JP2010046914A - Laminate and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate suitable for printed wiring substrate, and excellent in low water absorption properties, soldering heat resistance after moisture absorption, soldering heat resistance, electric characteristics, coefficient of linear expansion, property of having no air bubble, peeling strength to copper foil, and presentable appearance. <P>SOLUTION: The laminate is composed of (A) a thermoplastic resin composition containing not less than 80 mass% of polyphenylene ether and (B) a fibrous glass material. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a laminate of a thermoplastic resin composition and a glass fiber fabric excellent in low water absorption, electrical characteristics, low linear expansion coefficient, copper foil peel strength, and appearance. In particular, the present invention relates to a laminate of a resin composition containing a thermoplastic polyphenylene ether and a glass fiber fabric excellent in electrical characteristics, a low linear expansion coefficient, and a copper foil peel strength.

In recent years, as electronic devices have become smaller, thinner, lighter, and more advanced, various electronic components that make up electronic devices have become smaller and thinner, and printed circuit boards on which these electronic components are mounted In addition, various technological developments that enable high-density mounting are also active. Therefore, the characteristics required for films for electronic materials such as printed wiring boards are higher than before, and conventional epoxy resin laminates are related to electrical characteristics, heat resistance, dimensional stability (low linear expansion coefficient), and low water absorption. It has become difficult to satisfy the required characteristics.
A candidate for a new printed wiring board material that solves this problem is polyphenylene ether excellent in electrical characteristics, heat resistance, low water absorption, and flame retardancy.

  So far, many studies have been made on applying polyphenylene ether as a component of a cured resin to a laminate. For example, a technique in which a composition comprising polyphenylene ether, triallyl isocyanurate, epoxy resin and allyl glycidyl ether is dissolved in a solvent, impregnated into a glass fiber fabric, and heated to obtain a thermosetting composition (Patent Document 1) In addition, a technique (Patent Document 2) has been proposed in which a composition comprising polyphenylene ether, triallyl isocyanurate, and allyl alcohol is dissolved in a solvent, impregnated into a glass fiber fabric, and a thermosetting composition is obtained by heating. It was. However, these are all unsuitable from the viewpoint of becoming a thermosetting resin and recycling the product. Moreover, since it contains many additional components, it cannot be said that it is a laminated board for printed wiring boards that sufficiently utilizes the original characteristics of polyphenylene ether, such as electrical characteristics and water absorption.

In addition, the use of a thermosetting resin as well as the use of a thermoplastic resin as a material to be laminated with a glass fiber fabric has been proposed. However, there is no suggestion about the proportion of polyphenylene ether, and there is no specific disclosure. It cannot be said that it is a laminated board for printed wiring boards that fully utilizes the inherent properties of ether. (Patent Document 3)
In addition, as a material laminated with glass fiber fabric, as a thermoplastic resin, polyether ether ketone (PEEK), polyether imide (PEI), liquid crystal polymer (LCP), polyether sulfone (PES), polyphenylene ether (PPE) Polystyrene naphthalate (PEN) and a styrene resin having a syndiotactic structure have been proposed, but there is no suggestion of a specific content ratio and no specific disclosure of polyphenylene ether. The water absorption rate is not sufficient. (Patent Document 4)
Liquid crystal polymer (LCP) is also a resin excellent in heat resistance, flame retardancy, and electrical properties, but has a drawback of being expensive and having large anisotropy. In order to alleviate the anisotropy, various measures are taken when forming the film, but all of them lead to an increase in cost in order to obtain a resin film.

Generally, polyphenylene ether itself cannot be said to have sufficient adhesion with copper foil. Therefore, studies have been made on using an adhesive or roughening the surface of the copper foil. However, using an adhesive causes a decrease in electrical characteristics (low dielectric constant, low dielectric loss tangent). On the other hand, when the surface of the copper foil becomes rough, the frequency becomes high, and when an electric signal passes through the conductor, it causes a loss and a malfunction. Therefore, there has been a demand for a technique that gives high adhesion between polyphenylene ether and copper foil without using an adhesive and having a low copper foil surface roughness.
JP-A-6-32875 JP-A-6-206955 Japanese Patent Laid-Open No. 11-158771 JP 2008-141008 A

  The object of the present invention is suitable for a printed wiring board, and has not been able to be achieved by the above-described technique, low water absorption, solder heat resistance after moisture absorption, solder heat resistance, electrical characteristics, coefficient of linear expansion, no bubble, and peel with copper foil It is to provide a laminate having excellent strength and appearance.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have included a specific amount of polyphenylene ether in a specific amount of resin composition, so that low water absorption, moisture absorption after moisture absorption, solder heat resistance, electrical characteristics, wire The inventors have found that a laminate having excellent expansion coefficient, no bubbles, peel strength with copper foil, and appearance can be obtained, and the present invention has been achieved.
Next, in order to facilitate understanding of the present invention, basic features and preferred embodiments of the present invention will be listed.
(1) A laminate comprising (A) a thermoplastic resin composition containing 80% by mass or more of polyphenylene ether and (B) a glass fiber fabric.
(2) The laminate according to 1 above, wherein the polyphenylene ether in the laminate contains 0.9 or more phenolic hydroxyl groups per 100 phenylene ether units.

(3) (C) A thermoplastic resin other than (A) is an aromatic vinyl compound polymer, an aromatic vinyl compound copolymer, polypropylene, polyethylene, polyamide 6, polyamide 66, polyamide 66/6, containing an aromatic ring It is at least one selected from polyamide, aliphatic ring-containing polyamide, polyphenylene sulfide, liquid crystal polymer, polyether ether ketone, polyarylate, polyether sulfone, polysulfone, and the resin composition is the sum of (A) and (C) The laminated body in any one of said 1 or 2 which contains 20 mass parts or less of (C) with respect to 100 mass parts.
(4) The laminate according to 3 above, wherein the component (C) is a liquid crystal polymer and / or an aromatic vinyl-maleimide copolymer.
(5) The resin composition according to the above 1-4, wherein the resin composition contains 3 parts by mass or less of a compound containing (D) Zn element and / or Mg element with respect to a total of 100 parts by mass of (A) and (C). The laminated body in any one.

(6) The laminate according to any one of (1) to (5) above, wherein the resin composition contains 1 to 10 parts by mass of (E) phosphinic acid salt with respect to 100 parts by mass in total of (A) and (C).
(7) The laminate according to any one of the above 1 to 6, wherein copper is further bonded.
(8) The multilayer laminate according to any one of 1 to 7 above, wherein the glass fiber fabric is composed of two or more layers.
(9) The laminate according to any one of 1 to 8 above, wherein the thermoplastic resin composition film and the glass fiber fabric are hot press molded at a temperature of 240 ° C. or higher and 340 ° C. or lower and at a pressure of 1 MPa to 40 MPa. Manufacturing method.
(10) The manufacturing method according to 9 above, wherein hot press molding is performed in a vacuum state of 30 kPa or less.
(11) The laminate according to any one of 1 to 6 above, wherein the thermoplastic resin composition is dissolved in a good solvent in advance and the glass fiber fabric is impregnated with the solution, and then the solvent is distilled off by heating and / or decompression. Manufacturing method.

(12) Manufacture of a laminate to be hot press-molded at a temperature of 240 ° C. or higher and 340 ° C. or lower and a pressure of 1 MPa to 40 MPa in order to bond the laminate obtained in 11 above to a copper foil. Method.
(13) The production method according to the above 9 to 12, wherein continuous forming is performed with a roll tow roll.
(14) An electric circuit board using the laminate according to any one of 1 to 8 above.
(15) An interlayer insulating film using the laminate according to any one of 1 to 8 above.
(16) A flexible circuit board using the laminate according to any one of 1 to 8 above.
(17) A rigid circuit board using the laminate according to any one of 1 to 8 above.
(18) A multilayer circuit board for build-up using the laminate according to any one of 1 to 8 above.

  It is suitable for a printed wiring board, and can provide a laminate having low water absorption, solder heat resistance after moisture absorption, solder heat resistance, electrical characteristics, linear expansion coefficient, no bubble, peel strength with copper foil, and excellent appearance.

Next, each component that can be used in the present invention will be described in detail.
The polyphenylene ether of component (A) is a homopolymer and / or copolymer composed of the structural unit of the formula (1).

