dissolved in water to prepare a treating agent-containing aqueous solution. Or a small amount of a water-soluble organic solvent may be used.

  Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Among these, workability and characteristics, as well as ion migration, etc. It is preferable to use a nonionic surfactant because it is less likely to occur. By using a surfactant, the coupling agent (A) and the coupling agent (B) can be uniformly dispersed in the treating agent-containing aqueous solution, and the effect of suppressing the condensation reaction by hydrolysis is enhanced and storage stability is improved. Can be improved.

  Specific examples of such nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene octyl ether and polyoxyethylene second alkyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, Polyoxyethylene alkylphenyl ethers such as oxyethylene phenyl ether; alkylcarbonyloxypolyoxyethylenes; aliphatic polyhydric alcohol esters; aliphatic polyhydric alcohol polyoxyethylenes; aliphatic sucrose esters; be able to. These may be used alone or in combination of two or more.

  The amount of the surfactant used is preferably 0.01 to 5% by weight, more preferably 0.05 to 1% by weight in terms of solid content in the treatment agent-containing aqueous solution.

  Examples of the water-soluble organic solvent include alcohols, ketones, pyrrolidones, furans, amines, and carboxylic acids, among which alcohols and ketones are preferable, alcohols are more preferable, methanol and Ethanol is particularly preferred. The water-soluble solvents can be used alone or in combination of two or more.

(resin)
Next, the resin constituting the composite material of the present invention will be described. The resin constituting the composite material of the present invention is not particularly limited as long as it can be in close contact with or integrated with the above-described base material of the present invention.

  Examples of such polymers include polyethers such as polyphenylene ether and polyphenylene oxide; conjugated diene polymers such as polybutadiene, polyisoprene and butadiene-isoprene copolymers; polyolefins such as poly-4-methylpentene and polystyrene; wholly aromatic polyesters Liquid crystalline polymers such as cycloaliphatic polymers, alicyclic structure-containing polymers such as cycloolefin polymers, and the like. Among these, a polymer having a low polarity is preferred, and a polymer having a dielectric loss at 1 GHz of 0.01 or less is preferred from the viewpoint that it can be suitably used particularly for high-frequency circuit board applications. Specifically, An alicyclic structure-containing polymer is preferable, and a cycloolefin polymer is more preferable.

  Among cycloolefin polymers, a polymer obtained by bulk polymerization of a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst is particularly preferable. By using such a polymerizable composition and performing bulk polymerization in the presence of the base material of the present invention described above, a polymerization reaction and a step of forming a resin layer made of resin on the base material are simultaneously performed. This can improve productivity. Here, “performing bulk polymerization in the presence of the base material” means that the surface of the base material of the present invention is in a state where the portion treated with the treatment agent and the polymerizable composition are in contact with each other. It means performing polymerization.

Examples of a method for performing bulk polymerization of a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst include the following methods.
That is, when the substrate is in the form of particles or short fibers, a method in which the substrate is dispersed in the polymerizable composition and then bulk polymerization is used. In this case, the bulk polymerization may be performed in a mold, or the polymerizable composition may be cast on a support such as a resin film and polymerized on the support.

  When the substrate is a glass cloth, a method in which the substrate is impregnated with the polymerizable composition and then bulk polymerization is performed. As a specific method, there is a method in which a glass cloth is placed in a mold, a polymerizable composition is injected into the mold, the glass cloth is impregnated with the polymerizable composition, and then bulk polymerization is performed. Alternatively, a method in which a glass cloth is placed on a support such as a resin film, the polymerizable composition is cast on the glass cloth, the glass cloth is impregnated with the polymerizable composition, and then bulk polymerization is performed on the support. Can be mentioned.

  Furthermore, when the substrate is in the form of a sheet or plate, a method of casting the polymerizable composition on the substrate and then performing bulk polymerization, or placing the substrate in a mold, the mold Examples thereof include a method in which a polymerizable composition is injected into the inside and then bulk polymerization is performed.

(Polymerizable composition)
The polymerizable composition used in the present invention contains a cycloolefin monomer and a metathesis polymerization catalyst.

  The cycloolefin monomer constituting the polymerizable composition used in the present invention has a ring structure formed of carbon atoms, and a compound having one polymerizable carbon-carbon double bond in the ring structure It is. In the present specification, “polymerizable carbon-carbon double bond” refers to a carbon-carbon double bond capable of chain polymerization (ring-opening polymerization). There are various types of ring-opening polymerization, such as ionic polymerization, radical polymerization, and metathesis polymerization. In the present invention, it usually refers to metases ring-opening polymerization.

Examples of the ring structure of the cycloolefin monomer include monocycles, polycycles, condensed polycycles, bridged rings, and polycycles obtained by combining these. Although there is no limitation in particular in carbon number which comprises each ring structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces.
The cycloolefin monomer may have a hydrocarbon group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkylidene group or an aryl group, or a polar group such as a carboxyl group or an acid anhydride group as a substituent. However, from the viewpoint of making the resulting polymer a low dielectric loss tangent, those having no polar group, that is, those composed only of carbon atoms and hydrogen atoms are preferred.

  As the cycloolefin monomer, either a monocyclic cycloolefin monomer or a polycyclic cycloolefin monomer can be used. From the viewpoint of highly balancing the dielectric properties and heat resistance properties of the composite material obtained, polycyclic cycloolefin monomers are preferred. As the polycyclic cycloolefin monomer, a norbornene-based monomer having a norbornene ring structure in the molecule is particularly preferable. Examples of norbornene monomers include norbornenes, dicyclopentadiene, tetracyclododecenes, and the like.

