JP2009013261A - Crosslinkable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a crosslinkable resin composition of high moldability, capable of giving a crosslinked resin and a crosslinked resin composite each having excellent electrical properties, heat resistance and adhesivity, and to provide to use of the composition. <P>SOLUTION: The crosslinkable resin composition comprises: a terminal-modified polyphenylene ether resin having a carbon-carbon unsaturated bond on at least one molecular chain terminal; and a nonpolar radical generator. A crosslinkable resin composite containing the above composition is also provided. Besides, a crosslinked resin and a crosslinked resin composite, obtained by crosslinking the above composition and the above composite, respectively, are provided. These crosslinked resin and crosslinked resin composite are suitable as electrical materials or the like for use in electrical circuit boards. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a crosslinkable resin composition and uses thereof. More specifically, the present invention relates to a crosslinkable resin composition having excellent moldability and capable of obtaining a crosslinked resin and a crosslinked resin composite having excellent electrical characteristics, heat resistance and adhesion.

  With higher speed and higher frequency of communication, insulating materials such as communication circuit boards and antenna boards, and printed wiring boards are required to have insulating materials with better electrical characteristics than ever. As an insulating material having a small dielectric loss tangent and excellent electrical characteristics, a polyphenylene ether resin and a crosslinked resin obtained by crosslinking the polyphenylene ether resin are used. For example, Patent Document 1 discloses a method for producing a prepreg in which a base material is impregnated with a polyphenylene ether resin. However, this prepreg may be inferior in moldability. Moreover, the crosslinked resin obtained by crosslinking the prepreg may have insufficient heat resistance, adhesion and electrical characteristics.

  As a resin composition having excellent moldability, Patent Document 2 discloses a resin composition containing a polyphenylene ether resin having a specific number average molecular weight. Patent Document 3 discloses a resin composition containing a polyphenylene ether resin whose end is blocked with a methacryloyl group or the like. However, the cross-linked resins obtained using these resin compositions have insufficient electrical characteristics.

  Patent Document 4 discloses a polyphenylene ether resin composition containing diisopropylbenzene oligomer as a curing agent. Furthermore, it is described that when such a composition is used, the polyphenylene ether resin can be efficiently cured to obtain a crosslinked resin. However, the crosslinked resin obtained by this production method sometimes lacks heat resistance and adhesion. Moreover, the electrical characteristics may not be sufficient.

JP-A-8-259712 JP 2002-265777 A Special table 2003-515642 gazette JP 2000-336108 A

  An object of this invention is to provide the crosslinkable resin composition which is excellent in a moldability which can obtain the crosslinked resin and crosslinked resin composite which have the outstanding electrical property, heat resistance, and adhesiveness, and its use.

  As a result of intensive studies, the present inventors have used a crosslinkable resin composition containing a terminal-modified polyphenylene ether resin having a carbon-carbon unsaturated bond at the end of at least one molecular chain and a nonpolar radical generator. The present inventors have found that the above problems can be solved, and have completed the present invention based on this finding.

Thus, according to the present invention, the following [1] to [15] are provided.
[1] A crosslinkable resin composition comprising a terminal-modified polyphenylene ether resin having a carbon-carbon unsaturated bond at at least one molecular chain terminal and a nonpolar radical generator.
[2] The crosslinkable resin composition according to [1], wherein the carbon-carbon unsaturated bond forms a conjugated system.
[3] The crosslinkable resin composition according to [1] or [2], wherein the terminal-modified polyphenylene ether resin contains 90% by weight or more of a repeating unit represented by the following formula (1).

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom, a halogen atom, or an alkyl group, alkenyl group, alkynyl group, aryl group, or haloalkyl group having 1 to 20 carbon atoms.)

[4] The crosslinkable resin composition according to any one of [1] to [3], wherein the nonpolar radical generator is a hydrocarbon compound having a structure represented by the following formula (4).

(In the formula, R ⁵ , R ⁶ , R ⁷ , R ′ ⁵ , R ′ ⁶ , and R ′ ⁷ are each independently a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, or an alicyclic carbonization. Represents a hydrogen group or an aromatic hydrocarbon group.)

[5] The crosslinkable resin composition according to any one of [1] to [3], wherein the nonpolar radical generator is a hydrocarbon compound having a structure represented by the following formula (5).

(In the formula, R ⁸ represents an aromatic hydrocarbon group, and R ⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)

[6] The crosslinkable resin composition according to any one of [1] to [5], wherein the nonpolar radical generator has a one-minute half-life temperature of 150 ° C to 350 ° C.
[7] The crosslinkable resin composition according to any one of [1] to [6], further including a crosslinkable compound.
[8] The crosslinkable resin composition according to any one of [1] to [7], wherein the number average molecular weight of the terminal-modified polyphenylene ether resin is 2,000 to 15,000.

[9] A crosslinkable resin composite obtained by coating or impregnating a support with the crosslinkable resin composition according to any one of [1] to [8].
[10] A crosslinked resin obtained by crosslinking the crosslinkable resin composition according to any one of [1] to [8].
[11] A crosslinked resin composite obtained by crosslinking the crosslinkable resin composition according to any one of [1] to [8] on a support.
[12] A crosslinked resin composite obtained by crosslinking the crosslinkable resin composite according to [9].
[13] The crosslinked resin composite according to [11], wherein the crosslinking is performed on another support.
[14] A method for producing a crosslinkable resin composite, comprising a step of applying or impregnating a varnish of the crosslinkable resin composition according to any one of [1] to [8] to a support and drying.
[15] A method for producing a crosslinked resin, comprising a step of crosslinking the crosslinkable resin composition according to any one of [1] to [8].