[Wherein O is an oxygen atom, R is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy (provided that At least two carbon atoms separating the halogen atom and the oxygen atom). ]

  Specific examples of the polyphenylene ether of the present invention include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (For example, a copolymer with 2,3,6-trimethylphenol or a copolymer with 2-methyl-6-butylphenol as described in JP-B-52-17880) Polyphenylene ether copolymers may also be mentioned. When using a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol as polyphenylene ether, the ratio of each monomer unit is based on the total amount of polyphenylene ether copolymer being 100% by mass. Further, a copolymer composed of 60 to 90% by mass of 2,6-dimethylphenol and 10 to 40% by mass of 2,3,6-trimethylphenol is preferable. The ratio of 2,3,6-trimethylphenol is 10% by mass or more from the viewpoint of heat resistance, and 40% by mass or less from the viewpoint of the degree of polymerization. More preferably, a copolymer comprising 60 to 85% by mass of 2,6-dimethylphenol and 15 to 40% by mass of 2,3,6-trimethylphenol is more preferable, and 70 to 85% by mass of 2,6 More preferred is a copolymer comprising dimethylphenol and 15 to 30% by mass of 2,3,6-trimethylphenol.

Among these, particularly preferred polyphenylene ethers include poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or these It is a mixture.
The reduced viscosity (η _{sp / c} : 0.5 g / dl, chloroform solution, measured at 30 ° C.) of the polyphenylene ether that can be used in the present invention is preferably in the range of 0.15 to 0.70 dl / g. More preferably, it is in the range of 0.20 to 0.60 dl / g, more preferably in the range of 0.40 to 0.55 dl / g.
In the present invention, two or more polyphenylene ethers having different reduced viscosities may be blended. For example, a mixture of a polyphenylene ether having a reduced viscosity of 0.45 dl / g or less and a polyphenylene ether having a reduced viscosity of 0.50 dl / g or more, a low molecular weight polyphenylene ether having a reduced viscosity of 0.40 dl / g or less, and a reduced viscosity of 0.50 dl / g or more. A mixture of polyphenylene ethers, etc., of course, is, of course, not limited to these.

The polyphenylene ether in the thermoplastic resin composition preferably contains 0.9 or more phenolic hydroxyl groups per 100 phenylene ether units. The greater this value, the better the peel strength with the copper foil. In this respect, the value is preferably 0.90 or more, more preferably 1.10 or more, and particularly preferably 1.70 or more.
This phenolic hydroxyl group is quantified according to a method such as EHUD SH CHORI (Journal of Applied Polymers Science; Applied Polymer Symposium, 34, pages 103 to 117, (1978)). That is, as a measurement sample, 1) In the case of raw polyphenylene ether which is a raw material of the composition, 2) The thermoplastic resin composition is a strand or pellet obtained at the time of extrusion, 3) Melt molding 4) Laminated body with glass fiber, 5) In the case of a laminated body obtained by laminating with copper foil, after etching the copper foil with an etching solution, 1) as it is, the following weighing (W In the case of 2) to 5), the sample is first dissolved in chloroform at 30 ° C., the insoluble matter is removed, and the solution is poured into a large amount of methanol (reprecipitation) to obtain a powder. ,dry. Next, the sample was dissolved in methylene chloride while heating and left standing overnight in a freezer (−5 ° C.) to obtain a precipitate, which was filtered and washed with cold methylene chloride. The polyphenylene ether is obtained by washing with methanol and vacuum drying at 140 ° C. for 1 hour. This polyphenylene ether was accurately weighed (W (mg)), dissolved in 25 ml of methylene chloride, added with 20 μl of 10 wt% ethanol solution of tetraethylammonium hydroxide, and UV spectrophotometer (Hitachi Co., Ltd.). The absorbance (Abs) at 318 nm is measured using U-3210), and can be calculated based on the following equation.

n (OH) = 63.9 × (Abs) / (W)
(However, n (OH): Number of phenolic hydroxyl groups per 100 phenylene ether units)

  The method for producing polyphenylene ether is not particularly limited as long as it can be obtained by a known method. For example, a method in which a phenolic compound is directly oxidatively polymerized, and a phenolic compound is used as a solvent using supercritical carbon dioxide. It can be obtained by a method of oxidative polymerization, a method of oxidative polymerization of a phenolic compound in a mixed solvent composed of a good solvent and / or a poor solvent. In the method of oxidative polymerization in a mixed solvent, by selecting the ratio of a good solvent and a poor solvent, solution polymerization in a state in which polyphenylene ether is dissolved in the reaction solvent can be achieved even at the end of polymerization, and the ratio of the poor solvent can be reduced. Increasing the size also leads to precipitation precipitation polymerization in which the polymer cannot be completely dissolved in the reaction solvent as the reaction proceeds and precipitates as particles. The good solvent here is a solvent that can dissolve poly (2,6-dimethylphenylene) ether obtained by a conventionally known method, and the poor solvent is a poly (2,6-dimethyl) obtained by a conventionally known method. (Phenylene) ether is a solvent that does not dissolve at all or hardly dissolves.

Further, the polyphenylene ether that can be used in the present invention may be a polyphenylene ether functionalized in whole or in part.
The functionalized polyphenylene ether as used herein means at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group in the molecular structure, or It refers to at least one functionalized compound having a glycidyl group, or a polyphenylene ether functionalized with an epoxy resin.
The method for producing the functionalized polyphenylene ether is as follows: (1) in the presence or absence of a radical initiator, at a temperature in the range of 100 ° C. or higher and lower than the glass transition temperature of the polyphenylene ether without melting the polyphenylene ether. A method of reacting with a functionalized compound, (2) a method of reacting by melting and kneading with a functionalized compound at a temperature in the range of the glass transition temperature of polyphenylene ether to 360 ° C. in the presence or absence of a radical initiator, (3) Examples include a method of reacting polyphenylene ether and a functionalized compound in a solution at a temperature lower than the glass transition temperature of polyphenylene ether in the presence or absence of a radical initiator, and any of these methods may be used.

Next, at least one functionalization having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl group in the molecular structure The compound will be specifically described.
Examples of functionalized compounds having a carbon-carbon double bond, a carboxylic acid group, and an acid anhydride group in the molecule include maleic acid, fumaric acid, chloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and These acid anhydrides are mentioned. Fumaric acid, maleic acid, and maleic anhydride are particularly preferable, and fumaric acid and maleic anhydride are particularly preferable.
In addition, those in which one or two of the carboxyl groups of the unsaturated dicarboxylic acid are esters can be used.

Examples of the functionalized compound having a carbon-carbon double bond and a glycidyl group in the molecule include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and epoxidized natural oil.
Among these, glycidyl acrylate and glycidyl methacrylate are particularly preferable.
Examples of the functionalized compound having both a carbon-carbon double bond and a hydroxyl group in the molecule include general formulas C _n H _2n-3 such as allyl alcohol, 4-penten-1-ol, and 1,4-pentadien-3-ol. Examples thereof include unsaturated alcohols of OH (n is a positive integer), general alcohols such as C _n H _2n-5 OH, C _n H _2n-7 OH (n is a positive integer), and the like.

As the epoxy resin, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, triglycidyl isocyanurate, 1,3-diglycidyl hydantrain, bisphenol A type epoxy resin, Examples include cresol novolac type epoxy resins, ethylene glycol diglycidyl ether, diglycidyl aniline, and the like. Among them, bisphenol A type epoxy resins and cresol novolac type epoxy resins are preferable.
The functionalized compounds described above may be used alone or in combination of two or more.

The addition amount of the functionalized compound in producing the functionalized polyphenylene ether is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polyphenylene ether.
A preferable amount of the radical initiator when producing the functionalized polyphenylene ether using the radical initiator is 0.001 to 1 part by mass with respect to 100 parts by mass of the polyphenylene ether.
The addition rate of the functionalized compound in the functionalized polyphenylene ether is preferably 0.01 to 30% by mass. More preferably, it is 0.1-20 mass%. Even more preferably, it is 0.1 to 10% by mass.
In the functionalized polyphenylene ether, an unreacted functional compound and / or a polymer of the functional compound may remain.
Furthermore, you may add the well-known additive etc. which can be added to polyphenylene ether in the quantity of less than 10 mass parts with respect to 100 mass parts of polyphenylene ether.
From the viewpoint of electrical characteristics and water absorption, the content of (A) in the resin composition is 80% by mass or more, preferably 85% by mass or more, and more preferably 90% by mass or more.