  Here, the cycloolefin monomer is classified into those having no crosslinkable carbon-carbon unsaturated bond and those having one or more crosslinkable carbon-carbon unsaturated bonds. As used herein, “crosslinkable carbon-carbon unsaturated bond” refers to a carbon-carbon unsaturated bond that does not participate in ring-opening polymerization and can participate in a crosslinking reaction. The crosslinking reaction is a reaction that forms a bridge structure, and there are various forms such as a condensation reaction, an addition reaction, a radical reaction, and a metathesis reaction. In the present invention, usually, a radical crosslinking reaction or a metathesis crosslinking reaction is performed. In particular, it refers to a radical crosslinking reaction. Crosslinkable carbon-carbon unsaturated bonds include carbon-carbon unsaturated bonds other than aromatic carbon-carbon unsaturated bonds, that is, aliphatic carbon-carbon double bonds or aliphatic carbon-carbon triple bonds. In the present invention, it usually means an aliphatic carbon-carbon double bond. In the cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds, the position of the unsaturated bond is not particularly limited, and within the ring structure formed of carbon atoms, any other than the ring structure For example, at the end or inside of the side chain.

  Examples of cycloolefin monomers having no crosslinkable carbon-carbon unsaturated bond include cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, and 3-chlorocyclopentene. , Cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene and other monocyclic cycloolefin monomers; norbornene, 5-methyl-2-norbornene, 5 -Ethyl-2-norbornene, 5-propyl-2-norbornene, 5,6-dimethyl-2-norbornene, 1-methyl-2-norbornene, 7-methyl-2-norbornene, 5,5,6-trimethyl-2 -Norbornene, 5-Fe Lu-2-norbornene, tetracyclododecene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5 , 8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5 , 8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1 , 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4 , 4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-di Tano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5 8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro- 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3 4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloro-2-norbornene, 5,5-dichloro-2-norbornene, 5-fluoro-2-norbornene, 5 , 5,6-trifluoro-6-trifluoromethyl 2-norbornene, 5-chloromethyl-2-norbornene, 5-methoxy-2-norbornene, 5,6-dicarboxyl-2-norbornene anhydrate, 5-dimethylamino-2-norbornene, 5-cyano-2 -Norbornene monomers such as norbornene; and the like, preferably norbornene monomers having no crosslinkable carbon-carbon unsaturated bond.

Examples of the cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds include 3-vinylcyclohexene, 4-vinylcyclohexene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4- Monocyclic cycloolefin monomers such as cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene; 5-ethylidene-2-norbornene, 5-methylidene -2-norbornene, 5-isopropylidene-2-norbornene, 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 5,6-diethylidene-2-norbornene, dicyclopentadiene, 2,5-norbornadiene, etc. Norbornene-based monomers; Sexual carbon - is a norbornene-based monomer having one or more carbon unsaturated bond.
These cycloolefin monomers can be used alone or in combination of two or more.

As the cycloolefin monomer used in the present invention, one containing a cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds is preferable because the reliability of the resulting composite material is improved.
A cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond and a cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond in the cycloolefin monomer to be blended in the polymerizable composition of the present invention. The blending ratio is appropriately selected as desired, but usually in a weight ratio (cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds / cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bonds). 0.01 / 99.9 to 100/0, preferably 1/99 to 90/10, more preferably 5/95 to 80/20. When these compounding ratios are in such a range, the heat resistance of the obtained composite material can be further improved.

  As the metathesis polymerization catalyst constituting the polymerizable composition used in the present invention, any catalyst capable of metathesis ring-opening polymerization of a cycloolefin monomer may be used, but usually a plurality of ions, atoms having a transition metal atom as a central atom. And a complex formed by bonding polyatomic ions and / or compounds. As transition metal atoms, atoms of Group 5, Group 6, and Group 8 (long period periodic table, the same applies hereinafter) are used. Although the atoms of each group are not particularly limited, examples of the Group 5 atom include tantalum, examples of the Group 6 atom include molybdenum and tungsten, and examples of the Group 8 atom include ruthenium and osmium. Can be mentioned. Among these, a group 8 ruthenium or osmium complex is preferably used as a metathesis polymerization catalyst, and a ruthenium carbene complex is particularly preferable. The ruthenium carbene complex has excellent catalytic activity during bulk polymerization, and therefore has excellent productivity, and has low odor derived from unreacted monomers and excellent workability. The ruthenium carbene complex is relatively stable to oxygen and moisture in the air and is not easily deactivated, so that it can be used for production in the atmosphere.

Examples of the ruthenium carbene complex include those represented by the following general formula (3) or general formula (4).

In the general formula (3) and the general formula (4), R ² and R ³ each independently represent a hydrogen atom, a halogen atom, or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. The C1-C20 hydrocarbon group which may be included is represented.

Z ¹ and Z ² each independently represents an arbitrary anionic ligand. An anionic ligand is a ligand having a negative charge when pulled away from a central metal atom, such as a halogen atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxyl group, an aryloxy group, A carboxyl group etc. can be mentioned. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

L ¹ and L ² each independently represents a hetero atom-containing carbene compound or a neutral electron donating compound. A hetero atom means an atom of Group 15 and Group 16 of the Periodic Table, and specific examples thereof include N, O, P, S, As, and Se atoms. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, S atoms and the like are preferable, and N atoms are particularly preferable.

