JP2000239516A - Curable polyphenylene ether resin composition with low thermal expansion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject inexpensive composition giving high flame retardancy, chemical resistance, heat resistance, etc., after cured by including a polyphenylene ether resin, a specific compound, and inorganic powder in specified proportions. SOLUTION: This composition is obtained by including 100 pts.wt. of a mixture of (A) 98-20 pts.wt. of a polyphenylene ether resin of the formula: Q-[j-H]m [m is 1-6; J is a polyphenylene ether chain composed of unit of the formula (R1 to R4 are each H, a lower alkyl or the like); Q is such that when m is 1, being H, or when m is >=2, being the residue of a multifunctional phenolic compound having 2-6 phenolic hydroxyl groups in one molecule and having polymerization-inert substituents at ortho- and para-positions of the phenolic hydroxyl groups] and (B) 2-80 pts.wt. of a 3,4-dihydro-3-substituted-1,3- benzoxazine-type compound (a mixture thereof with the ring-opening polymerized product thereof) and (C) 1-800 pts.wt. of inorganic powder (e.g. silica).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a curable polyphenylene ether resin composition and a cured product obtained by curing the same. Further, the present invention relates to a composite material comprising the resin composition and a substrate, a cured product thereof, and a laminate comprising a cured product and a metal foil. The resin composition of the present invention exhibits excellent chemical resistance, dielectric properties, heat resistance, and flame retardancy after curing, and is used in the fields of electric industry, electronic industry, space and aircraft industry, etc. It can be used for materials and the like.

[0002]

2. Description of the Related Art In recent years, there has been a remarkable tendency toward miniaturization and high-density mounting methods in the field of electronic devices for communication, consumer use, industrial use, and the like. Heat resistance, flame retardancy, dimensional stability, and electrical properties are being demanded. For example, a copper-clad laminate made of a thermosetting resin such as a phenol resin or an epoxy resin has been used as a printed wiring board. Although these have various performances in a well-balanced manner, they have a drawback that electric characteristics, particularly dielectric characteristics in a high frequency range are poor. In recent years, polyphenylene ether resins have attracted attention as a new material for solving this problem, and applications to copper-clad laminates have been attempted.

[0003] One of the methods utilizing polyphenylene ether is a method in which a curable polymer or monomer is blended and used. By combining with a curable polymer or monomer, it is possible to improve the chemical resistance of polyphenylene ether and to obtain a material utilizing excellent dielectric properties. However, since polyphenylene ether has a higher coefficient of thermal expansion than conventional polyimide resins and the like, it is sometimes insufficient in terms of dimensional stability as a material for a laminate or as a sealing material.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been made without impairing the excellent dielectric and mechanical properties of polyphenylene ether.
An object of the present invention is to provide a novel curable polyphenylene ether resin composition which is inexpensive and has a low coefficient of thermal expansion in addition to excellent flame retardancy, chemical resistance and heat resistance after curing and has toughness. . Although the above description has been made with reference to the laminate for a printed wiring board and the sealing material as an example, the resin composition of the present invention provides better dimensional stability and a tough cured product. Needless to say, the product can be suitably used for the production of other molded articles.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result,
(A) polyphenylene ether resin, (b) 3,4-dihydro-3-substituted-1,3-benzoxazine type compound,
Or a mixture of the compound and its ring-opening polymer, and (c) an inorganic powdered silica, having a low coefficient of thermal expansion in addition to excellent flame retardancy, chemical resistance and heat resistance after curing. The present inventors have found that a novel curable polyphenylene ether resin composition can be obtained, and have completed the present invention.

That is, a first aspect of the present invention is (a) a polyphenylene ether resin, and (b) a 3,4-dihydro-3-substituted resin.
A curable polyphenylene ether resin composition comprising (c) an inorganic powder, a mixture of a 1,3-benzoxazine type compound or a compound thereof and a ring-opening polymer thereof,
(A) based on 100 parts by weight of the sum of component (b) and component (b)
A curable polyphenylene ether resin composition comprising 98 to 20 parts by weight of a component, 2 to 80 parts by weight of a component (b), and 1 to 800 parts by weight of a component (c). A second aspect of the present invention provides a curable polyphenylene ether resin composition, wherein the inorganic powder of the first aspect is silica.