(B) The glass fiber fabric may be any glass fiber fabric such as E glass, C glass, D glass, and S glass. The glass fiber fabric has a weaving density of 10 to 200/25 mm, preferably 15 to 100/25 mm, and a mass of 5 to 400 g / m ² , preferably 8 to 300 g / m ^2. Plain weave, satin weave, twill weave, Nanako weave, etc. can be used. Further, a glass fiber fabric in which both or one of the warp and the weft is woven with a textured glass yarn may be used. In addition, a glass fiber woven fabric at a stage where a sizing agent necessary for weaving is attached, a glass fiber woven fabric at a stage where the sizing agent is removed, or a silane coupling agent already treated by a known surface treatment method. Any of glass fiber fabrics may be used. Further, it may be a glass fiber fabric subjected to physical processing such as opening, flattening, etc. by columnar flow or water flow by a high frequency vibration method.

Although there is no restriction | limiting in particular in the thickness of a glass fiber fabric, As preferable thickness, it is 0.005 mm-0.5 mm, More preferably, it is 0.007 mm-0.3 mm, More preferably, it is 0.008 mm-0.2 mm. And particularly preferably from 0.008 mm to 0.15 mm.
This glass fiber fabric is effective in reducing the inherent large linear expansion coefficient of the thermoplastic resin. Furthermore, strength and strain can be imparted. In particular, when the resin film is thin, the reinforcing effect by the glass fiber fabric is essential from the viewpoint of strength and linear expansion coefficient.

  Component (C) is a thermoplastic resin other than component (A), and is an aromatic vinyl compound polymer, aromatic vinyl compound copolymer, polypropylene, polyethylene, polyamide 6, polyamide 66, polyamide 66/6, aromatic ring. It is at least one selected from the group containing polyamide, aliphatic ring-containing polyamide, polyphenylene sulfide, liquid crystal polymer, polyether ether ketone, polyarylate, polyether sulfone, and polysulfone. More preferably, at least one selected from an aromatic vinyl compound copolymer, an aromatic ring-containing polyamide, an aliphatic ring-containing polyamide, polyphenylene sulfide, a liquid crystal polymer, polyether ether ketone, polyarylate, polyether sulfone, and polysulfone. It is. More preferably, it is at least one selected from an aromatic vinyl compound copolymer, an aromatic ring-containing polyamide, an aliphatic ring-containing polyamide, and a liquid crystal polymer.

Here, as an aromatic vinyl compound, 1 type (s) or 2 or more types can be selected from styrene, (alpha) -methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene etc., for example, Styrene is preferable. Specific examples of the aromatic vinyl compound polymer include atactic polystyrene, syndiotactic polystyrene, and high impact polystyrene.
The aromatic vinyl compound copolymer is, for example, a copolymer obtained by copolymerizing a compound copolymerizable with the aromatic vinyl compound as described above. Examples of the copolymerizable compound include unsaturated dicarboxylic acid imide derivatives, unsaturated dicarboxylic acid anhydrides, and other vinyl compounds.

Specific examples of the unsaturated dicarboxylic acid imide derivative include N-alkylmaleimide such as maleimide, N-methylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, and N-arylmaleimide (the aryl group includes, for example, phenyl, chloro And maleimide derivatives such as phenyl, methylphenyl, methoxyphenyl, and tribromophenyl). Among these, N-phenylmaleimide is particularly preferable. Moreover, these derivatives can also be used in mixture of 2 or more types.
Specific examples of the unsaturated dicarboxylic acid anhydride include anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid. Among these, maleic anhydride is particularly preferable.

Specific examples of other vinyl compounds include vinyl cyanide compounds such as butadiene, acrylonitrile and methacrylonyl, acrylic acid ester compounds such as methyl acrylate and ethyl acrylate, and methacrylate esters such as methyl methacrylic acid and ethyl methacrylic acid ester. Compounds, vinyl carboxylic acid compounds such as acrylic acid and methacrylic acid, and compounds such as acrylic acid amide and methacrylic acid amide are exemplified, and among these, acrylonitrile is particularly preferable.
Preferable examples of the aromatic vinyl compound copolymer include acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, aromatic vinyl-maleimide copolymer, and the like, from the viewpoint of heat resistance. A vinyl-maleimide copolymer, (1) a method of copolymerizing a mixture of an aromatic vinyl compound, an unsaturated dicarboxylic imide derivative, and other copolymerizable vinyl compounds as required, (2) aromatic After copolymerizing a mixture of a vinyl compound, an unsaturated dicarboxylic acid anhydride and, if necessary, another copolymerizable vinyl compound, ammonia and / or a primary amine is reacted to convert the acid anhydride group into an imide group. It can obtain by the method of converting to. In the production method (1), unsaturated dicarboxylic acid anhydrides are also included as examples of other copolymerizable vinyl compounds. In the production method (2), acid anhydride groups are not converted to imide groups. There is no problem in remaining, and as a result, an acid anhydride group can be introduced into the copolymer.

Ammonia and primary amine used in the production method (2) may be either anhydrous or in an aqueous solution. Examples of primary amines include alkylamines such as methylamine, ethylamine, butylamine, and cyclohexylamine, Aromatic amines such as aniline, toluidine, chloraniline, methoxyaniline and tribromoaniline are exemplified, and among these, aniline is particularly preferable.
As a method for polymerizing these aromatic vinyl compound copolymers, a known polymerization method can be used. In the case of the production method (1), suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization are preferable. ) Is preferably bulk-suspension polymerization, solution polymerization, or bulk polymerization.

As these aromatic vinyl-maleimide copolymers, styrene / N-phenylmaleimide copolymers, styrene / N-phenylmaleimide / maleic anhydride copolymers, and styrene / N-phenylmaleimide / acrylonitrile copolymers are suitable. Can be used for
The aromatic vinyl-maleimide copolymer is a copolymer comprising 30 to 70% by mass of an aromatic vinyl compound, 30 to 70% by mass of an unsaturated dicarboxylic imide derivative and 0 to 20% by mass of a copolymerizable vinyl compound. More preferably, the aromatic vinyl compound is 40 to 69.99 mass%, the unsaturated dicarboxylic imide derivative is 30 to 59.99 mass%, and the other copolymerizable vinyl compound is 0.01 to 15 mass%. And more preferably 40 to 69.9% by mass of an aromatic vinyl compound, 30 to 59.9% by mass of an unsaturated dicarboxylic imide derivative, and 0.1 to 15% by mass of a copolymerizable vinyl compound. When the ratio of the aromatic vinyl compound is less than 30% by mass, the compatibility with the polyphenylene ether is deteriorated, resulting in a decrease in tensile elongation. When the ratio of the unsaturated dicarboxylic imide derivative is less than 30% by mass, Heat resistance decreases. Moreover, when the ratio of the other copolymerizable vinyl compound exceeds 20% by mass, the heat resistance is lowered or the thermal stability is deteriorated.

  The aromatic vinyl compound copolymer preferably has a weight average molecular weight of 70,000 to 250,000. The weight average molecular weight here is a molecular weight converted with polystyrene as a standard sample, and can be calculated by gel permeation chromatography (GPC) measurement using tetrahydrofuran as a solvent. The weight average molecular weight is 70,000 or more from the viewpoint of tensile elongation, and 250,000 or less from the viewpoint of fluidity. More preferably, it is 100,000-250,000, More preferably, it is 100,000-200,000. Further, these copolymers may be one kind of aromatic vinyl compound copolymer, which is a mixture of two or more kinds of aromatic vinyl compound copolymers having different weight average molecular weights, and the weight average molecular weight of the mixture is It may be in the range of 70,000 to 250,000.

  The liquid crystal polymer is a liquid crystal polyester, which is a polyester called a thermotropic liquid crystal polymer, and known ones can be used. For example, a thermotropic liquid crystal polyester mainly composed of p-hydroxybenzoic acid and polyethylene terephthalate, a thermotropic liquid crystal polyester mainly composed of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, p-hydroxybenzoic acid Examples thereof include thermotropic liquid crystal polyesters mainly composed of acid, 4,4'-dihydroxybiphenyl and terephthalic acid, and are not particularly limited. The liquid crystalline polyester used in the present invention is preferably composed of the following structural units (a) and / or (b) and, if necessary, the following structural units (c) and / or (d).