Examples of the heteroatom-containing carbene compound include compounds represented by the following general formula (5) or general formula (6).

In the formula, R ^{4 to} R ⁷ are each independently a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms that may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Represents a hydrogen group. R ^{4 to} R ⁷ may be bonded to each other in any combination to form a ring.

  The neutral electron donating compound may be any ligand as long as it has a neutral charge when separated from the central metal. Specific examples thereof include phosphines, ethers and pyridines, and trialkylphosphine is more preferable.

In the above formulas (3) and (4), R ² and R ³ may be bonded to each other to form a ring, and further R ² , R ³ , Z ¹ , Z ² , L ¹ and L ² May be bonded together in any combination to form a multidentate chelating ligand.

  In the present invention, the use of a ruthenium catalyst having a compound having a heterocyclic structure as a ligand as a metathesis polymerization catalyst can highly balance the high-frequency characteristics and heat resistance characteristics of the obtained composite material. Therefore, it is preferable. Examples of the hetero atom constituting the heterocyclic structure include an O atom and an N atom, and an N atom is preferable. Moreover, as a heterocyclic structure, an imidazoline structure and an imidazolidine structure are preferable.

As a ruthenium catalyst having such a compound having a heterocyclic structure as a ligand, a ligand composed of a heteroatom-containing carbene compound represented by the above formula (3) or (4) is used as L ¹ or L ^2. The ruthenium catalyst which has can be used suitably. As a hetero atom constituting the hetero atom-containing carbene compound, an N atom is preferable. Specific examples of such heteroatom-containing carbene compounds include, for example, 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1 , 3-di (1-phenylethyl) -4-imidazoline-2-ylidene, benzylidene (1,3-dimesitylimidazolidin-2-ylidene), 1,3-dimesitylimidazolidin-2-ylidene, Examples include 1,3-dicyclohexylimidazolidine-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene, and the like.

  Specific examples of the ruthenium catalyst having a ligand composed of a heteroatom-containing carbene compound include benzylidene (1,3-dimesityrylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3 -Dimesitylimidazolidin-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) Tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydro Imidazole-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-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityloimidazolidine-2-ylidene) Examples thereof include a ruthenium complex compound in which a hetero atom-containing carbene compound and a neutral electron donating compound are bonded as a ligand, such as pyridine ruthenium dichloride.

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

  If necessary, the metathesis polymerization catalyst can be used by dissolving or suspending in a small amount of an inert solvent. Examples of such solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin, and mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, Alicyclic hydrocarbons such as diethylcyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; and alicyclic rings such as indene and tetrahydronaphthalene And hydrocarbons having an aromatic ring; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, and acetonitrile; oxygen-containing hydrocarbons such as diethyl ether and tetrahydrofuran; Among these, it is preferable to use aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and hydrocarbons having an alicyclic ring and an aromatic ring.

  In addition to the cycloolefin monomer and the metathesis polymerization catalyst, the polymerizable composition used in the present invention may optionally include a chain transfer agent, a crosslinking agent, a filler, a polymerization regulator, a polymerization reaction retarder, an antiaging agent, Other compounding agents can be added.

  Examples of the chain transfer agent used in the present invention include compounds having a vinyl group. Specific examples of such chain transfer agents include 1-hexene, 2-hexene, styrene, vinylcyclohexane, allylamine, glycidyl acrylate, allyl glycidyl ether, ethyl vinyl ether, methyl vinyl ketone, 2- (diethylamino) ethyl acrylate, A chain transfer agent having no crosslinkable carbon-carbon unsaturated bond, such as 4-vinylaniline; divinylbenzene, vinyl methacrylate, allyl methacrylate, styryl methacrylate, allyl acrylate, undecenyl methacrylate, styryl acrylate, Chain transfer agent having one crosslinkable carbon-carbon unsaturated bond, such as ethylene glycol diacrylate; Chain transfer agent having two or more crosslinkable carbon-carbon unsaturated bonds, such as allyltrivinylsilane and tetraallylsilane Is It is. Among these, those having one crosslinkable carbon-carbon unsaturated bond are preferable, chain transfer agents having one vinyl group and one methacryl group are more preferable, vinyl methacrylate, allyl methacrylate, methacrylic acid. Styryl and undecenyl methacrylate are particularly preferred.

  These chain transfer agents can be used alone or in combination of two or more. The amount of the chain transfer agent is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the cycloolefin monomer.

  Examples of the crosslinking agent include radical generators, epoxy compounds, isocyanate group-containing compounds, Lewis acids and the like, and radical generators are particularly preferable. By containing a crosslinking agent in the polymerizable composition, a polymer obtained by polymerizing the polymerizable composition can be made into a crosslinkable polymer.

  Examples of the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators. From the viewpoint that the dielectric loss tangent of the obtained resin can be lowered, organic peroxides, Polar radical generators are preferred.

  Examples of the organic peroxide include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (t- Butylperoxy-m-isopropyl) benzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5-di ( dialkyl peroxides such as t-butylperoxy) hexane; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,2-di (t-butylperoxy) butane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -2-methyl Peroxyketals such as chlorocyclohexane and 1,1-di (t-butylperoxy) cyclohexane; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropylcarbonate, di (isopropylperoxy) ) Peroxycarbonates such as dicarbonate; alkylsilyl peroxides such as t-butyltrimethylsilyl peroxide; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, 3,6,9-triethyl-3 , 6,9-trimethyl-1,4,7-triperoxonane, cyclic peroxides such as 3,6-diethyl-3,6-dimethyl-1,2,4,5-tetroxane; Among these, dialkyl peroxides, peroxyketals, and cyclic peroxides are preferable in that there are few obstacles to the polymerization reaction.