  The crosslinkable resin composition of the present invention is excellent in moldability, and by crosslinking this, a crosslinkable resin and a crosslinkable resin composite having excellent electrical properties, heat resistance and adhesion can be obtained. The cross-linked resin and the cross-linked resin composite of the present invention are suitable as an electric material used for an electric circuit board.

(Terminal-modified polyphenylene ether resin)
The crosslinkable resin composition of the present invention contains at least one terminal-modified polyphenylene ether resin having an unsaturated hydrocarbon group at the molecular chain terminal and a nonpolar radical generator. The terminal-modified polyphenylene ether resin used in the present invention is a polymer having a repeating unit formed by 1,4-bonding a phenyleneoxy group which may have a substituent. Such a repeating unit is represented by the following formula (1).

In the formula, each of R ^{1 to} R ⁴ independently represents a hydrogen atom, a halogen atom, or an alkyl group, alkenyl group, alkynyl group, aryl group, or haloalkyl group having 1 to 20 carbon atoms. Among these, R ¹ and R ⁴ are preferably an alkyl group or an alkenyl group, and more preferably a methyl group. R ² and R ³ are preferably hydrogen atoms.

  The content of the repeating unit represented by the formula (1) in the terminal-modified polyphenylene ether resin is preferably 80% by weight or more, more preferably 90% by weight or more. The terminal-modified polyphenylene ether resin used in the present invention may have a repeating unit other than the repeating unit represented by the formula (1). Such a repeating unit is not particularly limited as long as it is a divalent organic group. Specific examples include an alkylene group, an arylene group, and an oxygen atom.

  The terminal-modified polyphenylene ether resin may be a linear polymer formed from these repeating units, or may be a branched polymer having a structure in which a plurality of such polymers are bonded.

  The terminal-modified polyphenylene ether resin used in the present invention has a carbon-carbon unsaturated bond at the end of at least one molecular chain. The terminal-modified polyphenylene ether resin preferably has a carbon-carbon unsaturated bond at 80% or more of all molecular chain terminals, and particularly preferably has a carbon-carbon unsaturated bond at 90% or more of molecular chain terminals.

  In the present invention, “having a carbon-carbon unsaturated bond at the molecular chain terminal” means that the repeating unit represented by the formula (1) at the molecular chain terminal is at the 1-position (ie, oxygen atom) or 4-position. It represents that a vinyl group; or an ethynyl group is present directly or through another divalent organic group. As such a group, a vinyl group is preferable because it has a high crosslinking reactivity. By crosslinking, the molecular weight after crosslinking is increased, the glass transition point is increased, and heat resistance and the like are improved.

  The carbon-carbon unsaturated bond preferably forms a conjugated system. Here, forming a conjugated system means that the carbon-carbon unsaturated bond and another unsaturated bond exist with one single bond in between. Examples of the other unsaturated bond include a carbon-carbon double bond, a carbon-carbon triple bond, and an aromatic ring, and a carbon-carbon double bond and an aromatic ring are preferable.

  As a method for introducing an unsaturated hydrocarbon group by modifying the molecular chain terminal of an unmodified polyphenylene ether resin, a carbon-carbon unsaturated bond is added to the unmodified polyphenylene ether resin in the presence of a basic hydroxide. And a method of reacting a halogenated hydrocarbon compound having the following. Examples of the basic hydroxide include sodium hydroxide, potassium hydroxide and tetraalkylammonium hydroxide. Examples of the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond include p-chloromethylstyrene, m-chloromethylstyrene, p-bromomethylstyrene, m-bromomethylstyrene, and allyl bromide. . Further, in order to accelerate the reaction, a quaternary ammonium salt such as tetra-n-butylammonium bromide may be used as a phase transfer catalyst. Although reaction conditions are not specifically limited, Reaction temperature is 30-100 degreeC normally, and reaction time is 0.5 to 20 hours normally. Since the polar structure in the polyphenylene ether resin is reduced by modifying the terminal, the cross-linked resin obtained using this has excellent electrical characteristics.

  The molecular weight of the terminal-modified polyphenylene ether resin used in the present invention is a number average molecular weight in terms of standard polystyrene measured by gel permeation chromatography, preferably 2,000 to 15,000, more preferably 2, 000 to 10,000. When the number average molecular weight is within this range, it becomes possible to produce a resin having both excellent fluidity and heat resistance.

(Method for producing unmodified polyphenylene ether resin)
Any known method can be adopted as a method for producing an unmodified polyphenylene ether resin used as a precursor of a terminal-modified polyphenylene ether resin, and there is no particular limitation, but an oxidation polymerization method is preferred. The oxidative polymerization method is a method in which monovalent phenol represented by formula (2) and / or divalent phenol represented by formula (3) is oxidatively polymerized in the presence of a catalyst. According to the oxidative polymerization method, a polyphenylene ether resin having the above molecular weight range can be easily obtained. Examples of the oxidation method include a method using oxygen gas or air directly, or an electrode oxidation method.

In formula (2) and formula (3), R ^{1 to} R ⁴ represent the same meaning as in formula (1). In the formula (3) represent the same meaning as ^R 1 to R ⁴ of R ^'1 to ^{R' 4} each formula (1).