  Here, the structural units (A) and (B) are respectively a structural unit of a polyester generated from p-hydroxybenzoic acid and a structural unit generated from 2-hydroxy-6-naphthoic acid. By using the structural units (a) and (b), it is possible to obtain the thermoplastic resin composition of the present invention having an excellent balance of mechanical properties such as excellent heat resistance, fluidity and rigidity. X in the structural units (c) and (d) can be independently selected from the following (Formula 2), or one or more of them can be selected.

  In the structural formula (c), preferred are structural units formed from ethylene glycol, hydroquinone, 4,4′-dihydroxybiphenyl, 2,6-dihydroxynaphthalene and bisphenol A, and more preferred are ethylene glycol, Structural units formed from 4,4'-dihydroxybiphenyl and hydroquinone, and particularly preferred are structural units formed from ethylene glycol and 4,4'-dihydroxybiphenyl.

In the structural formula (d), preferred are structural units formed from each of terephthalic acid, isophthalic acid and 2,6-dicarboxynaphthalene, and more preferred are structural units formed from each of terephthalic acid and isophthalic acid. It is.
In the structural formula (c) and the structural formula (d), at least one or two or more of the structural units listed above can be used in combination. Specifically, when two or more kinds are used in combination, in the structural formula (c), 1) a structural unit generated from ethylene glycol / a structural unit generated from hydroquinone, 2) a structural unit generated from ethylene glycol / 4,4 Examples include structural units formed from '-dihydroxybiphenyl, 3) structural units formed from hydroquinone / 4, structural units formed from 4,4'-dihydroxybiphenyl, and the like.
In the structural formula (d), 1) a structural unit generated from terephthalic acid / a structural unit generated from isophthalic acid, 2) a structural unit generated from terephthalic acid / 2, a structural unit generated from 2,6-dicarboxynaphthalene , Etc. The proportion of the structural units (A), (B), (C) and (D) used in the liquid crystal polyester component is not particularly limited. However, the structural units (c) and (d) are basically in equimolar amounts.

  Further, the following structural unit (e) composed of the structural units (c) and (d) can also be used as the structural unit in the liquid crystal polyester component. Specifically, 1) a structural unit produced from ethylene glycol and terephthalic acid, 2) a structural unit produced from hydroquinone and terephthalic acid, 3) a structural unit produced from 4,4'-dihydroxybiphenyl and terephthalic acid, 4) And structural units formed from 4,4'-dihydroxybiphenyl and isophthalic acid, and 5) structural units formed from bisphenol A and terephthalic acid.

The liquid crystalline polyester component of the present invention includes structural units formed from other aromatic dicarboxylic acids, aromatic diols, and aromatic hydroxycarboxylic acids within a small range that does not impair the features and effects of the present invention as necessary. Can be introduced.
The resin composition of the present invention may be (A) polyphenylene ether alone or a composition of (A) and (C).
(A) In the case of polyphenylene ether alone, since melt processability is insufficient, after dissolving in a good solvent and impregnating the solution into a glass fiber fabric, the solvent is distilled off by heating and / or decompression, It is preferable to obtain a laminate by drying.

In the case of the composition of the components (A) and (C), the above-described impregnation method using a good solvent can be selected, but not all resin components have high solubility in the solvent, rather Since the melt processability of polyphenylene ether is improved by component (C), a film is formed by an extrusion molding machine, and the obtained film and (B) glass fiber fabric can be laminated by hot pressing. preferable. At this time, the copper foil (F) can be laminated simultaneously by hot pressing.
From the viewpoint of the melt film-forming property of the resin composition film of the present invention and the film thickness uniformity of the film obtained, (C) is preferably a liquid crystal polymer and / or an aromatic vinyl-maleimide copolymer.

A preferred content ratio of the components (A) and (C) is 80 parts by mass or more of (A) polyphenylene ether with respect to a total of 100 parts by mass of (A) and (C), and the component (C) is 20 parts by mass. Or less.
From the viewpoint of peel strength, the content of the component (C) is 20 parts by mass or less, preferably 15 parts by mass or less, and more preferably 10 parts by mass or less.

(D) The compound containing Zn element and / or Mg element is an inorganic compound or organic compound containing metal. The component (D) of the present invention is a compound essentially comprising a Zn element and / or a Mg element as a main component. As the component (D), oxides, hydroxides, aliphatic carboxylates and acetates of the above metal elements are preferable. Examples of preferable oxides include ZnO and MgO. Examples of preferable hydroxides include Zn (OH) 2 and Mg (OH) 2. Examples of preferred aliphatic carboxylates include zinc stearate and magnesium stearate. Examples of preferred acetates include zinc acetate and magnesium acetate.
These components (D) have the effect of partially compatibilizing the inherently low miscibility (A) polyphenylene ether resin and the liquid crystal polyester (C), and tend to increase the strength of the resulting film. is there. In particular, from the viewpoint of partial compatibilization, ZnO and Mg (OH) 2 can be mentioned.

This component (D) is 0.01 parts by mass or more, preferably 0.1 parts or more, more preferably 0.5 parts or more from the viewpoint of miscibility. Moreover, from a viewpoint of an electrical property, 3 mass parts or less are preferable, More preferably, it is 2 mass parts or less.
(E) As the phosphinic acid salt, at least one selected from phosphinic acid salts represented by the following formula (3) and / or diphosphinic acid salts represented by the following formula (4), or condensates thereof: The phosphinates are preferred.

Wherein R ¹ and R ² are the same or different and are linear or branched C ₁ -C ₆ -alkyl and / or aryl or phenyl, and R ³ is linear or branched C ₁ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, C ₆ -C ₁₀ -alkylarylene or C ₆ -C ₁₀ -arylalkylene, M is calcium (ion), magnesium (ion), aluminum ( Ion), zinc (ion), bismuth (ion), manganese (ion), sodium (ion), potassium (ion), and protonated nitrogen base, and m is 2 or 3 , N is 1 to 3, and x is 1 or 2.)

The phosphinic acid salt may be mixed in any composition as long as the effect of the present invention is not impaired. From the viewpoint of flame retardancy, the phosphinic acid salt represented by the above (3) is added in an amount of 90 mass. % Or more, more preferably 95% by mass or more, and most preferably 98% by mass or more.
Specific examples of phosphinic acid that can be preferably used in the present invention include dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), benzene-1,4- (Dimethylphosphinic acid), methylphenylphosphinic acid, diphenylphosphinic acid, and mixtures thereof.
The metal component that can be preferably used is at least one selected from calcium ions, magnesium ions, aluminum ions, zinc ions, bismuth ions, manganese ions, sodium ions, potassium ions) and / or protonated nitrogen bases. More preferably, it is at least one selected from calcium ions, magnesium ions, aluminum ions, and zinc ions.

  Specific examples of phosphinates that can be preferably used include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate , Zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n-propyl Aluminum phosphinate, zinc methyl-n-propylphosphinate, calcium methanedi (methylphosphinate), meta Di (methylphosphinic acid) magnesium, methanedi (methylphosphinic acid) aluminum, methanedi (methylphosphinic acid) zinc, benzene-1,4- (dimethylphosphinic acid) calcium, benzene-1,4- (dimethylphosphinic acid) magnesium, Benzene-1,4- (dimethylphosphinic acid) aluminum, benzene-1,4- (dimethylphosphinic acid) zinc, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, Examples include calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate.

Particularly from the viewpoint of flame retardancy, calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, Zinc diethylphosphinate is preferred. Of these, aluminum diethylphosphinate is particularly preferable.
(E) Content of a phosphinate is 1 mass part or more from a flame-retardant viewpoint, Preferably it is 2 mass parts or more, More preferably, it is 3 mass parts or more. From the viewpoint of water absorption, it is 10 parts by mass or less, preferably 8 parts by mass or less, more preferably 6 parts by mass or less.

In the laminate of the present invention, copper may be bonded as a conductor. A copper foil may be laminated, or the surface of the resin may be surface-treated by a known method and then copper-plated.
Examples of the copper foil include rolled copper foil and electrolytic copper foil. The thickness of the copper foil is preferably 5 to 35 μm. Further, the laminated surface of the copper foil and the opposite surface thereof may be subjected to roughening treatment, rust prevention treatment, bumping treatment, easy adhesion treatment, and the like, if necessary.
Since the laminate of the present invention has a high polyphenylene ether content, it has excellent electrical properties such as low dielectric constant and low dielectric loss tangent. In addition, since it is difficult to absorb moisture, changes in physical properties due to moisture absorption are small. In addition, since the glass transition temperature (210 to 240 ° C.) of the resin is high, physical properties represented by electrical characteristics in a wide temperature range are stable. Furthermore, since the dielectric constant and dielectric loss tangent of polyphenylene ether have low frequency dependence, they have stable electrical characteristics for high-frequency substrate applications.