A third aspect of the present invention is the first or second aspect.
Provided is a cured polyphenylene ether resin composition obtained by curing the curable polyphenylene ether resin composition according to the invention. A fourth aspect of the present invention is (a) a polyphenylene ether resin, (b) 3,4-dihydro-3-substituted-1,
3-benzoxazine-type compound or a mixture of the compound and its ring-opening polymer, (c) an inorganic powder, (d) consisting of a base material, based on 100 parts by weight of the sum of components (a) and (b) ( 98% by weight of the component (a) and 2 to 8 of the component (b)
0 parts by weight, the component (c) is 1 to 800 parts by weight,
A curable composite material characterized in that the component (d) is 5 to 90 parts by weight based on 100 parts by weight of the sum of the components (a) to (d).

A fifth aspect of the present invention provides a curable composite material, wherein the inorganic powder of the fourth aspect is silica. A sixth aspect of the present invention provides a cured composite material obtained by curing the curable composite material according to the fourth or fifth aspect. A seventh aspect of the present invention provides a laminate comprising the cured composite material of the sixth aspect and a metal foil. The above invention will be described in detail below. The polyphenylene ether resin used as the component (a) of the curable resin composition of the present invention is represented by the following general formula (I).

[0009]

Embedded image [Wherein, m is an integer of 1 to 6, and J is a polyphenylene ether chain substantially composed of a unit represented by the following formula (II).

[0010]

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(Wherein, R _{1 to} R ₄ each independently represent a lower alkyl group, an aryl group, a haloalkyl group, a halogen atom, or a hydrogen atom.) Q represents a hydrogen atom when m is 1, and m represents 2 In the above case, one molecule has 2 to 6 phenolic hydroxyl groups,
A residue of a polyfunctional phenol compound having a polymerization-inactive substituent at the ortho and para positions of the phenolic hydroxyl group. Examples of the lower alkyl group represented by R _{1 to} R ₄ in the general formula (II) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a sec-
Butyl group and the like. Examples of the aryl group include a phenyl group. Examples of the haloalkyl group include a bromomethyl group and a chloromethyl group.
Examples of the halogen atom include bromine and chlorine. Representative examples of Q in the general formula (I) include compounds represented by the following four general formulas.

[0012]

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Wherein A ₁ and A ₂ represent the same or different linear alkyl groups having 1 to 4 carbon atoms, and X represents an aliphatic hydrocarbon residue or a substituted derivative thereof, an aralkyl group or a substituted Derivatives, oxygen, sulfur, sulfonyl groups,
Y represents an aliphatic hydrocarbon group and a substituted derivative thereof, an aromatic hydrocarbon residue and a substituted derivative thereof, an aralkyl group and a substituted derivative thereof, and Z represents oxygen, sulfur, a sulfonyl group, a carbonyl group. represents a group, two phenyl groups attached directly a _2, a ₂
And X, A ₂ and Z indicate the ortho and para positions of the phenolic hydroxyl group, r is 0 to 4, and s is 2 to 2.
Represents an integer of 6. Specific examples of such a compound include the following compounds.

[0014]

Embedded image [However, X is _{-CH 2 -, - C (CH} 3) 2 -, - O
-, - S -, - SO 2 -, - it represents a CO-. ]

[0015]

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In the polyphenylene ether chain represented by J in the general formula (I), in addition to the units represented by the general formula (II), the heat resistance and the thermal stability of the polyphenylene ether resin are not reduced. The following general formula (III)
May be included.