  Examples of the diazo compound include 4,4'-bisazidobenzal (4-methyl) cyclohexanone and 2,6-bis (4'-azidobenzal) cyclohexanone.

  Nonpolar radical generators include 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1,1,2-triphenylethane, 1,1,1- And triphenyl-2-phenylethane.

  These crosslinking agents can be used alone or in combination of two or more. The amount of the crosslinking agent to be added to the polymerizable composition is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, and still more preferably 0.5 to 100 parts by weight of the cycloolefin monomer. The range is ˜5 parts by weight.

  The filler is not particularly limited as long as it is generally used industrially, and any of inorganic fillers and organic fillers can be used, but inorganic fillers are preferred. By blending a filler with the polymerizable composition of the present invention, the mechanical strength and heat resistance of the resulting composite material can be improved.

  Examples of the inorganic filler include metal particles such as iron, copper, nickel, gold, silver, aluminum, lead, and tungsten; carbon particles such as carbon black, graphite, activated carbon, and carbon balloon; silica, silica balloon, alumina, Inorganic oxide particles such as titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, beryllium oxide, barium ferrite, strontium ferrite; inorganic carbonate particles such as calcium carbonate, magnesium carbonate, sodium hydrogen carbonate; calcium sulfate, etc. Inorganic sulfate particles; inorganic silicate particles such as talc, clay, mica, kaolin, fly ash, montmorillonite, calcium silicate, glass, glass balloon; titanate particles such as calcium titanate and lead zirconate titanate; Aluminum nitride, silicon carbide particles Whiskers, and the like. Examples of the organic filler include compound particles such as wood powder, starch, organic pigments, polystyrene, nylon, polyolefins such as polyethylene and polypropylene, vinyl chloride, and waste plastics. These fillers can be used alone or in combination of two or more. These are preferably surface-treated with a silane coupling agent or the like.

  The blending amount of the filler is usually 1 to 1,000 parts by weight, preferably 10 to 500 parts by weight, and more preferably 50 to 350 parts by weight with respect to 100 parts by weight of the cycloolefin monomer.

  The polymerization regulator is blended for the purpose of controlling the polymerization activity or improving the polymerization reaction rate. Examples of the polymerization regulator include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium. , Tetraalkoxytin, tetraalkoxyzirconium and the like. These polymerization regulators can be used alone or in combination of two or more. In the case of using a polymerization regulator, the blending amount of the polymerization regulator is a molar ratio (metal atom in the metathesis polymerization catalyst: polymerization regulator), preferably 1: 0.05 to 1: 100, more preferably 1: It is in the range of 0.2 to 1:20, more preferably 1: 0.5 to 1:10.

  A polymerization reaction retarder can suppress an increase in viscosity of the polymerizable composition of the present invention. Polymerization reaction retarders include phosphine compounds such as triphenylphosphine, tributylphosphine, trimethylphosphine, triethylphosphine, dicyclohexylphosphine, vinyldiphenylphosphine, allyldiphenylphosphine, triallylphosphine, styryldiphenylphosphine; Lewis bases such as aniline and pyridine Etc. can be used. What is necessary is just to adjust suitably the compounding quantity of a polymerization reaction retarder in the case of using a polymerization reaction retarder as needed.

  Examples of the anti-aging agent include phenol-based anti-aging agents, amine-based anti-aging agents, phosphorus-based anti-aging agents, sulfur-based anti-aging agents and the like. By blending these anti-aging agents, a crosslinking reaction can be performed. This is preferable because the heat resistance of the resulting composite material can be improved to a high degree without hindering. Among these, a phenolic antiaging agent and an amine antiaging agent are preferable, and a phenolic antiaging agent is more preferable. These anti-aging agents can be used alone or in combination of two or more. In the case of using an anti-aging agent, the amount of the anti-aging agent used is preferably 0.0001 to 10 parts by weight, more preferably 0.001 to 5 parts by weight, further preferably 100 parts by weight of the cycloolefin monomer. Is in the range of 0.01 to 2 parts by weight.

  Moreover, other compounding agents other than the above-mentioned compounding agents can be blended in the polymerizable composition used in the present invention. As other compounding agents, colorants, light stabilizers, pigments, foaming agents and the like can be used. As the colorant, dyes, pigments and the like are used. There are various kinds of dyes, and known ones may be appropriately selected and used. These other compounding agents can be used alone or in combination of two or more, and the amount used is appropriately selected within a range not impairing the effects of the present invention.

  The polymerizable composition used in the present invention can be obtained by mixing the above components. As a mixing method, a conventional method may be followed. For example, a liquid (catalyst liquid) in which a metathesis polymerization catalyst is dissolved or dispersed in an appropriate solvent is prepared, and a cycloolefin monomer and a phenoxy group-containing oligomer are separately required. The liquid (monomer liquid) which mix | blended the component and the other compounding agent as needed can be prepared, a catalyst liquid is added to this monomer liquid, and it can prepare by stirring.

And the composite material which consists of resin which consists of cycloolefin polymer, and a base material can be obtained by carrying out bulk polymerization of such polymeric composition in presence of a base material. In addition, as a method of performing bulk polymerization in the presence of a substrate, any of the above-described methods can be employed.
The resin comprising the cycloolefin polymer used in the present invention and the resin portion constituting the composite material of the present invention have substantially no cross-linked structure, for example, are soluble in toluene and have a molecular weight of The weight average molecular weight in terms of polystyrene measured by permeation chromatography (eluent: toluene) is usually 1,000 to 1,000,000, preferably 5,000 to 500,000, more preferably 10,000. The range is from 000 to 100,000.