The laminate may have a single layer structure of resin / glass fiber fabric / resin, but may have a multilayer structure such as resin / glass fiber fabric / resin / glass fiber fabric /... / Glass fiber fabric / resin. In addition, as a laminate for a circuit having a conductor pattern, a single layer structure of copper / resin / glass fiber fabric / resin / copper, or copper / resin / glass fiber fabric / resin / glass fiber fabric /.../ glass fiber fabric / Multi-layer structure of resin / copper, and laminated structure for high-density mounting, copper / resin / copper / resin / glass fiber fabric / resin / copper / resin / glass fiber fabric /.../ glass fiber fabric / resin / copper structure You may have taken.
In the present invention, in addition to the above-described components, an inorganic filler can be added as necessary within the range not impairing the characteristics and effects of the present invention. Strengthening agents include metal fiber, potassium titanate, carbon fiber, silicon carbide, ceramic, silicon nitride, mica, nepheline cinnite, talc, wollastonite, slag fiber, ferrite, glass beads, glass powder, glass balloon, quartz And inorganic compounds such as quartz glass, fused silica, titanium oxide, and calcium carbonate. The shape of these inorganic fillers is not limited, and a fibrous shape, a plate shape, a spherical shape, and the like can be arbitrarily selected.

These inorganic fillers can be used in combination of two or more. Further, if necessary, it can be used after pretreatment with a coupling agent such as silane or titanium.
Further, in addition to the above-described components, other additional components as necessary, for example, antioxidants, flame retardants (organic phosphate ester compounds, phosphazene compounds, cyclic compounds, as long as the characteristics and effects of the present invention are not impaired. Nitrogen compounds, silicones, caged silsesquioxanes or partially cleaved structures thereof, silica), elastomers (ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / propylene / nonconjugated diene copolymers, Olefin copolymer such as ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / propylene-g-maleic anhydride copolymer, ABS Coalescence, polyester polyether elastomer, polyester polyester elast -Vinyl aromatic compound-conjugated diene compound block copolymer, hydrogenated vinyl aromatic compound-conjugated diene compound block copolymer), plasticizer (paraffin oil, low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol) , Fatty acid esters, etc.), flame retardant aids, weather resistance (light) improvers, and various colorants may be added.

As a manufacturing method of the laminated body of this invention, a thermoplastic resin film and glass fiber fabric can be set so that it may become layered, and it can shape | mold by hot press. It may be a batch press or a roll-to-roll continuous press molding. In the case of continuous forming, it is preferable to form with a device capable of controlling the pressing pressure, such as a double steel belt. For batch hot pressing, a known apparatus for producing a laminate can be selected. A single-stage type, a multi-stage type, an atmospheric pressure hot press machine, or a vacuum hot press machine may be used.
The temperature during hot press molding is preferably 240 ° C or higher and 340 ° C or lower. When the pressing temperature is low, the resin fluidity becomes insufficient, the resin does not flow into the glass fiber fabric, and bubbles are generated. From the viewpoint of bubbles, it is preferably 240 ° C. or higher, more preferably 245 ° C. or higher, and even more preferably 250 ° C. or higher. If the pressing temperature is too high, the resin begins to deteriorate, which causes insufficient strength. Therefore, from the viewpoint of resin deterioration, it is preferably 340 ° C. or lower, more preferably 320 ° C. or lower, and even more preferably 300 ° C. or lower.

The pressing pressure is preferably 1 MPa to 40 MPa. From the viewpoint of eliminating bubbles, it is preferably 1 MPa or more, more preferably 2 MPa, and even more preferably 4 MPa. From the viewpoint of suppressing the opening of the glass fiber fabric, it is preferably 40 MPa or less, more preferably 30 MPa, and even more preferably 15 MPa.
The atmosphere during hot press molding may be normal pressure or reduced pressure. It may be under air or inert gas. From the viewpoint of deterioration of the resin, it is preferable to hot press in an inert gas atmosphere. From the viewpoint of efficiently eliminating bubbles, it is preferable to perform hot press molding in a reduced pressure atmosphere, preferably 30 kPa or less, more preferably 15 kPa, and even more preferably 5 kPa or less.

The thermoplastic resin film of the present invention can be formed by various conventionally known methods such as injection molding, extrusion molding, and hollow molding. Extrusion molding is particularly preferred from the viewpoint of productivity.
Then, the resin composition pellets can be put into an extrusion sheet molding machine and molded, or each component of the raw material of the present invention can be directly fed into the extrusion sheet molding machine to carry out melt kneading and sheet molding at the same time. Can also be obtained. The screw may be a single shaft or a biaxial type. In the case where the melt kneading and the sheet forming are performed simultaneously, a biaxial screw is preferable from the viewpoint of the kneading effect.

The thermoplastic resin sheet of the present invention can be produced by an extrusion tubular method, and sometimes a method called an inflation method. It is extremely important to make the sheet thickness uniform by appropriately selecting from the temperature range of 50 to 290 ° C so that the parison coming out of the cylinder does not cool down immediately. is there.
On the other hand, the polyphenylene ether resin sheet of the present invention can be produced by T-die extrusion. In this case, it may be used without stretching, may be uniaxially stretched, or may be obtained by biaxially stretching. When it is desired to increase the strength of the sheet, it can be achieved by stretching. You may use a gear pump and a screen changer suitably according to the objective.

In the case of a resin composition containing polyphenylene ether as a main component, it is easy to generate a scum at the time of film formation, and it is effective to provide a vacuum vent in order to suppress the scum. It is also effective to blow an inert gas typified by nitrogen or the like around the feed port and the vent port.
The thickness of the thermoplastic resin film used in the present invention is not particularly limited, but is preferably 0.005 to 1.0 mm. More preferably, it is 0.010-0.5 mm, 0.010-0.3 mm is preferable, More preferably, it is 0.01-0.1 mm.
From the viewpoint of the balance between the electrical characteristics and the linear expansion coefficient, the thickness of the film used and the thickness of the glass fiber fabric can be appropriately selected.

The laminate comprising the glass fiber fabric and the thermoplastic resin film of the present invention may have a single layer structure or a multilayer structure. Although there is no restriction | limiting in particular about those thickness, The preferable thickness of the laminated body of a single layer structure is 0.005-2.5 mm, More preferably, it is 0.010-1.5 mm, More preferably, it is 0.00. It is 020-0.8 mm, Most preferably, it is 0.020-0.5 mm. A preferable thickness of the multilayer structure is 0.010 to 10 mm, more preferably 0.030 to 5.0 mm, still more preferably 0.050 to 2.0 mm, and particularly preferably 0.080. -1.0 mm.
(A) In the case of polyphenylene ether alone, since melt processability is insufficient, after dissolving in a good solvent and impregnating the solution into a glass fiber fabric, the solvent is distilled off by heating and / or decompression, It is preferable to obtain a laminate by drying.

When a conductor layer typified by copper is further laminated on the laminate obtained by these methods, a plating method may be used, or a copper foil may be press-molded or laminated via an adhesive. However, in order not to deteriorate the electrical characteristics, it is preferable to suppress the amount of the adhesive layer, and it is preferable not to use it. Moreover, the method by a hot press is preferable from a viewpoint of peel strength with copper foil.
Also in the case of this hot press molding, 240 degreeC or more and 340 degrees C or less are preferable similarly to the conditions mentioned above. From the viewpoint of bubbles, it is preferably 240 ° C. or higher, more preferably 245 ° C. or higher, and even more preferably 250 ° C. or higher. From the viewpoint of deterioration of the resin, it is preferably 340 ° C. or lower, more preferably 320 ° C. or lower, and even more preferably 300 ° C. or lower.

The pressing pressure is preferably 1 MPa to 40 MPa. From the viewpoint of eliminating bubbles, it is preferably 1 MPa or more, more preferably 2 MPa, and even more preferably 4 MPa. From the viewpoint of suppressing the opening of the glass fiber fabric, it is preferably 40 MPa or less, more preferably 30 MPa, and even more preferably 15 MPa.
From the viewpoint of improving the peel strength between the copper foil and the resin, as described above, the polyphenylene ether in the thermoplastic resin composition contains 0.9 or more phenolic hydroxyl groups per 100 phenylene ether units. It is preferable. The number of hydroxyl groups can also be controlled during polymerization. In the case of polyphenylene ether, it can be increased by a well-known redistribution reaction called quinone coupling. In addition, the powder after polymerization can be increased by heating such as melt kneading. This is considered to be due to an increase in phenolic hydroxyl groups in the main chain due to the Fries transition reaction in the polyphenylene ether main chain.