As a catalyst for oxidative polymerization using oxygen gas or air, a catalyst in which a copper salt and an amine are combined is used. The copper _{salt, CuCl, CuBr, Cu 2 SO} 4, CuCl 2, CuBr 2, CuSO 4, CuI , and the like. Examples of amines include pyridine, methylpyridine, N, N-dimethyl-4-aminopyridine, poly-4-vinylpyridine, piperidine, morpholine, triethanolamine, n-butylamine, octylamine, dibutylamine, N, N- Dimethyl-n-hexylamine, N, N-dimethyl-n-butylamine, triethylamine, (N, N-di-tert-butyl) ethylenediamine 2-aminoethanethiol, 2-mercapto-1-ethanol, 1,2-dimercapto -4-methylbenzene and the like.

  The solvent used in the polymerization is not particularly limited, and the temperature of the polymerization reaction is not limited, but it is preferably performed at 0 to 50 ° C.

  The high molecular weight polyphenylene ether resin can be used in the above molecular weight range by reducing the molecular weight by a redistribution reaction disclosed in The Journal of Organic Chemistry, 1969, Vol. 34, 297. The redistribution reaction is a method of reducing the molecular weight by reacting a polyphenylene ether resin with phenols in the presence of a radical initiator.

  The phenols used in the redistribution reaction include phenol, o-bromophenol, m-bromophenol, p-bromophenol, p-chlorophenol, 2,6-dichlorophenol, pentachlorophenol, o-cresol, and m-cresol. P-cresol, 2,6-xylenol, mesitol, 2,6-dimethyl-4- (benzoyloxy) phenol, p-methoxyphenol, p-phenoxyphenol, hydroquinone monobenzoate, β-naphthol, p-hydroxybenzonitrile, Examples include 2,6-dimethylphenol, p-nitrophenol, methyl p-hydroxybenzoate, methyl salicylate, bisphenol A, 2,6-dimethylphenol, 4,4′-dihydroxydiphenyl ether. Although the usage-amount of phenols can be suitably adjusted according to the molecular weight of desired polyphenylene ether, 0.5-10 weight part is preferable with respect to 100 weight part of polyphenylene ether resin.

  As radical initiators, benzoyl peroxide, 3,3 ′, 5,5′-tetramethyl-1,4-diphenoquinone, chloranil, 2,4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl Examples thereof include monocarbonate and azobisisobutyronitrile. The amount of the radical initiator used is preferably 0.5 to 5.0 parts by weight with respect to 100 parts by weight of the polyphenylene ether resin. Moreover, it is preferable to use metal carboxylates such as cobalt naphthenate and manganese naphthenate as the reaction accelerator.

  The redistribution reaction is preferably performed in a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction, but aromatic hydrocarbons such as toluene, benzene and xylene are preferable. The redistribution reaction can be carried out by dissolving or dispersing the polyphenylene ether resin, the phenols, the radical initiator, and the carboxylic acid metal salt used as required in a solvent and heating them. The reaction temperature is preferably 60 to 120 ° C., and the reaction time is preferably 10 minutes to 6 hours.

  The polyphenylene ether resin obtained as described above usually has a hydroxyl group at the terminal or a phenyl group which may have a substituent at the ortho or meta position. A terminal-modified polyphenylene ether resin used in the present invention can be obtained by modifying the terminal of this unmodified polyphenylene ether resin by the above method.

(Non-polar radical generator)
The crosslinkable resin composition of the present invention contains a nonpolar radical generator. A nonpolar radical generator is a compound that can generate a radical by heating and initiate a crosslinking reaction when the dipole moment is 0.5 or less. The dipole moment is preferably 0.3 or less, more preferably 0.15 or less.
The nonpolar radical generator used in the present invention preferably has a 1 minute half-life temperature of 150 to 350 ° C, more preferably 200 to 300 ° C.
As said nonpolar radical generating agent, what has the structure in any one of Formula (4)-(6) is preferable, and what has the structure of Formula (4) or Formula (5) is more preferable.

In formula (4), R ⁵ , R ⁶ , R ⁷ , R ′ ⁵ , R ′ ⁶ , and R ′ ⁷ are each independently a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, an aliphatic group Represents a cyclic hydrocarbon group or an aromatic hydrocarbon group. Of R ⁵ , R ⁶ , and R ⁷ , at least one is preferably an aromatic hydrocarbon group. In addition, at least one of R ′ ⁵ , R ′ ⁶ and R ′ ⁷ is preferably an aromatic hydrocarbon group.

In the formula (5), R ⁸ represents an aromatic hydrocarbon group, and R ⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

  In formula (6), n represents the number average degree of polymerization, and is usually 2 to 50, preferably 3 to 40.

  Specific examples of the nonpolar radical generator include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diphenylbutane, 1,4-diphenylbutane, and 3,4-dimethyl-3,4-diphenylhexane. 1,1,2,2-tetraphenylethane, 2,2,3,3-tetraphenylbutane, 3,3,4,4-tetraphenylhexane, 1,1,2-triphenylpropane, 1,1 , Hydrocarbon compounds represented by the formula (4) such as 2-triphenylethane;

Triphenylmethane, 1,1,1-triphenylethane, 1,1,1-triphenylpropane, 1,1,1-triphenylbutane, 1,1,1-triphenylpentane, 1,1,1- Hydrocarbon compounds represented by the formula (5) such as triphenyl-2-propene, 1,1,1-triphenyl-4-pentene, 1,1,1-triphenyl-2-phenylethane; It is done. In addition to those represented by the formulas (4) to (6), 2,3-trimethylsilyloxy-2,3-diphenylbutane can also be used.
Among these, 2,3-dimethyl-2,3-diphenylbutane and triphenylmethane are preferable.
By using a nonpolar radical generator, the electrical properties of the resulting crosslinked resin composite can be significantly improved. The principle is unknown, but it is presumed that polar substances are not included in the decomposition products of the nonpolar radical generator.