  Here, bulk polymerization is started by heating the polymerizable composition to a temperature at which the metathesis catalyst contained in the polymerizable composition exhibits a function. The temperature at which the polymerization reaction is initiated is usually 50 to 250 ° C, preferably 100 to 200 ° C. The polymerization time may be appropriately selected, but is usually 10 seconds to 20 minutes, preferably within 5 minutes.

  Here, the bulk polymerization reaction is an exothermic reaction, and once the bulk polymerization starts, the temperature of the polymerizable composition rapidly increases and reaches the peak temperature in a short time (for example, about 10 seconds to 5 minutes). When the polymerizable composition contains a crosslinking agent, if the peak temperature during the polymerization reaction becomes too high, the polymerization reaction and the crosslinking reaction proceed at the same time. The resulting polymer. Therefore, when a crosslinkable polymer is obtained, the peak temperature of the polymerizable composition in the bulk polymerization is preferably set so that only the polymerization reaction proceeds and the crosslinking reaction does not proceed. It is preferable to control it to 1 minute half-life temperature or less, more preferably to 1 minute half-life temperature of 10 ° C. or less, and even more preferably to 1 minute half-life temperature of 20 ° C. or less.

  And the cycloolefin polymer which is a crosslinkable polymer obtained in this way can be made into a crosslinked polymer by crosslinking. Crosslinking may be performed, for example, by maintaining a temperature above the temperature at which an uncrosslinked portion in the resin undergoes a crosslinking reaction by heating and melting the composite material obtained by bulk polymerization of the polymerizable composition. it can. The temperature at which the cross-linked moiety is crosslinked is usually at least 1 minute half-life temperature of the radical generator, preferably at least 5 ° C. higher than the 1-minute half-life temperature, more preferably at least 10 ° C. above the 1-minute half-life temperature. High temperature. The crosslinking time is not particularly limited, but is usually from several minutes to several hours.

  When the composite material is in the form of a sheet or a film, a laminate may be formed by laminating a plurality of the composite materials as necessary, followed by hot pressing and crosslinking. As such a sheet-like or film-like composite material, a prepreg in which a resin layer containing a crosslinkable polymer is impregnated into a cloth of a base material, or a crosslinkable polymer and a metal foil are laminated. A metal foil with a resin and the like are preferably exemplified. The pressure of the hot press is usually 0.5 to 20 MPa, preferably 3 to 10 MPa. The hot pressing may be performed in a vacuum or a reduced pressure atmosphere. The hot pressing can be performed using a known press having a press frame mold for flat plate forming, a press molding machine such as a sheet mold compound (SMC) or a bulk mold compound (BMC).

  The composite material of the present invention thus obtained has high-frequency characteristics, adhesion between the substrate and the resin (particularly adhesion when a resin having high fluidity is used), and heat resistance (particularly, solder). Since it is excellent in adhesion between the base material and the resin after the treatment, it can be used widely as a high-frequency substrate material. Specifically, the composite material of the present invention can be suitably used for a microwave or millimeter wave high frequency circuit board for use in communication equipment. Furthermore, when the composite material of the present invention is made by subjecting a glass cloth to a surface treatment as a base material, the impregnation property of the resin into the base material can be improved, whereby the resin and the base material can be improved. In addition, it is possible to improve the crack resistance in the thermal shock test.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on weight unless otherwise specified.
The test and evaluation were as follows.

(1) Molecular weight The molecular weight of the resin in the crosslinkable resin molded article (prepreg) was measured by gel permeation chromatography (eluent: toluene), and the weight average molecular weight (Mw) was determined in terms of polystyrene.

(2) Copper foil appearance The copper foil appearance was evaluated by visually observing treatment spots such as streaks and speckled patterns of the copper foil after the surface treatment, and evaluated the following criteria. The smaller the treatment spots, the more uniformly the treatment agent is applied.
○: No treatment spots were observed on the copper foil surface.
(Triangle | delta): The spot was seen in less than 10 area% among the whole copper foil surfaces.
X: Spots were observed in 10% by area or more of the entire copper foil surface.

(3) Resin fluidity One sheet of crosslinkable resin molded product (prepreg) is sandwiched between an IPC substrate (IPC standard multipurpose substrate) and an electrolytic copper foil (Type GTS, thickness 0.018 mm, manufactured by Furukawa Circuit Foil), and hot pressed. The machine was hot pressed while maintaining the flat plate shape. The conditions of hot pressing were a temperature of 200 ° C., a time of 15 minutes, and a pressure of 5 MPa. After completion of the hot press, the resin embedding evaluation into the IPC substrate was visually evaluated.
○: No voids are observed between the substrates, and the resin follows the irregularities and is neatly embedded. ×: The voids are confirmed throughout the substrate, and the irregularities are not sufficiently embedded.