The laminate thus obtained has excellent low water absorption, excellent electrical characteristics such as dielectric constant and dielectric loss tangent, can further reduce the linear expansion coefficient, and is excellent in heat resistance, copper foil peel strength, appearance, and flexibility. In addition, non-halogen materials can be used. Therefore, it is environmentally friendly because it does not generate toxic gases during incineration. Furthermore, since the resin component is a thermoplastic resin, it is easily separated from the metal part and can be recycled, so that it is a highly environmentally friendly laminate. Further, the electrical characteristics are characterized by stable characteristics in a wide temperature range, wide frequency range, and high humidity environment.
Therefore, the laminate of the present invention is suitably used for applications requiring the above characteristics.
For example, an electric circuit board, a printed board material, a flexible circuit board, a rigid circuit board, a build-up multilayer circuit board, an interlayer insulating film, and the like can be given. The low dielectric material is suitable for applications such as satellite broadcasting, automotive radar, wireless LAN, optical module high-frequency components, antennas, base station amplifiers, various high-speed transmission devices, tester satellite communication devices, and high-frequency cables. .

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to what was shown by this Example.
(Raw materials used)
(A) Polyphenylene ether (hereinafter abbreviated as PPE)
Each PPE was adjusted according to the production example described below.
(PPE-1): (2,6-dimethyl-1,4-phenylene ether) powder Reduced viscosity: 0.52 dl / g, (0.5 g / dl, chloroform solution, 30 ° C. measurement)
n (OH) = 0.78
(However, n (OH): Number of phenolic hydroxyl groups per 100 phenylene ether units. The same applies hereinafter.)
Glass transition temperature: 215 ° C. (DSC method, heating rate 20 ° C./min)
(PPE-2): (2,6-dimethyl-1,4-phenylene ether) powder reduced viscosity: 0.54 dl / g, (0.5 g / dl, chloroform solution, measured at 30 ° C.)
n (OH) = 0.32.
(PPE-3): (2,6-dimethyl-1,4-phenylene ether) powder reduced viscosity: 0.41 dl / g, (0.5 g / dl, chloroform solution, measured at 30 ° C.) n (OH) = 1 .12
(PPE-4): (2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer) Powder copolymerization ratio: 2,6-dimethylphenol / 2,3,6-trimethylphenol = 76/24 (Mass ratio)
Reduced viscosity: 0.50 dl / g, (0.5 g / dl, chloroform solution, measured at 30 ° C.)
n (OH) = 0.49
Glass transition temperature: 230 ° C. (DSC method, heating rate 20 ° C./min)

[Production Example 1] (Synthesis of PPE-1)
(1) Polymer preparation A 10 L jacketed reactor equipped with an oxygen gas introduction pipe, a stirring turbine blade and baffle at the bottom of the reactor, and a reflux condenser for condensation in the vent gas line at the top of the reactor, 2052 g of toluene, 178 g of methanol, 0.6 g of cuprous oxide as a catalyst component, 2.8 g of hydrogen bromide (47% aqueous solution) as an acid, 2.3 g of di-t-butylethylenediamine, and 26.5 g of butyldimethylamine , 4.2 g of di-n-butylamine was charged. Next, after introducing nitrogen into the reaction vessel gas phase at a flow rate of 10 NL / min, oxygen is introduced from the gas introduction pipe at a flow rate of 1 NL / min, while 400 g of 2,6-dimethylphenol dissolved in 1330 g of toluene. Was fed into the reactor over 40 minutes (time required for monomer addition). The reaction temperature was adjusted by passing a heating medium through the jacket so as to maintain 40 ° C.

(2) Catalyst deactivation 66 minutes after the start of monomer addition (polymerization stop time), the polymerization was stopped by switching oxygen to nitrogen and adding 20 g of 38% EDTA · 3Na aqueous solution and 380 g of water.
(3) Quinone coupling reaction The tetramethyldiphenoquinone (TMDQ) -containing reaction mixture thus obtained was heated at 70 ° C. for 180 minutes under nitrogen. (Quinone Coupling Reaction) At this point, the reaction mixture no longer showed a color characteristic of TMDQ. The solution was cooled to 50 ° C., and the aqueous layer containing the copper salt and some amine was removed by a liquid-liquid centrifuge. About 10 times volume of methanol was added to the reaction mixture after centrifugation to precipitate a polymer. Such a polymer was furnace separated, washed with methanol, and then dried in a hot air dryer at 80 ° C.

[Production Example 2] (Synthesis of PPE-2)
(1) Polymer adjustment was carried out in the same manner as in Production Example 1.
(2) In the catalyst deactivation process, after 61 minutes from the start of monomer addition (polymerization stop time), the oxygen was switched to nitrogen, and the polymerization was stopped by adding 20 g of 38% EDTA · 3Na aqueous solution and 380 g of water. I let you. Next, without performing quinone coupling, 9 g of hydroquinone was added to the reaction mixture, and tetramethyldiphenoquinone (TMDQ) present in the system was reduced. This solution was heated to 50 ° C., and the aqueous layer containing the copper salt and some amine was removed by a liquid-liquid centrifuge. About 10 times volume of methanol was added to the reaction mixture after centrifugation to precipitate a polymer. Such a polymer was furnace separated, washed with methanol, and then dried in a hot air dryer at 80 ° C.

[Production Example 3] (Synthesis of PPE-3)
(2) In the catalyst deactivation process, PPE-3 was obtained in the same manner as in Production Example 1 except that the oxygen was switched to nitrogen after 52 minutes (polymerization stop time) from the start of monomer addition. .

[Production Example 4] (Synthesis of PPE-4)
While blowing nitrogen gas at a flow rate of 500 ml / min into a 10 L jacketed polymerization tank equipped with an oxygen gas introduction tube, a stirring turbine blade and baffle at the bottom of the reactor, and a reflux condenser for condensation at the vent gas line at the top of the reactor 1.099 g cupric chloride dihydrate, 4.705 g 35% hydrochloric acid, 41.971 g N, N, N ′, N′-tetramethylpropanediamine, 31.658 g di-n-butylamine 1264 g of n-butanol, 544 g of methanol, 3792 g of xylene, 121.6 g of 2,6-dimethylphenol and 38.4 g of 2,3,6-trimethylphenol were added to form a homogeneous solution, and the inside of the reactor Stir until the temperature is 40 ° C.
In addition, 720 g of methanol was blown into the 5 L storage tank equipped with a nitrogen gas introduction pipe, a stirring turbine blade and baffle in the storage tank, and a reflux condenser in the vent gas line at the top of the storage tank at a flow rate of 200 ml / min. 1094.4 g of 2,6-dimethylphenol and 345.6 g of 2,3,6-trimethylphenol were added and stirred until a homogeneous solution was prepared to prepare a mixed solution.

Next, oxygen gas is started to be introduced into the polymerization tank through the gas introduction pipe at a rate of 1000 ml / min into the vigorously stirred polymerization tank, and at the same time, the mixed solution in the storage tank is 21. Sequential additions were made at a rate of 6 g / min. Aeration was performed for 310 minutes, and the internal temperature of the reactor was controlled to 40 ° C. In addition, 140 minutes after starting supply of oxygen gas, polyphenylene ether was precipitated to show a slurry form, and the addition of the mixed solution was completed before starting to show the slurry form. The form of the polymerization solution at the end of the polymerization is precipitation polymerization.
Stop the ventilation of the oxygen-containing gas, add 11.5 g of 50% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) to the polymerization mixture, stir the polymerization mixture for 60 minutes, and then hydroquinone (Wako Pure Chemical Industries, Ltd.) And the stirring was continued until the slurry polyphenylene ether became white.
The internal temperature of the reactor was controlled to 40 ° C.