  These nonpolar radical generators can be used alone, or a mixture of nonpolar radical generators in which two or more of these are mixed can also be used. It is possible to freely control the molten state of the resulting crosslinkable resin by using two or more kinds of nonpolar radical generators together and changing the mixing ratio.

  The usage-amount of a nonpolar radical generator is 0.2-20 weight part normally with respect to 100 weight part of terminal modified polyphenylene ether resin, Preferably it is 1-10 weight part. If the amount of the nonpolar radical generator is too small, crosslinking may be insufficient, and a crosslinked resin having a high crosslinking density may not be obtained. When the amount of the nonpolar radical generator is too large, the crosslinking effect is saturated, but a crosslinked resin having desired physical properties may not be obtained.

  In the present invention, the above-mentioned nonpolar radical generator is used as a crosslinking agent. However, the crosslinkable resin composition of the present invention contains a crosslinking agent other than the nonpolar radical generator as long as the effects of the present invention are not impaired. You may not. Examples of other crosslinking agents include peroxides.

(Crosslinkable compound)
The crosslinkable resin composition of the present invention preferably further contains a crosslinkable compound. The crosslinkable compound is a low molecular or high molecular compound having a radical reactive unsaturated group in the molecule. The crosslinkable compound is preferably a compound having two or more unsaturated groups in the molecule and excellent compatibility with the terminal-modified polyphenylene ether resin. Examples of crosslinkable compounds include polyfunctional vinyl compounds such as divinylbenzene and divinylnaphthalene; cyanuric acids such as triallyl isocyanurate, triallyl cyanurate, and trimethallyl cyanurate; diallyl phthalate, diallyl isophthalate, diallyl maleate, diallyl fuma Diallyl esters of polyhydric acids such as dirate, diallyl sebacate, triallyl phosphate; diethylene glycol bisallyl carbonate; allyl ethers such as ethylene glycol diallyl ether, allyl ether of trimethylolpropane, partial allyl ether of pentaerythritol; Allyl-modified resins such as modified novolak and allylated resole resin; trimethylolpropane trimethacrylate (TMTP) and trimethylolpropane triac Such as rate, 3-5 functional methacrylate compound and acrylate compound; can be used. Of these, triallyl cyanurate and triallyl isocyanurate are preferred because of their high crosslinking reactivity, and triallyl isocyanurate is particularly preferred because transmission loss can be kept small without deteriorating the dielectric loss tangent.
Moreover, you may use together two types of crosslinkable compounds as needed. By using two or more kinds of crosslinkable compounds in combination, heat resistance can be improved while maintaining electrical characteristics. Specifically, it is preferable to use triallyl isocyanurate in combination with a 3-5 functional methacrylate compound or acrylate compound.

  The total amount of the crosslinkable compound is appropriately selected depending on the kind thereof, but is usually 10 to 100 parts by weight, preferably 10 to 70 parts by weight with respect to 100 parts by weight of the terminal-modified polyphenylene ether resin. When triallyl isocyanurate and a 3 to 5 functional methacrylate compound or acrylate compound are used in combination, the amount of the latter is preferably 5 to 15 parts by weight with respect to 100 parts by weight of the terminal-modified polyphenylene ether resin. If the amount is less than 5 parts by weight, the effect of improving the heat resistance of the laminate may not be sufficiently obtained. Conversely, if the amount exceeds 15 parts by weight, the dielectric properties may be deteriorated.

(Other additives)
The crosslinkable resin composition of the present invention can contain various additives such as reinforcing materials, compatibilizers, antioxidants, flame retardants, fillers, colorants, and light stabilizers.

  Examples of the reinforcing material include glass fiber, glass cloth, paper base material, and glass nonwoven fabric.

  Examples of compatibilizers include styrene / butadiene block copolymers, styrene / isoprene block copolymers, 1,2-polybutadiene, 1,4-polybutadiene, maleic-modified polybutadiene, acrylic-modified polybutadiene, epoxy-modified polybutadiene, and vinylbenzyl ether resins. It is done.

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

  Examples of the flame retardant include phosphorus-containing flame retardants, nitrogen-containing flame retardants, halogen-containing flame retardants, metal hydroxide flame retardants such as aluminum hydroxide, and antimony compounds such as antimony trioxide. Among them, a halogen-containing flame retardant is preferable, and a brominated organic compound that contains a bromine atom as a halogen and does not have an unsaturated bond is more preferable because it does not affect the crosslinking reaction. As such brominated organic compounds, aromatic brominated compounds such as decabromodiphenylethane, 4,4-dibromobiphenyl, and ethylenebistetrabromophthalimide are particularly preferable. Furthermore, a halogenated triallyl isocyanurate, a fluorinated aliphatic resin, or the like can be used as the halogen-containing flame retardant. Moreover, as a flame retardant, what has a true specific gravity in the range of 2.0-3.5 is preferable. The amount of the flame retardant is preferably 10 to 40 parts by weight with respect to 100 parts by weight of the polyphenylene ether resin.

  As fillers, powders of metal hydrates such as silica, aluminum hydroxide, magnesium hydroxide; metal oxides such as boron nitride, wollastonite, talc, kaolin, clay, mica, alumina, zirconia, titania, And inorganic fillers such as nitrides, silicides or borides. By adding fillers, the coefficient of thermal expansion of the resulting cross-linked resin and cross-linked resin composite can be reduced, reducing the rate of dimensional change during heating and improving reliability when used for multilayer printed wiring boards, etc. Can be improved. Two or more of these fillers may be used in combination. As the filler, one that has been surface-treated with a silane coupling agent or the like can also be used. The amount of the filler is usually 0 to 200 parts by weight, preferably 5 to 60 parts by weight with respect to 100 parts by weight of the terminal-modified polyphenylene ether resin.