[0017]

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[Wherein, R _{5 to} R ₉ each independently represent a hydrogen atom, a halogen atom, a lower alkyl group, an aryl group, or a haloalkyl group; R ₁₀ and R ₁₁ each independently represent a hydrogen atom, an alkyl group, Represents an alkyl group, an aryl group, or a substituted aryl group, and R ₁₀ and R ₁₁ are not simultaneously hydrogen. Examples of the unit of the general formula (III) include the following compounds.

[0019]

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In addition, units obtained by graft polymerizing a polymerizable monomer having an unsaturated bond such as styrene or methyl methacrylate to the units of the above formulas (II) and (III), acid anhydrides or unsaturated carboxylic acids It may be reacted with an acid to contain a unit substantially free of a polymerizable double bond resulting therefrom. Examples of the acid anhydride and unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, glutagonic anhydride, citraconic anhydride and the like. The reaction is carried out by heating the polyphenylene ether resin and the unsaturated carboxylic acid or acid anhydride in a temperature range of 100 to 390C, more preferably 260 to 360C. At this time, a radical initiator may coexist. Although both the solution method and the melt mixing method can be used, the melt mixing method using an extruder or the like can be more easily performed and is suitable for the purpose of the present invention. The proportion of the unsaturated carboxylic acid or acid anhydride is 0.01 to 5.0 parts by weight, preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the polyphenylene ether resin.
To 3.0 parts by weight.

Preferred examples of the polyphenylene ether resin (a) of the general formula (I) used in the present invention include:
Poly (2,6-dimethyl-1,4-phenylene ether) obtained by homopolymerization of 2,6-dimethylphenol and its styrene graft copolymer, 2,6-dimethylphenol and 2,3,6-trimethylphenol Copolymer of 2,6-dimethylphenol and 2,6-dimethyl-
Copolymer of 3-phenylphenol, 2,6-dimethylphenol is converted to a polyfunctional phenol compound Q- (H) m
(M is an integer of 2 to 6) in the presence of a polyfunctional polyphenylene ether resin obtained by polymerization, for example,
And copolymers containing units of general formulas (II) and (III) as disclosed in JP-A-301222 and JP-A-1-297428. Regarding the molecular weight of the polyphenylene ether resin, 30 ° C., 0.5 g / d
1 having a viscosity number ηsp / C in the range of 0.1 to 1.0 measured with 1 chloroform solution can be used favorably.

The component (b) of the curable polyphenylene ether resin composition of the present invention may be a 3,4-dihydro-3-substituted-1,3-benzoxazine-type compound, or the compound and a ring-opened polymer thereof. And mixtures thereof.
The compound having a 3,4-dihydro-3-substituted-1,3-benzoxazine ring can be obtained by various methods.
It can be synthesized from amines and formaldehyde. Further, monohydric and polyhydric phenols can be used as the phenol, and monohydric and polyhydric amines can be used as the amine.

That is, the 3,4-dihydro-3 of the present invention
Specific examples of the phenol used in the synthesis of the substituted-1,3-benzoxazine-type compound include phenol, cresol, ethylphenol and naphthol and anthrole as monohydric phenols, and dihydric phenol as the polyhydric phenol. Examples include catechol, resorcinol, hydroquinone, bis (hydroxyphenyl) propane, dihydroxydiphenylsulfone, bis (hydroxyphenyl) methane, dihydroxybiphenyl, etc. Examples of trivalent or higher phenols include trihydroxynaphthalene, trihydroxyanthracene, and novolak resins. And phenolic resins such as resole resins.

Specific examples of amines include aniline, methylamine, and cyclohexylamine as monovalent amines. Examples of polyvalent amines include paraphenylene diamine as divalent amines, and trivalent or higher amines. Include triaminonaphthalene and triaminoanthracene. Further, it is preferable to use an aromatic amine as a kind of amine in order to improve flame retardancy. The combination of these phenol, amine and formaldehyde can be arbitrarily selected depending on the application, but it is preferable to obtain a structure having a plurality of benzoxazine rings in the structural unit in order to improve the crosslink density, A combination of a monohydric phenol, a dihydric amine and formaldehyde, and a combination of a dihydric phenol, a monohydric amine and formaldehyde are preferred. One example thereof is the following formula (IV).