Thereafter, the wet polyphenylene ether remaining after filtration was placed in a 10 L washing tank and dispersed together with 6400 g of methanol, stirred for 30 minutes, and then filtered again to obtain wet polyphenylene ether. The internal temperature of the washing tank was controlled to 40 ° C. This was repeated three times, and then vacuum-dried at 140 ° C. for 150 minutes to obtain dry polyphenylene ether (PPE-4).
(B) (GC-1) Glass fiber fabric (Asahi Kasei Electronics 1000 / AS750, thickness 10 μm)
(C) Liquid crystalline polyester (LCP)

[Production Example 5] (Synthesis of LCP)
Under a nitrogen atmosphere, p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, and acetic anhydride were charged, heated, melted, and polycondensed to obtain a liquid crystal polyester (LCP) having the following theoretical structural formula. . In addition, the component ratio of a composition represents molar ratio.

(C) (PMI) Styrene-N phenylmaleimide copolymer (MS-NA, manufactured by Denki Kagaku Kogyo Co., Ltd.)
(D) (ZnO) zinc oxide (Ginbae A (registered trademark), manufactured by Toho Zinc Co., Ltd.)
(E) (P-1) Phosphinate (Exolit OP930 (registered trademark), manufactured by Clariant Japan)
(Additional component) (N-1) Polyethyleneimine (Epomin SP-018 (registered trademark), manufactured by Nippon Shokubai Co., Ltd.)

(Evaluation methods)
The evaluation method is described below.
<Measurement of the number of phenolic hydroxyl groups in polyphenylene ether>
(1) In the case where the sample was a powder of PPE-1 to PPE-1 or a pellet after melt-kneading by extrusion, the sample was subjected to the following weighing (W (mg)) as it was.
(2) When the sample is a laminate After etching the sample, removing the copper foil, washing with water and drying, the sample is first dissolved in chloroform at 30 ° C., the insoluble matter is removed, and the solution is poured into a large amount of methanol. By performing (reprecipitation), powder is obtained and dried. Next, the sample was dissolved in methylene chloride while heating and left standing overnight in a freezer (−5 ° C.) to obtain a precipitate, which was filtered and washed with cold methylene chloride. The polyphenylene ether is obtained by washing with methanol and vacuum drying at 140 ° C. for 1 hour. This polyphenylene ether was accurately weighed (W (mg)), dissolved in 25 ml of methylene chloride, added with 20 μl of 10 wt% ethanol solution of tetraethylammonium hydroxide, and UV spectrophotometer (Hitachi Co., Ltd.). The absorbance (Abs) at 318 nm is measured using U-3210), and can be calculated based on the following equation.
n (OH) = 63.9 × (Abs) / (W)
(However, n (OH): Number of phenolic hydroxyl groups per 100 phenylene ether units)

<Water absorption rate>
The copper foils on both sides of the laminates obtained in Examples and Comparative Examples were etched with an etching solution, washed with water, air-dried, cut into 40 mm × 40 mm, and saturated moisture 121 ° C. after absorbing moisture under 2 atm. The water absorption was measured.
<Solder heat resistance after moisture absorption>
The sample after moisture absorption, which was carried out by the above water absorption measurement, was floated on a molten solder at 260 ° C. for 1 minute, and was judged by the defects produced.
○: No change in appearance was observed.
Δ: blistering was observed on the surface.
<Solder heat resistance after moisture absorption>
The laminates with copper foils obtained in the examples and comparative examples were floated on molten solder at 260 ° C. for 1 hour, and were judged by the resulting defects.
○: No change in appearance was observed.
X: Swelling on the surface and peeling of the copper foil were observed.

<Electrical properties (dielectric constant, dielectric loss tangent)>
(In the case of 1 MHz) Automatic equilibrium bridge method The copper foils on both sides of the laminates obtained in the examples and comparative examples are etched with an etching solution, washed with water, air-dried, cut into 40 mm x 40 mm, and in accordance with JIS-K6911. Then, the measurement was performed at room temperature using a precision LCR meter HP-4285A (manufactured by Agilent Technologies). The results are shown in Tables 1 and 2.
In addition, about the comparative example 3, in order not to laminate | stack with copper foil, it used for the measurement as it was the film.
(Case of 1 GHz) Cylindrical cavity resonator method The copper foils on both sides of the laminates obtained in the examples and comparative examples were etched with an etchant, washed with water, air-dried, cut into 80 mm × 130 mm, and a vector network analyzer HP8510C. (Agilent Technology Co., Ltd.), synthesized swipeper HP83651A (Agilent Technology Co., Ltd.), test set HP8517B (Agilent Technology Co., Ltd.), using a device with an inner diameter of 229 mm and a height of 40 mm Measurement was performed at room temperature using a cylinder. The results are shown in Table 2.
(Case of 10 GHz) Cylindrical cavity resonator method Same as in the case of 1 GHz except that the sample size is 65 mm x 80 mm and a cylinder with an inner diameter of φ42 mm and a height of 30 mm is used as the resonator. did. The results are shown in Table 2.

<Linear expansion coefficient>
The copper foils on both sides of the laminates obtained in Examples and Comparative Examples were etched with an etching solution, washed with water and air-dried, and each of MD and TD of the laminate was cut into 10 mm × 5 mm in the longitudinal direction, and JIS- In accordance with K7197, using a thermomechanical analyzer (TMA, TMA / SS6100 type manufactured by SII NanoTechnology Co., Ltd.), in a temperature range of 30-190 ° C., at a heating rate of 5 ° C./min. The tensile load was 29.4 [mN] and measured in air.
<Bubble>
The copper foils on both sides of the laminates obtained in Examples and Comparative Examples were etched with an etching solution, washed with water, air-dried, cut into a substrate size of about 10 mm × 10 mm, embedded in a resin, polished on a cross section, and then subjected to SEM. Observation was performed with a scanning electron microscope. Ten warps and wefts of glass fiber fabric were observed, and the ratio of the number of yarn bundles in which voids were found was calculated, and the presence or absence of bubbles was determined below.
○: 0%
Δ: Over 0%, 30% or less x: Over 30%.
Those without voids (bubbles) are preferred.

<Peel strength>
Using the laminates obtained in Examples and Comparative Examples, a sample was cut out to a width of 10 mm, a 90-degree peel peel test was performed according to TPC-TM-650 standard 2.4.9, and the adhesion to copper foil was evaluated. did. The higher the value, the better the adhesion.
<Appearance>
The copper foils on both sides of the laminates obtained in the examples and comparative examples were etched with an etching solution, washed with water and air-dried, and the appearance of the substrate was visually determined based on the following criteria.
○: There is no coloring, the surface appearance is uniform, and there are no bubbles, gels, or fluffing.
(Triangle | delta): Although there is no coloring, a gel is observed a little.
X: There is a color derived from deterioration or many gels are observed.

[Example 1 and Example 2]
A polymer solution prepared by dissolving polyphenylene ether powder (PPE-1 or PPE-2) in toluene at 50 ° C. at a concentration of 8% by weight is prepared in a container, and (B) the glass woven fiber (GC-1) is removed from the roll. While feeding, the polymer solution was impregnated, passed through an explosion-proof heating furnace with a roll toe roll, the solvent was distilled off, and the operation was repeated twice. A polyphenylene ether laminate (a) was obtained. The thickness was 30 μm.

  This was cut out to a size of 290 mm × 200 mm (MD × TD), and vacuum hot press was performed with the following configuration. That is, <1> stainless steel plate, <2> cushion material (stainless steel mesh material, Naslon (registered trademark) manufactured by Nippon Seisen Co., Ltd., 1 mm thickness), <3> copper foil (electrolytic copper foil SF F2-WS, Furukawa Circuit) Foil, 12 μm thickness (for protection), <4> polyimide film (50 μm thickness, Apical (registered trademark, manufactured by Kaneka) × 6 sheets (for cushion), <5> copper foil (electrolytic copper foil SF F2- WS, manufactured by Furukawa Circuit Foil Co., Ltd., 12 μm thick) (glossy surface <4> side, rough surface <6> side) (for laminate lamination), <6> Polyphenylene ether laminate (A), <7> Same as <5>, <8> <4>, <9> <3>, <10> <2>, <11> <1> Using Kitagawa Seiki KVHCII-PRESS), the temperature was raised under a pressure of 4 kPa and 10 MPa. After reaching the setting of 4 ° C./min and 260 ° C., holding was performed for 30 minutes and hot press molding was performed, and the cooling time was about 30 minutes. The results are shown in Table 1.