  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.

(Method for producing crosslinkable resin composition)
The crosslinkable resin composition of the present invention is obtained by mixing the above-mentioned terminal-modified polyphenylene ether resin, a nonpolar radical generator, and optional components such as a crosslinkable compound and additives used as necessary. The method of mixing is not particularly limited, but these components are uniformly dissolved or dispersed in a solvent to obtain a crosslinkable resin composition as a varnish, or terminal-modified polyphenylene ether resin is heated and melted using an extruder or the like. And a method of uniformly kneading.

  The solvent used for obtaining the crosslinkable resin composition as a varnish is not particularly limited as long as it can uniformly dissolve or disperse the above components, but ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ethers such as dibutyl ether and tetrahydrofuran; esters such as ethyl acetate; amides such as dimethylformamide; aromatic hydrocarbons such as benzene, toluene and xylene; chlorinated hydrocarbons such as dichloromethane and trichloroethylene; Can be mentioned. These can be used individually by 1 type or in mixture of 2 or more types.

(Crosslinkable resin composite)
The crosslinkable resin composite of the present invention is formed by applying or impregnating a support with the crosslinkable resin composition of the present invention. The crosslinkable resin composition may be used for coating or impregnation by heating and melting it, but it can be uniformly applied or impregnated and used as the varnish from the viewpoint of excellent workability. Is preferred. The crosslinkable resin composite of the present invention is obtained by applying or impregnating a varnish to a support and removing the solvent by drying. The concentration of the terminal-modified polyphenylene ether resin in the varnish is preferably 40 to 70% by weight. The drying conditions are appropriately set according to the composition of the crosslinkable resin composition, but the temperature is preferably 110 to 130 ° C., and the drying time is preferably 5 to 10 minutes.

  As a support used for application of the crosslinkable resin composition, resins such as polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, and nylon; iron, stainless steel, copper, aluminum, nickel, chromium, gold, Examples thereof include a metal material such as silver. Moreover, when using metal foil as a support body, it is preferable from an adhesive viewpoint that the surface is surface-treated with the silane coupling agent etc.

  The method for applying the crosslinkable resin composition to the support is not particularly limited, and known coating methods such as spin coating, spray coating, dip coating, roll coating, curtain coating, die coating, and slit coating may be used. Can be mentioned.

  The support used for the impregnation of the crosslinkable resin composition is a fiber material. According to this method, a prepreg that is a crosslinkable resin composite in which a fiber material is impregnated with a crosslinkable resin composition can be obtained. The material of the fiber material used here is organic and / or inorganic fiber, for example, inorganic fiber such as glass fiber, carbon fiber, metal fiber, ceramic fiber; aramid fiber, polyethylene terephthalate fiber, vinylon fiber, polyester fiber Organic fibers such as polyamide fiber and polyacrylic fiber. These can be used alone or in combination of two or more. Examples of the shape of the fiber material include mat, cloth, and non-woven fabric. Among these, glass cloth such as E-type, NE-type, S-type, T-type, and D-type; and organic fibers such as aramid fiber, polyester fiber, polyimide fiber, and polyacrylic fiber are preferable. Moreover, it is preferable that the surface of these fiber materials is surface-treated with a silane coupling agent or the like.

  For impregnation of the crosslinkable resin composition into the fiber material, for example, a predetermined amount of the polymerizable composition is added to a known amount such as a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a die coating method, or a slit coating method. This is achieved by applying the fiber material by a method.

(Crosslinked resin)
The cross-linked resin of the present invention is obtained by cross-linking the cross-linkable resin composition of the present invention. Crosslinking of the crosslinkable resin composition is maintained at a temperature equal to or higher than the temperature at which the terminal-modified polyphenylene ether resin and the crosslinkable compound in the composition cause a crosslinking reaction by, for example, heating and melting the crosslinkable resin composition of the present invention. Can be done. The temperature for crosslinking the crosslinkable resin is usually 170 to 250 ° C, preferably 180 to 230 ° C. The time for crosslinking is not particularly limited, but is usually from several minutes to several hours.

  When the crosslinkable resin composition is a sheet-shaped or film-shaped molded body, a method of laminating the molded body as necessary and hot pressing is preferable. The pressure at the time of hot pressing is usually 0.5 to 20 MPa, preferably 2 to 5 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).

(Crosslinked resin composite)
The cross-linked resin composite of the present invention is obtained by (A) cross-linking the cross-linkable resin composition of the present invention on a support, and (B) cross-linking the cross-linkable resin composite of the present invention. And (C) The crosslinkable resin composite of the present invention is cross-linked on another support.

  Examples of the method for obtaining the crosslinked resin composite according to the above (B) include a method of laminating the crosslinkable resin composite as necessary and hot pressing. The conditions for hot pressing are the same as those for crosslinking the crosslinkable resin.

  As a method for obtaining the crosslinked resin composite according to the above (A) or (C), a crosslinkable resin composition or a crosslinkable resin composite molded into a plate shape or a film shape is laminated on a support by hot pressing. And a method of crosslinking the terminal-modified polyphenylene ether resin and the crosslinkable compound by further heating. The conditions for hot pressing are the same as those for crosslinking the crosslinkable resin.