(4) Stripping strength of copper foil The peeling strength of the copper foil in the laminate using the surface-treated copper foil was measured based on JIS C6481, and evaluated according to the following criteria. It represents that copper foil and resin are firmly and uniformly adhered, so that peeling strength of copper foil is large.
◎: 0.6 kN / m or more ○: 0.5 kN / m or more, less than 0.6 kN / m Δ: 0.4 kN / m or more, less than 0.5 kN / m ×: Less than 0.4 kN / m

(5) Heat resistance The laminate using the surface-treated copper foil was subjected to a solder test under the condition that the test was floated for 10 seconds in a solder bath having a solder temperature of 260 ° C. and allowed to stand at room temperature for 30 seconds three times. About the laminated body after performing a solder test, the peeling strength of copper foil was measured similarly to said (4), and it evaluated on the basis similar to said (4). The greater the peel strength of the copper foil, the stronger and evenly the copper foil and the resin are adhered even after soldering, and the heat resistance is better.

(6) Adhesion between glass cloth and resin (impregnation)
The laminate using the surface-treated glass cloth was cut, the cross section was observed with a scanning electron microscope (SEM), and the adhesion between the resin and the glass cloth was evaluated according to the following criteria.
○: The part which did not adhere was not able to be confirmed.
X: The part which was not closely_contact | adhering was confirmed.

(7) Crack resistance About the laminated body using the surface-treated glass cloth, a thermal shock test of 300 cycles is performed in a temperature range of −40 ° C. to + 150 ° C., and the laminated body after the thermal shock test has an arbitrary 1 cm square. The surface was observed with an optical microscope at a magnification of 50 times, and crack resistance was evaluated according to the following criteria. In addition, the thermal shock test was done with the thermal shock test apparatus (The product made by ESPEC company, model number; TSA-71H-W).
○: The occurrence of cracks was not confirmed.
(Triangle | delta): Generation | occurrence | production of the crack was confirmed in 1-10 places.
X: Generation | occurrence | production of the crack was confirmed by 11 or more places.

(8) Dissipation factor (tan δ)
For a laminate using a surface-treated copper foil and a laminate using a surface-treated glass cloth, a dielectric loss tangent (tan δ) at a frequency of 1 GHz at 20 ° C. using an impedance analyzer (manufactured by Agilent Technologies, model number E4991A) is a capacitance method. And evaluated according to the following criteria.
A: 0.002 or less B: More than 0.002, 0.003 or less C: More than 0.003

Example 1
<Preparation of treatment agent-containing aqueous solution>
P-Styryltrimethoxysilane (KBM-1403, manufactured by Shin-Etsu Chemical Co., Ltd.) as the coupling agent (A) and bis (trimethoxysilyl) octane (SIB1824.0, manufactured by Asmax Co., Ltd.) as the coupling agent (B) ) Was dissolved in methanol at a ratio of “bis (trimethoxysilyl) octane” / “p-styryltrimethoxysilane” = 0.05 (weight ratio) to a concentration of 50%. Next, the solution is dissolved by sequentially dropping it into an aqueous solution containing 0.06% of polyoxyethylene octylphenol ether (trade name: HS-210, manufactured by NOF Corporation, HLB value 13, 5) as a surfactant. I let you. The dropping speed was 5 ml / min per liter of the surfactant-containing aqueous solution. Further, acetic acid was added dropwise so that the pH of this solution was 4.0, to obtain a treatment agent-containing aqueous solution having a silane coupling agent concentration of 0.03%.

<Surface treatment of copper foil>
The treating agent-containing aqueous solution obtained above was applied to a 1 m square copper foil (electrolytic copper foil having a thickness of 12 μm, surface chromate treatment, roughness Rz = 0.8 μm, manufactured by Furukawa Circuit Foil Co., Ltd.) at a temperature of 23 ° C. and humidity In a 50% environment, the coating was uniformly applied to a coating thickness of 4 μm using a bar coater. Next, this was immediately dried at 120 ° C. for 5 minutes under a nitrogen stream to obtain a surface-treated copper foil.

<Preparation of polymerizable composition>
In a glass flask, 51 parts of benzylidene (1,3-dimethyl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and 79 parts of triphenylphosphine were dissolved in 952 parts of toluene to form a catalyst. A liquid was prepared. On the other hand, in addition to this, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-ene (TCD) 80 parts and a mixture of dicyclopentadiene 20 parts, where 3.5 parts of allyl methacrylate as a chain transfer agent and di-tert-butyl peroxide ( A monomer solution was prepared by adding 1.2 parts of 1-minute half-life temperature of 186 ° C. and 100 parts of silica (average particle size 0.5 μm, silane coupling agent-treated product, manufactured by Admatechs) and mixing them. And the catalyst liquid prepared above was added to the obtained monomer liquid in the ratio of 0.12 mL per 100 g of cycloolefin monomers, and it stirred, and prepared the polymeric composition.

<Preparation of laminate using surface-treated copper foil>
Next, 100 parts of the obtained polymerizable composition was cast on a polyethylene naphthalate film (type Q51, thickness 75 μm, manufactured by Teijin DuPont Films), and a glass cloth (product number 2116, thickness 92 μm) was spread thereon. Further, 80 parts of the polymerizable composition was cast thereon. Further, a polyethylene naphthalate film was covered thereon, and the entire glass cloth was impregnated with the polymerizable composition using a roller. Next, this was heated for 1 minute in a heating furnace heated to 145 ° C., and the polymerizable composition was subjected to bulk polymerization to obtain a crosslinkable resin molded article (prepreg) having a thickness of 0.13 mm.
Next, the obtained prepreg was cut out to a size of 100 mm square, the polyethylene naphthalate film was peeled off, and eight sheets thereof were stacked, and the surface-treated copper foil obtained above was placed on the outermost surface. It arrange | positioned so that it might contact, and heat-pressed for 15 minutes on the conditions of 3 Mpa and 200 degreeC with the hot press, and the laminated body using surface-treated copper foil was produced. And about each obtained laminated body using the surface-treated copper foil, according to the said method, each evaluation of the peeling strength of copper foil, heat resistance, and dielectric loss tangent (tan-delta) was performed. Moreover, about the surface treatment copper foil, the external appearance was also evaluated according to the said method. The results are shown in Table 1.