[Example 3]
A twin-screw extruder having an upstream supply port in the first barrel from the upstream side of the extruder and having L / D (extruder cylinder length / extruder cylinder diameter) = 48 (number of barrels: 12) [ ZSK-26MC: manufactured by Coperion Co., Ltd.], the upstream feed port to the die is set at 290 ° C., the screw rotation speed is 300 rpm, the discharge rate is 8 kg / h, and polyphenylene ether (PPE-2) is supplied upstream. The raw material was supplied from the mouth and melt-kneaded to produce thermoplastic resin composition pellets. At this time, volatile components were removed from a vacuum vent installed in the 10th barrel.
In addition, the phenolic hydroxyl group concentration of the polyphenylene ether of the obtained pellet was 0.98 (pieces / 100 units).
The obtained pellet was dissolved in a toluene solution and impregnated into a glass fiber fabric, except that it was used in place of the polyphenylene ether (PPE-2) powder of Example 2. After that, a laminate with a copper foil was similarly obtained by vacuum hot pressing. The evaluation results are shown in Table 1.
From the comparison between Example 2 and Example 3, even when PPE-2 is used as the raw material, the phenolic hydroxyl group concentration of polyphenylene ether is different by controlling the thermal history, and there is a difference in copper foil peel strength. Recognize.

[Examples 4 to 7, Example 11, Comparative Example 1]
The pellets of the thermoplastic resin composition were obtained in the same manner as in Example 3 except that the raw materials were changed to the ratios shown in Table 1 and the discharge rate was 12 kg / h during melt kneading with an extruder.
(1) T-die extrusion molding Screws obtained by blowing nitrogen into the hopper port, cylinder temperature 300 ° C, gear pump, screen mesh 200, T-die width 300mm, T-die temperature 300 ° C Using a bent twin screw extruder (TEM26SS, manufactured by Toshiba Machine Co., Ltd.) with a diameter of 26 mm, the film was formed at a first metal roll of 150 ° C., a discharge rate of 4 kg / hr, a rotation speed of 120 rpm, and a take-off speed of 25 m / min. . The obtained film thickness was 13 μm.
The film (I) thus obtained was replaced with (I) / (GC-1) / (I) instead of <6> (Laminate (A)) of Example 1, A vacuum hot press was performed in the same manner as in Example 1 to obtain a copper-clad laminate.
The obtained laminate was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
For Example 4, the measurement results of electrical characteristics at 1 GHz and 10 GHz in addition to 1 MHz are shown in Table 2. It can be seen that the dielectric constant and dielectric loss tangent are stable in a wide frequency range.

[Example 8]
Instead of <6> ((I) / (GC-1) / (I)) in Example 4, (I) / (GC-1) / (I) / (I) / (GC-1) / Example 1 except that (b) / (b) / (GC-1) / (b) / (b) / (GC-1) / (b) and glass fiber woven fabric were made into four layers and stacked. In the same manner as above, vacuum hot pressing was performed to obtain a copper-clad laminate.
The obtained laminate was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[Example 9]
Evaluation was conducted in the same manner as in Example 4 except that the temperature (260 ° C.) of the hot press in Example 4 was 230 ° C., and the results are shown in Table 1.
It can be seen that when the press temperature is low, voids (bubbles) are generated and the solder heat resistance is poor after moisture absorption.

[Example 10]
Evaluation was conducted in the same manner as in Example 4 except that the temperature (260 ° C.) of the hot press in Example 4 was set to 350 ° C., and the results are shown in Table 1.
When the press temperature is too high, voids (bubbles) disappear, but it is understood that the appearance and solder heat resistance after moisture absorption are poor.

[Comparative Example 2]
A glass cloth (GC-1) was immersed in a varnish having the following composition and dried in an oven at 125 ° C. for 10 minutes to form a B-staged resin.
(Varnish composition)
Epicoat E157S70B75 30.0% by weight
(High heat-resistant novolac epoxy resin, oil-coated shell epoxy)
Epicoat E5050T60 30.0% by weight
(High Bromine Flame Retardant Epoxy Resin Yuka Shell Epoxy)
Epicoat 828 4.0% by weight
(Bisphenol A type epoxy resin made by Yuka Shell Epoxy)
EpiCure YLH129B70 29.0 weight (High heat resistance phenol novolac resin, Yuka Shell Epoxy)
2E4MZ 0.1% by weight
Methyl cellosolve 6.9% by weight
────────────────────────────────────
100% by weight

The glass transition temperature by the RDA method of the laminated board (c) thus obtained was 200 ° C.
This laminate (c) was used in place of <6> (laminate (a)) of Example 1, the hot press temperature was 220 ° C., the pressurization time was 60 minutes, and the press pressure was 5 MPa. Example 1 was carried out in the same manner as in Example 1, and the evaluation results are shown in Table 1.
From the above, it can be seen that the examples of the present invention are superior as laminates in comparison with the water absorption, electrical characteristics, linear expansion coefficient, and peel strength of Comparative Example 2.

[Comparative Example 3]
Instead of <6> (laminate (I) / (GC-1) / (I)), the film (I) obtained in Example 4 was used as it was without using a glass fiber fabric. Except for (a) x 2), vacuum hot pressing was performed in the same manner as in Example 4 to obtain a copper-clad laminate. The evaluation results are shown in Table 1. Although it is excellent in electrical characteristics, it can be seen that the coefficient of linear expansion is very large and is not suitable for a wiring board material.
As a result of solder heat resistance after water absorption, there was no blistering, but a large warp was observed after taking out and cooling.
The peel strength of the film was broken because the adhesive strength with the copper foil was good.

  The laminate of the present invention is a laminate of a thermoplastic resin composition and a glass fiber fabric excellent in low water absorption, electrical properties, low linear expansion coefficient, copper foil peel strength, and appearance. Since it is a material excellent in heat resistance and flame retardancy, it can be widely used in a wide range of fields such as electronic and electronic parts such as printed wiring board materials, especially for high frequency wiring materials, and non-halogen wiring material requirements.

Claims (18)

  (A) A laminate comprising a thermoplastic resin composition containing 80% by mass or more of polyphenylene ether and (B) a glass fiber fabric.   The laminate according to claim 1, wherein the polyphenylene ether in the laminate contains 0.90 or more phenolic hydroxyl groups per 100 phenylene ether units.   (C) A thermoplastic resin other than (A) is an aromatic vinyl compound polymer, an aromatic vinyl compound copolymer, polypropylene, polyethylene, polyamide 6, polyamide 66, polyamide 66/6, aromatic ring-containing polyamide, fat Group ring-containing polyamide, polyphenylene sulfide, liquid crystal polymer, polyether ether ketone, polyarylate, polyether sulfone, and polysulfone, and the resin composition has a total of 100 parts by mass of (A) and (C) On the other hand, the laminated body in any one of Claim 1 or 2 which contains 20 mass parts or less of (C).   The laminate according to claim 3, wherein the component (C) is a liquid crystal polymer and / or an aromatic vinyl-maleimide copolymer.   The resin composition contains 3 parts by mass or less of a compound containing (D) Zn element and / or Mg element with respect to 100 parts by mass in total of (A) and (C). The laminated body as described in.   The laminate according to any one of claims 1 to 5, wherein the resin composition contains 1 to 10 parts by mass of (E) phosphinate with respect to 100 parts by mass of the total of (A) and (C).   The laminated body in any one of Claims 1-6 with which copper foil was further bonded together.   The multilayer laminate according to any one of claims 1 to 7, wherein the glass fiber fabric comprises two or more layers.   The production of the laminate according to claim 1, wherein the thermoplastic resin composition film and the glass fiber fabric are hot press molded at a temperature of 240 ° C. or higher and 340 ° C. or lower and at a pressure of 1 MPa to 40 MPa. Method.   The manufacturing method according to claim 9, wherein hot press molding is performed in a vacuum state of 30 kPa or less.   The thermoplastic resin composition is preliminarily dissolved in a good solvent, the solution is impregnated into a glass fiber fabric, and then the solvent is distilled off by heating and / or decompression. Method.   The manufacturing method of the laminated body which carries out hot press molding at the temperature of 240 degreeC or more and 340 degrees C or less, and the pressure of 1 Mpa-40 Mpa in order to stick together with the laminated body obtained in Claim 11.   The production method according to claim 9, wherein the continuous forming is performed by a roll toe roll.   The electric circuit board using the laminated body in any one of Claims 1-8.   The interlayer insulation film using the laminated body in any one of Claims 1-8.   The flexible circuit board using the laminated body in any one of Claims 1-8.   The rigid circuit board using the laminated body in any one of Claims 1-8.   A multilayer circuit board for buildup using the laminate according to any one of claims 1 to 8.