  New supports used here include metal foils such as copper foil, aluminum foil, nickel foil, chrome foil, gold foil, and silver foil; printed wiring boards; films such as conductive polymer films and other resin films; Is mentioned. Further, when a printed wiring board is used as the support, a multilayer printed wiring board can be manufactured.

  The surface of the conductive layer on the metal foil such as copper foil or printed wiring board is preferably treated with a silane coupling agent, a thiol coupling agent, a titanate coupling agent, or various adhesives. Of these, those treated with a silane coupling agent are particularly preferred.

  Since the crosslinkable resin composition and the crosslinkable resin composite of the present invention are excellent in fluidity and adhesion, it is possible to obtain a crosslinkable resin composite excellent in flatness and excellent in adhesion to the support. it can. The crosslinked resin and crosslinked resin composite of the present invention are excellent in electrical insulation, mechanical strength, heat resistance, dielectric properties and the like. Further, the crosslinked resin composite has good adhesion to the support and is suitable as an electric material.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. In the examples and comparative examples, “part” and “%” are based on weight unless otherwise specified. In the examples and comparative examples, each characteristic was measured according to the following method.

(1) Number average molecular weight (Mn)
The number average molecular weight (Mn) of the polyphenylene ether resin was determined as a standard polystyrene conversion value by gel permeation chromatography measurement using toluene as a developing solvent.

(2) Formability The moldability of the prepreg was evaluated from the unevenness and creaking of the crosslinked resin composite A. First, unevenness was evaluated from observation of the surface state of the crosslinked resin composite A. Next, the crosslinked resin composite A was immersed in a ferric chloride solution (manufactured by Sanhayato) at 50 ° C. and etched to peel off the copper foil. The state of the crosslinked resin composite after peeling the copper foil was observed and evaluated from both the surface and the cross section. The surface was observed visually, and the cross-sectional observation was performed using an optical microscope after polishing the cross section of the crosslinked resin composite using a polishing machine.
The evaluation criteria are as follows. Here, the unevenness means that the unevenness along the IPC standard wiring pattern is observed visually, and the blur is copper foil and resin, resin and glass cloth, resin and IPC substrate, etc. A space is generated between different materials. If there is no unevenness, the laminate is flat regardless of the presence or absence of the wiring pattern.
A: There is no unevenness, no blur, and it is flat.
B: Either the unevenness | corrugation on the surface of copper foil, or a blurring generate | occur | produced in a part of whole area.
C: There were irregularities on the surface of the copper foil, and scouring occurred entirely on the surface and cross-sectional observation after peeling the copper foil.

(3) Glass transition temperature (Tg)
About the crosslinked resin composite B from which the copper foil was removed, the glass transition temperature was measured by dynamic viscoelasticity measurement. The higher the glass transition temperature, the more excellent the heat resistance of the crosslinked resin composite.

(4) Peel strength The strength when peeling the copper foil from the crosslinked resin composite C was measured based on JIS C6481. The following indices were used for evaluation according to the peel strength value. It represents that it is excellent in adhesiveness with copper foil, so that peel strength is large.
A: More than 0.50 kN / m B: More than 0.35 kN / m and 0.50 kN / m or less C: 0.35 kN / m or less

(5) Dielectric loss The dielectric loss (tan δ) of the crosslinked resin composite C from which the copper foil was removed at a frequency of 1 GHz was measured by a capacitance method using an impedance analyzer (manufactured by Agilent Technologies, model number E4991A).

Production Example 1: Production of Modified PPE- (1) Polyphenylene ether resin (PPE; manufactured by Nippon GE Plastics Co., Ltd .: trade name “Noryl PX9701”, Mn = 14,000) 36 parts, 2,6-phenol as phenols 1.54 parts of dimethylphenol, 1.06 parts of t-butylperoxyisopropyl monocarbonate (manufactured by NOF Corporation: trade name “Perbutyl I”) as a radical initiator, and 0.0015 part of cobalt naphthenate as a toluene solvent Add to 90 parts and mix. The obtained mixed solution was heated to 80 ° C., and redistribution reaction was performed while stirring for 1 hour. After completion of the reaction, a large amount of methanol was added to reprecipitate PPE to remove impurities, followed by drying at 80 ° C. under reduced pressure for 3 hours to completely remove the solvent. Mn of the obtained PPE was 2,400.

  In a flask equipped with a temperature controller, a stirrer, a cooling facility and a dropping funnel, 200 parts of PPE (Mn = 2400) having a reduced molecular weight as described above, chloromethylstyrene (p-chloromethylstyrene and m-chloromethylstyrene) The ratio was 50/50, manufactured by Tokyo Chemical Industry Co., Ltd.) 14.51 parts, 0.818 parts tetra-n-butylammonium bromide, and 400 parts toluene were mixed. The temperature of the mixture was 75 ° C., 22 parts of a 50% aqueous solution of sodium hydroxide was added dropwise over 20 minutes while stirring, and the mixture was further stirred at 75 ° C. for 4 hours to carry out a modification reaction. Next, after neutralizing the mixed solution with a 10% aqueous hydrochloric acid solution, a large amount of methanol was added, and the product was reprecipitated and then filtered. The filtrate was washed 3 times with a mixed solution of methanol: water = 80: 20 and then dried at 80 ° C. under reduced pressure for 3 hours to obtain modified PPE- (1). The Mn of this modified PPE- (1) was 2,700.