[0025]

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Wherein R ₁₃ is a phenyl group, a substituted phenyl group, a methyl group or a cyclohexyl group;
Divalent aliphatic hydrocarbon atomic groups and their derivatives, divalent aromatic hydrocarbon atomic groups and their derivatives, divalent heterocyclic compound atomic groups and their derivatives, oxygen, sulfur, sulfonyl group, carbonyl group, etc. Represents a functional group of
N is 0 or 1. As shown in US Pat. No. 5,152,939, these 3,4-dihydro-3-substituted-1,3-benzoxazine-type compounds form a crosslinked structure by a ring-opening polymerization reaction by appropriate heating. .

The molecular weight of the 3,4-dihydro-3-substituted-1,3-benzoxazine type compound, which is the component (b) of the present invention, or a mixture of the compound and its ring-opening polymer is number average. The molecular weight is preferably in the range of 200 to 200,000, more preferably 300 to 150,000, and particularly preferably 400 to 100,000. As the number average molecular weight increases by ring-opening polymerization, an increase in viscosity is seen,
If the number average molecular weight is less than 200, it takes a long time for the curing reaction to be unsuitable in terms of productivity, and if the molecular weight exceeds 200,000, it is difficult to knead with the polyphenylene ether resin due to high viscosity. This is not preferable because operability is reduced. Therefore, if necessary, a part of the 3,4-dihydro-3-substituted-1,3-benzoxazine type compound is preliminarily polymerized at 50 to 250 ° C., preferably 80 to 180 ° C. It is preferable to adjust so as to keep the number average molecular weight.

The number average molecular weight can be measured by a known method, and examples thereof include gel permeation chromatography, light scattering, and osmotic pressure. This 3,4-dihydro-3
Specific examples of the substituted-1,3-benzoxazine-type compound or a mixture of the compound and its ring-opening polymer include the following compounds and their dimers, oligomers and mixtures thereof. In carrying out the above, the 3,4-dihydro-3-substituted-1,3-benzoxazine type compound is used not only alone, but also in the presence of several kinds of 3,4-dihydro-3-substituted-1,3
-It is possible to mix and use benzoxazine type compounds in any proportion.

[0029]

Embedded image In the present invention, 3,4-dihydro-3-substituted-1,3-
The benzoxazine-type compound is solid or liquid at ordinary temperature, and can be arbitrarily operated at a curing speed for curing while being melted at ordinary temperature to 250 ° C. Therefore, in the present composition, it exerts its effects as a plasticizer for improving fluidity and a curing agent during curing until curing. That is, the resin flow at the time of pressing and the curability are improved.

The inorganic powder used as the component (c) of the curable polyphenylene ether resin composition of the present invention includes silica, talc, calcium silicate and the like. Among these, silica is particularly preferred. Silica is chemically silicon dioxide (SiO2). Hereinafter, silica, which is commonly used, is used. In the polyphenylene ether resin composition of the present invention, a component (c) previously treated with a coupling agent can be used, if necessary, for the purpose of improving the adhesion at the interface between the component (c) and the resin. As the coupling agent, a silane coupling agent, a titanate coupling agent,
General ones such as an aluminum-based coupling agent and a zircoaluminate coupling agent can be used. Also (a) ~
When mixing the component (d), the above-mentioned coupling agent may be added.

The particle shape and particle size of the component (c) are not particularly limited, but the particle shape is preferably a crushed type, and the particle size is preferably one having a particle size distribution with an average particle size of 1 to 100 μm, preferably 4 to 10 μm. The particle size distribution is more preferable. Further, a crushing type and a spherical type may be used in combination. The component (c) of the polyphenylene ether resin composition of the present invention has a feature that it contributes to improving the dimensional stability of the cured resin composition, and has an adverse effect on the mechanical properties and dielectric properties of the cured composition. Do not give.