Examples 2-5
The ratio of p-styryltrimethoxysilane as the coupling agent (A) and bis (trimethoxysilyl) octane as the coupling agent (B) in terms of weight ratio is “bis (trimethoxysilyl) octane”, respectively. /“P-styryltrimethoxysilane”=0.10 (Example 2), 0.20 (Example 3), 0.33 (Example 4), 0.50 (Example 5) In the same manner as in Example 1, a surface-treated copper foil and a laminate using the surface-treated copper foil were obtained and evaluated in the same manner. The results are shown in Table 1.

Example 6
As the coupling agent (B), bis (trimethoxysilyl) hexane (SIB1821.0, manufactured by Azmax) was used instead of bis (trimethoxysilyl) octane, and the ratio of the coupling agent was changed to “bis (trimethoxy). A surface-treated copper foil and a laminate using the surface-treated copper foil are obtained in the same manner as in Example 1 except that “silyl) hexane” / “p-styryltrimethoxysilane” = 0.10 (weight ratio). The same evaluation was performed. The results are shown in Table 1.

Example 7
As the coupling agent (B), 1,4-bis (triethoxysilylethyl) benzene (SIB1831.0, manufactured by Azmax) was used instead of bis (trimethoxysilyl) octane, and the ratio of the coupling agent was Surface treated copper foil and surface in the same manner as in Example 1 except that “1,4-bis (triethoxysilylethyl) benzene” / “p-styryltrimethoxysilane” = 0.15 (weight ratio). A laminate using the treated copper foil was obtained and evaluated in the same manner. The results are shown in Table 1.

Example 8
When preparing a crosslinkable resin molded article (prepreg), a surface-treated copper foil and a surface-treated copper foil were prepared in the same manner as in Example 2 except that a polybutadiene-based resin was used instead of the polymerizable composition containing a cycloolefin monomer. A laminate using a surface-treated copper foil was obtained and evaluated in the same manner. The results are shown in Table 1.

Example 9
<Surface treatment of glass cloth>
A glass cloth (thickness: 80 μm, weight per unit area: 85 g / m ² , E glass) not subjected to surface treatment was heat-treated at a temperature of 400 ° C. for 27 hours. Next, the glass cloth after the heat treatment was immersed in a treating agent-containing aqueous solution produced in the same manner as in Example 1, and the surplus was squeezed and dried to obtain a surface-treated glass cloth. The total adhesion amount of styryltrimethoxysilane and bis (trimethoxysilyl) octane to the glass cloth was 0.08%.

<Production of laminate using surface-treated glass cloth>
100 parts of the polymerizable composition obtained in the same manner as in Example 1 was cast on a polyethylene naphthalate film (type Q51, thickness 75 μm, manufactured by Teijin DuPont Films), and obtained above. A surface-treated glass cloth is laid, and then 80 parts of the polymerizable composition is cast thereon, and a polyethylene naphthalate film is further coated thereon, and the polymerizable composition is applied to the surface-treated glass cloth using a roller. Impregnated. Next, this was heated for 1 minute in a heating furnace heated to 145 ° C., and the polymerizable composition was subjected to bulk polymerization to obtain a crosslinkable resin molded article (prepreg) having a thickness of 0.13 mm.
Next, the obtained prepreg was cut to a size of 100 mm square, the polyethylene naphthalate film was peeled off, 8 sheets thereof were stacked, and a copper foil (thickness) on which the surface treatment with a coupling agent was not performed on the outermost surface. 12μm electrolytic copper foil, surface chromate treatment, roughness Rz = 0.8μm, manufactured by Furukawa Circuit Foil Co., Ltd.) and heat-pressed for 15 minutes under the conditions of 3MPa and 200 ° C with a hot press. The laminated body used was produced. And about the laminated body using the obtained surface treatment glass cloth, according to the said method, each evaluation of the adhesiveness of a glass cloth and resin, crack resistance, and dielectric loss tangent (tan-delta) was performed. The results are shown in Table 2.

Comparative Example 1
A laminate using the surface-treated copper foil and the surface-treated copper foil was obtained in the same manner as in Example 1 except that bis (trimethoxysilyl) octane as the coupling agent (B) was not used. Evaluation was performed. The results are shown in Table 1. In Comparative Example 1, the blending amount of styryltrimethoxysilane as the coupling agent (A) is as follows: styryltrimethoxysilane as the coupling agent (A) in Example 1 and coupling agent (B). The total amount of bis (trimethoxysilyl) octane was the same as that of Comparative Example 2-5 (hereinafter, also in Comparative Examples 2-5).

Comparative Example 2
A surface-treated copper foil and a laminate using the surface-treated copper foil were obtained in the same manner as in Example 1 except that styryltrimethoxysilane as a coupling agent (A) was not used, and evaluation was performed in the same manner. It was. The results are shown in Table 1.

Comparative Example 3
When preparing the surface-treated copper foil, styryltrimethoxysilane as a coupling agent (A) is not used, and when preparing a polymerizable composition, the amount of allyl methacrylate as a chain transfer agent is 3 A laminated body using the surface-treated copper foil and the surface-treated copper foil was obtained in the same manner as in Example 1 except that the amount was changed from 0.5 part to 2.6 parts, and evaluation was performed in the same manner. The results are shown in Table 1.