The modified PPE- (1) was subjected to infrared absorption spectrum (IR) measurement and ¹ H nuclear magnetic resonance spectrum ( ¹ H-NMR) measurement. As a result, the presence of a phenolic hydroxyl group by IR measurement and a signal indicating a vinylbenzyl group appearing in the vicinity of 5 to 6 ppm on the NMR chart are observed, whereby the modified PPE- (1) has a vinylbenzyl group at the molecular end. It was confirmed that this is a polyphenylene ether resin having

Production Example 2: Production of unmodified PPE- (1) 250 parts of PPE “Noryl PX9701”, 2.5 parts of bisphenol A as a phenol, and t-butylperoxyisopropyl monocarbonate (“Perbutyl I”) as a radical initiator Was added to 600 parts of toluene as a solvent, and mixed. The obtained mixed solution was heated to 90 ° C., and redistribution reaction was performed while stirring for 1 hour. After completion of the reaction, a large amount of methanol was added to reprecipitate the product, impurities were removed, and the solvent was completely removed by drying at 80 ° C. under reduced pressure for 3 hours to obtain unmodified PPE- (1). . Mn of unmodified PPE- (1) was 9,000.

Production Example 3: Production of Modified PPE- (2) 200 parts of unmodified PPE- (1) obtained in Production Example 2 was used instead of 200 parts of PPE with Mn = 2,400 by redistribution reaction. Then, a modification reaction was carried out in the same manner as in Production Example 1 to obtain a modified PPE- (2). The Mn of this modified PPE- (2) was 9,300. Further, in the same manner as in Production Example 1, it was confirmed that the modified PPE- (2) was a polyphenylene ether resin having a vinylbenzyl group at the molecular end.

Production Example 4: Production of Modified PPE- (3) A modification reaction was conducted in the same manner as in Production Example 3 except that 10.13 parts of 2-chloroethyl vinyl ether was used instead of 14.51 parts of chloromethylstyrene. Modified PPE- (3) was obtained. The Mn of this modified PPE- (3) was 9,200. Moreover, IR measurement and ¹ H-NMR measurement of the modified PPE- (3) were performed. As a result, the modified PPE- (3) has a vinyloxy group at the molecular end due to the absence of a phenolic hydroxyl group by IR measurement and a signal derived from a vinyloxy group appearing in the vicinity of 4 to 5 ppm on the NMR chart. It was confirmed to be a polyphenylene ether resin.

Example 1
70 parts of the modified PPE- (1) was added to 100 parts of toluene as a solvent, and stirred and mixed at 80 ° C. for 30 minutes to completely dissolve. In the obtained solution, 30 parts of triallyl isocyanurate (TAIC; manufactured by Nippon Kasei Co., Ltd.) as a crosslinkable compound, decabromodiphenylethane (Albemarle Asano Co., Ltd., trade name “SAYTEX8010”) as a brominated organic compound as a flame retardant, 2,3-dimethyl-2,3-diphenylbutane (manufactured by NOF Corporation: trade name “Nofmer BC-90”, dipole moment 0.00) as 20 parts of Br content 82%) and nonpolar radical generator 4.0 parts of was added. Further, 14 parts of spherical silica (trade name “FB3SDC” manufactured by Denki Kagaku Kogyo Co., Ltd.) was added as an inorganic filler, and these were mixed and dispersed to obtain a varnish of a crosslinkable resin composition.

  Next, this varnish was impregnated in an E type glass cloth (manufactured by Nitto Boseki Co., Ltd .: trade name “WEA2116E”), heated and dried at a temperature of 180 ° C. for 3 minutes, and the solvent was removed to prepare a prepreg having a resin content of 55%. A crosslinkable resin composite was obtained. Using the prepreg thus obtained, crosslinked resin composites were prepared by the following methods (A) to (C).

(A) One prepreg cut into a 100 mm square is sandwiched between an IPC substrate (IPC standard multipurpose substrate) and an electrolytic copper foil (Type F0, thickness 0.018 mm, manufactured by Furukawa Circuit Foil Co., Ltd.). While maintaining the above, it was hot pressed to obtain a crosslinked resin composite A. The conditions for hot pressing were a temperature of 220 ° C., a time of 60 minutes, and a pressure of 3 MPa. Using this crosslinked resin composite A, moldability was evaluated. The evaluation results are shown in Table 1.

(B) Both sides of one prepreg are sandwiched between electrolytic copper foils (Type F0, thickness 0.018 mm, manufactured by Furukawa Circuit Foil Co., Ltd.) and hot-pressed while maintaining a flat plate shape with a hot press machine, and a crosslinked resin composite B was obtained. The conditions for hot pressing were a temperature of 220 ° C., a time of 60 minutes, and a pressure of 3 MPa. Subsequently, this crosslinked resin composite B was immersed in a 50 ° C. ferric chloride solution (manufactured by Sanhayato Co., Ltd.) to remove the surface copper foil. About the crosslinked resin composite B from which the copper foil was removed, the glass transition temperature was measured using a dynamic viscoelasticity measuring apparatus. The evaluation results are shown in Table 1.

(C) 7 sheets of prepreg are stacked, and both sides are sandwiched between 2 sheets of electrolytic copper foil (Type F0, thickness 0.018 mm, manufactured by Furukawa Circuit Foil Co., Ltd.), and hot pressed while maintaining a flat plate shape with a hot press machine. A crosslinked resin composite C was obtained. The conditions for hot pressing were a temperature of 220 ° C., a time of 60 minutes, and a pressure of 3 MPa. The peel strength of the crosslinked resin composite C was measured. Further, this crosslinked resin composite C was cut into a size of 20 mm square, immersed in a ferric chloride solution (manufactured by Sanhayato) at 40 ° C., and the copper foil on the surface was removed. Dielectric loss was measured for the crosslinked resin composite C from which the copper foil was removed. The evaluation results are shown in Table 1.