Of the three components (a) to (c) described above, the mixing ratio of the component (a) and the component (b) is such that the component (a) is 98 to 20 based on 100 parts by weight of the sum of both. Parts by weight, component (b) is 2 to 80 parts by weight, preferably component (a) is 98 to 40 parts by weight, and component (b) is 2 to 60 parts by weight.
Parts by weight, more preferably 95 to 50 parts by weight of component (a).
Parts by weight, component (b) is in the range of 5 to 50 parts by weight.
When the amount of the component (b) is less than 2 parts by weight, the improvement of the chemical resistance is insufficient, which is not preferable. Conversely, if the amount exceeds 80 parts by weight, the dielectric properties deteriorate, which is not preferable.

The proportion of the component (c) used in the polyphenylene ether resin composition of the present invention is 1 to 800 parts by weight based on 100 parts by weight of the sum of the components (a) and (b). , Preferably 5 to 400 parts by weight, more preferably 10 to 200 parts by weight. When the component (c) is less than 1 part by weight, the thermal expansion characteristics of the cured resin composition are insufficiently improved, which is not preferable. If it exceeds 800 parts by weight, the fluidity of the resin at the time of melt molding and the adhesion to the metal foil when a laminate with the metal foil is formed are unpreferably reduced.

As a method of mixing the above components (a) to (c), a solution mixing method of uniformly dissolving or dispersing the three components in a solvent or a melt blending method of heating by an extruder or the like is used. Available. Solvents used for solution mixing include halogen-based solvents such as dichloromethane, chloroform, and trichloroethylene; aromatic solvents such as benzene, toluene, and xylene; ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; dimethylformamide; dimethyl sulfoxide And the like, and these are used alone or in combination of two or more.

The curable resin composition of the present invention may be formed into a desired shape in advance according to its use. The molding method is not particularly limited. Usually, a casting method in which the resin composition is dissolved in the above-described solvent and molded into a desired shape, or a heat melting method in which the resin composition is heated and melted and molded into a desired shape is used. The above-described casting method and heat melting method may be performed alone. Moreover, you may combine and perform each. For example, several to several tens of films of the present resin composition prepared by a casting method are laminated and heated and melted by a heat-melting method, for example, a press molding machine to obtain a sheet of the present resin composition.

The curable resin composition of the present invention can be used by blending additives in an amount that does not impair the original properties for the purpose of imparting desired performance according to the use.
Examples of the additives include a curing agent, an antioxidant, a heat stabilizer, an antistatic agent, a plasticizer, a pigment, a dye, a colorant, and rubber. In addition, it is preferable to use a rubber in combination to enhance the toughness. The rubber mentioned here is preferably a hydrogenated block copolymer. The structure of the hydrogenated block copolymer is a block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. Is obtained by hydrogenating, for example,

[0037]

Embedded image

A hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer having the above structure. This hydrogenated block copolymer contains 5 to 85% by weight, preferably 10 to 70% by weight of a vinyl aromatic compound. Further referring to the block structure, a polymer block A mainly composed of a vinyl aromatic compound
Is a polymer block comprising only a vinyl aromatic compound or a copolymer block of a vinyl aromatic compound containing more than 50% by weight, preferably 70% by weight or more of a vinyl aromatic compound and a hydrogenated conjugated diene compound. Having a structure, and further, a polymer block B mainly composed of a hydrogenated conjugated diene compound is a polymer block composed of only a hydrogenated conjugated diene compound, or a hydrogenated conjugated diene compound. It has a structure of a copolymer block of a hydrogenated conjugated diene compound and a vinyl aromatic compound containing more than 50% by weight, preferably 70% by weight or more. Further, these polymer blocks A mainly composed of a vinyl aromatic compound and the polymer blocks B mainly composed of a hydrogenated conjugated diene compound are each composed of a hydrogenated conjugated diene in the molecular chain of each polymer block. The distribution of the compound or vinyl aromatic compound may be random, tapered (the monomer component increases or decreases along the molecular chain), partially block-like, or any combination thereof; When there are two or more polymer blocks mainly containing the vinyl aromatic compound and two or more polymer blocks mainly containing the hydrogenated conjugated diene compound, even if each polymer block has the same structure, Well, different structures may be used.