Comparative Example 4
Except not having used bis (trimethoxysilyl) octane as a coupling agent (B), it carried out similarly to Example 9, and obtained the laminated body using the surface treatment glass cloth, and evaluated similarly. The results are shown in Table 2.

Comparative Example 5
A laminate using a surface-treated glass cloth was obtained in the same manner as in Example 9 except that styryltrimethoxysilane as a coupling agent (A) was not used, and evaluation was performed in the same manner. The results are shown in Table 2.

As shown in Table 1, the laminated body obtained using the copper foil surface-treated with the treatment agent containing the coupling agent (A) and the coupling agent (B) according to the present invention comprises a resin layer and copper. It became the result excellent in adhesiveness and heat resistance with foil (Examples 1-8).
Moreover, as shown in Table 2, the laminated body obtained using the glass cloth surface-treated with the treatment agent containing the coupling agent (A) and the coupling agent (B) according to the present invention comprises a resin and It was excellent in the adhesion between the glass cloth and the crack resistance (Example 9).
On the other hand, as shown in Table 1, the laminated body obtained using the copper foil surface-treated with only one of the coupling agent (A) and the coupling agent (B) is composed of a resin layer and a copper foil. The results were poor in adhesion and heat resistance (Comparative Examples 1 and 2).
When using a copper foil surface-treated only with the coupling agent (B) and using a cycloolefin polymer having a molecular weight of 25,000 as the prepreg, the resulting laminate has a molecular weight of Despite the use of a high resin, the adhesion and heat resistance between the resin layer and the copper foil are still inferior, and the fluidity is also inferior, which is not suitable for high frequency circuit board applications (Comparative Example) 3).
Moreover, as shown in Table 2, the laminated body obtained using the glass cloth surface-treated only with the coupling agent (A) resulted in inferior crack resistance (Comparative Example 4).
Furthermore, as shown in Table 2, the laminate obtained using the glass cloth surface-treated only with the coupling agent (B) resulted in inferior impregnation and crack resistance (Comparative Example 5). ).

Claims (5)

A composite material comprising a substrate and a resin layer comprising an alicyclic structure-containing polymer obtained by bulk polymerization of a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst,
The base is made is treated with a treating agent containing a coupling agent represented by the following general formula (1) (A), and a coupling agent represented by the following general formula (2) (B), wherein The ratio of the coupling agent (A) and the coupling agent (B) is, by weight ratio, coupling agent (B) / coupling agent (A) = 0.001 to 2.0,
The said resin layer is a composite material formed by carrying out block polymerization in the state which the part processed with the said processing agent and the said polymeric composition contacted among the surfaces of the said base material.

(In the above general formula (1), M ¹ represents Ti, Si, Al or Zr, R ¹ represents a hydrocarbon group having a double bond, a mercapto group or an amino group at the end, and X ¹ , X ² independently represents a hydrolyzable group, a hydroxyl group or an alkyl group, and X ³ represents a hydrolyzable group or a hydroxyl group, wherein M ² represents Ti, Si, Al or Zr in the general formula (2). X ⁴ and X ⁵ each independently represents a hydrolyzable group, a hydroxyl group or an alkyl group, X ⁶ represents a hydrolyzable group or a hydroxyl group, and Y represents a substituent containing a nitrogen atom, an oxygen atom or a sulfur atom. A linear, branched or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a group, or an aromatic carbon which may have a substituent containing a nitrogen atom, an oxygen atom or a sulfur atom Represents a hydrogen group.) The composite of claim 1 dielectric loss at 1GHz of the resin layer is 0.01 or less. The composite material according to claim 1, wherein the polymerizable composition further contains a chain transfer agent, a crosslinking agent, and a filler. The composite material according to claim 1, wherein the treatment agent further contains a surfactant. A method for producing a composite material comprising a substrate and a resin layer comprising an alicyclic structure-containing polymer obtained by bulk polymerization of a polymerizable composition containing a cycloolefin monomer and a metathesis polymerization catalyst,
A step of treating the base material with a treatment agent containing a coupling agent (A) represented by the following general formula (1) and a coupling agent (B) represented by the following general formula (2);
A step of forming the resin layer by bulk polymerization of the polymerizable composition in a state where the polymerizable composition is in contact with a portion of the surface of the substrate that has been treated with the treatment agent. And
A composite material in which the ratio of the coupling agent (A) to the coupling agent (B) is, by weight, coupling agent (B) / coupling agent (A) = 0.001 to 2.0. Manufacturing method.

(In the above general formula (1), M ¹ Represents Ti, Si, Al or Zr, and R ¹ Represents a hydrocarbon group having a double bond, a mercapto group or an amino group at the end, and X ¹ , X ² Each independently represents a hydrolyzable group, a hydroxyl group or an alkyl group; ³ Represents a hydrolyzable group or a hydroxyl group. In the general formula (2), M ² Represents Ti, Si, Al or Zr, and X ⁴ , X ⁵ Each independently represents a hydrolyzable group, a hydroxyl group or an alkyl group; ⁶ Represents a hydrolyzable group or a hydroxyl group, and Y represents a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent containing a nitrogen atom, an oxygen atom or a sulfur atom. Or an aromatic hydrocarbon group which may have a substituent containing a nitrogen atom, an oxygen atom or a sulfur atom. )