Examples 2 and 3
A prepreg and a crosslinked resin composite were prepared in the same manner as in Example 1 except that 70 parts of modified PPE- (2) and 70 parts of modified PPE- (3) were used instead of 70 parts of modified PPE- (1). Manufactured. Table 1 shows the results of evaluating the characteristics of these.

Example 4
Example 3 was used except that 3.9 parts of triphenylmethane (dipole moment 0.13) was used instead of 3.2 parts of 2,3-dimethyl-2,3-diphenylbutane as the nonpolar radical generator. In the same manner as in Example 2, a prepreg and a crosslinked resin composite were produced. Table 1 shows the results of evaluating the characteristics of these.

Example 5
As a nonpolar radical generator, instead of 3.2 parts of 2,3-dimethyl-2,3-diphenylbutane, 6.4 parts of 1,1,2,2-tetraphenylethane (dipole moment 0.18) A prepreg and a crosslinked resin composite were produced in the same manner as in Example 2 except that was used. Table 1 shows the results of evaluating the characteristics of these.

Comparative Example 1
A prepreg and a crosslinked resin composite were produced in the same manner as in Example 2 except that 70 parts of unmodified PPE- (1) was used instead of 70 parts of modified PPE- (2). Table 1 shows the results of evaluating the characteristics of these.

Comparative Example 2
Instead of 4.0 parts of 2,3-dimethyl-2,3-diphenylbutane as a crosslinking agent, 2.2 parts of di-t-butyl peroxide (manufactured by NOF Corporation: trade name “Perbutyl D”, dipole moment) A prepreg and a cross-linked resin composite were produced in the same manner as in Comparative Example 1, except that the temperature of the hot press was 200 ° C., the time was 20 minutes, and the pressure was 3 MPa. Table 1 shows the results of evaluating the characteristics of these.

Comparative Example 3
A prepreg and a crosslinked resin composite were produced in the same manner as in Comparative Example 2, except that 70 parts of modified PPE- (2) was used instead of 70 parts of unmodified PPE- (1). Table 1 shows the results of evaluating the characteristics of these.

  As is clear from the above, since the crosslinkable resin composition of the present invention is excellent in moldability, the crosslinkable resin composite obtained using this composition is flat without irregularities and blurring. Further, the crosslinked resin composite had high adhesion to the copper foil, high heat resistance, low dielectric loss, and excellent electrical characteristics (Examples 1 to 5).

  On the other hand, when (unmodified) polyphenylene ether resin having no carbon-carbon unsaturated bond at the molecular chain end is used, the resulting crosslinked resin composite has low heat resistance and insufficient electrical properties. (Comparative Example 1). Moreover, when di (2-t-butylperoxyisopropylbenzene) having polarity is used as a crosslinking agent, the moldability of the crosslinkable resin composition is low, and the resulting crosslinked resin composite has low adhesion to the copper foil. (Comparative Examples 2 and 3).

Claims (15)

A crosslinkable resin composition comprising a terminal-modified polyphenylene ether resin having a carbon-carbon unsaturated bond at at least one molecular chain terminal, and a nonpolar radical generator. The crosslinkable resin composition according to claim 1, wherein the carbon-carbon unsaturated bond forms a conjugated system. The crosslinkable resin composition according to claim 1 or 2, wherein the terminal-modified polyphenylene ether resin contains 90% by weight or more of a repeating unit represented by the following formula (1).

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom, a halogen atom, or an alkyl group, alkenyl group, alkynyl group, aryl group, or haloalkyl group having 1 to 20 carbon atoms.) The crosslinkable resin composition according to any one of claims 1 to 3, wherein the nonpolar radical generator is a hydrocarbon compound having a structure represented by the following formula (4).

(In the formula, R ⁵ , R ⁶ , R ⁷ , R ′ ⁵ , R ′ ⁶ , and R ′ ⁷ are each independently a hydrogen atom, a chain hydrocarbon group having 1 to 10 carbon atoms, or an alicyclic carbonization. Represents a hydrogen group or an aromatic hydrocarbon group.) The crosslinkable resin composition according to any one of claims 1 to 3, wherein the nonpolar radical generator is a hydrocarbon compound having a structure represented by the following formula (5).

(In the formula, R ⁸ represents an aromatic hydrocarbon group, and R ⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.) The crosslinkable resin composition according to any one of claims 1 to 5, wherein the nonpolar radical generator has a one-minute half-life temperature of 150C to 350C. Furthermore, the crosslinkable resin composition in any one of Claims 1-6 containing a crosslinkable compound. The crosslinkable resin composition according to claim 1, wherein the terminal-modified polyphenylene ether resin has a number average molecular weight of 2,000 to 15,000. A crosslinkable resin composite obtained by applying or impregnating a support with the crosslinkable resin composition according to claim 1. A cross-linked resin obtained by cross-linking the cross-linkable resin composition according to claim 1. A cross-linked resin composite obtained by cross-linking the cross-linkable resin composition according to claim 1 on a support. A cross-linked resin composite obtained by cross-linking the cross-linkable resin composite according to claim 9. The crosslinked resin composite according to claim 11, wherein the crosslinking is performed on another support. The manufacturing method of a crosslinkable resin composite including the process of apply | coating or impregnating the varnish of the crosslinkable resin composition in any one of Claims 1-8 on a support body, and drying. The manufacturing method of crosslinked resin including the process of bridge | crosslinking the crosslinkable resin composition in any one of Claims 1-8.