Examples of the vinyl aromatic compound constituting the hydrogenated block copolymer include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, p-tert.
One or more of butylstyrene and the like can be selected, and among them, styrene is preferable. Examples of the conjugated diene compound before hydrogenation that constitutes the hydrogenated conjugated diene compound include, for example, butadiene, isoprene, 1,3-
One or more kinds are selected from pentadiene, 1,3-dimethyl-1,3-butadiene and the like, and among them, butadiene, isoprene and a combination thereof are preferable.

Further, the present invention has the above structure.
The number average molecular weight of the hydrogenated block copolymer is not particularly limited.
However, the number average molecular weight is 5000 to 1,000,000, preferably 1
Used in the range of 10,000 to 500,000, more preferably 30,000 to 300,000
Can be Furthermore, the molecular structure of the hydrogenated block copolymer
Is linear, branched, radial or any combination of these
Any combination may be used. Also, the flame retardant effect
Chlorine, bromine, phosphorus, metal hydroxide and
Flame retardants such as organometallic compounds and Sb_TwoO_Three, Sb
_TwoO_Five, NaSbO_Three・ 1 / 4H _TwoO and other flame retardant aids
Can also be used.

Further, for example, crosslinking monomers such as allyl glycidyl ether, glycidyl methacrylate and glycidyl acrylate, polyethylene, polypropylene, polybutene, ethylene-polypropylene copolymer, nylon 4, nylon 6, nylon 6, 6 and polyethylene terephthalate Thermoplastic resins such as polycarbonate, polyacetal, polysulfone, polyvinyl chloride and polystyrene, or thermosetting resins such as epoxy resins, novolak-type phenol resins and melamine resins, and triallyl isocyanurate and triallyl cyanurate One or two or more crosslinking agents can be blended.

The cured polyphenylene ether resin composition of the present invention is obtained by curing the above-described curable resin composition. The method of curing is arbitrary, and a method using heat, light, or the like can be employed. When curing by heating, the temperature is selected in the range of 80 to 300 ° C, more preferably 150 to 250 ° C, depending on the presence or absence and the type of the curing agent. The time is from 1 minute to 10 hours, more preferably from 1 minute to 5 hours. The resin composition of the obtained cured resin composition can be analyzed using a method such as an infrared absorption spectrum method, a high-resolution solid nuclear magnetic resonance spectrum method, or a pyrolysis gas chromatography. In addition, this cured resin composition has fourth to
5 As in the case of the curable composite material described below as the invention, it can be used by being bonded to a metal foil and / or a metal plate.

Next, the fourth to fifth and sixth curable composite materials of the present invention and their cured products will be described. The fourth to fifth curable composite materials of the present invention are those in which the first or second curable resin composition of the present invention further contains a base material. As the base material used for the component (d), various glass cloths such as a roving cloth, a cloth, a chopped mat, a surfing mat or a glass nonwoven fabric; a ceramic fiber cloth, an asbestos cloth, a metal fiber cloth, and other synthetic or natural materials Inorganic fiber cloth; woven or non-woven fabric obtained from synthetic fibers such as polyvinyl alcohol fiber, polyester fiber, acrylic fiber, wholly aromatic polyamide fiber; natural fiber cloth such as cotton cloth, linen cloth and felt;
Carbon fiber cloth; natural cellulose-based cloths such as kraft paper, cotton paper, and paper-glass mixed paper are used alone or in combination of two or more.

The ratio of the base material in the curable composite material of the present invention is 5 to 90 parts by weight, more preferably 10 to 80 parts by weight, further preferably 20 to 70 parts by weight, based on 100 parts by weight of the curable composite material. Range of parts. If the amount of the substrate is less than 5 parts by weight, the dimensional stability and strength after curing of the composite material are insufficient, and if the amount of the substrate is more than 90% by weight, the dielectric properties of the composite material are unfavorably poor.

In the curable composite material of the present invention, if necessary, a coupling agent can be used for the purpose of improving the adhesion at the interface between the resin and the substrate. As the coupling agent, general ones such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, and a zircoaluminate coupling agent can be used. As a method for producing the curable composite material of the present invention, for example, (a) to (c) described in the first or second section of the present invention.
Components and, if necessary, other components, the above-mentioned halogen-based solvent, aromatic-based, ketone-based solvent, dimethylformamide,
Examples thereof include a method of uniformly dissolving or dispersing in a solvent such as dimethyl sulfoxide or a mixed solution thereof, impregnating the substrate, and then drying.

The impregnation is performed by dipping, coating, or the like. The impregnation can be repeated multiple times as necessary, and in this case, the impregnation can be repeated using multiple solutions having different compositions and concentrations to finally adjust the desired resin composition and resin amount It is. The sixth cured composite material of the present invention is obtained by curing the curable composite material thus obtained by a method such as heating. The production method is not particularly limited, for example, a plurality of the curable composite material is stacked,
The layers are adhered to each other under heat and pressure, and at the same time, thermosetting is performed to obtain a cured composite material having a desired thickness. Further, it is also possible to obtain a cured composite material having a new layer configuration by combining the cured composite material once cured by adhesion and the curable composite material.

The lamination molding and curing are usually performed simultaneously using a hot press or the like, but both may be performed independently. That is, the uncured or semi-cured composite material obtained by lamination molding in advance can be cured by heat treatment or another method. Molding and curing are performed at a temperature of 80 to 300 ° C and a pressure of 0.1 to 500k.
g / cm ² , time 1 minute to 10 hours, more preferably temperature 150 to 250 ° C., pressure 1 to 100 kg / cm
^{2. The} time can be from 1 minute to 5 hours.

Finally, a seventh embodiment of the present invention will be described. The seventh laminate of the present invention is a laminate composed of the cured composite material described above as the sixth of the present invention and a metal foil. Examples of the metal foil used here include a copper foil and an aluminum foil. The thickness is not particularly limited, but is in the range of 5 to 200 μm, more preferably 5 to 100 μm.

The method for producing the laminate of the present invention includes:
For example, a method of laminating and drying the curable composite material of the fourth to fifth inventions, or the cured composite material of the sixth invention and a metal foil and / or a metal plate in a layered structure according to the purpose, and, if necessary, Under heat and pressure, and at the same time thermosetting. In the laminate of the present invention, a film or a curable composite material made of a curable resin composition and a metal foil are laminated in an arbitrary layer configuration. The metal foil can be used as both a surface layer and an intermediate layer. In addition to the above, lamination and curing may be repeated a plurality of times to form a multilayer. An adhesive can be used for bonding the metal foil and the metal plate. Examples of the adhesive include an epoxy-based, acrylic-based, phenol-based, and cyanoacrylate-based adhesive, but are not particularly limited thereto.
The lamination and curing can be performed under the same conditions as in the fourth aspect of the invention.

[0050]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific examples of the present invention will be described below based on examples. In the examples, the following were used as each component. <Polyphenylene ether resin> (Polymer C) Poly (2,6-dimethyl-1,4-phenylene ether) ηsp / C = 0.56 (30 ° C., 0.5 g / dl, chloroform solution). (Polymer D) 100 parts by weight of polymer A, 1.5 parts by weight of maleic anhydride, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (Perhexa 25B manufactured by NOF Corporation) After 1.0 part by weight was dry-blended at room temperature, the mixture was extruded with a twin-screw extruder at a cylinder temperature of 300 ° C. and a screw rotation speed of 230 rpm. This polymer is designated as D.

<Dihydro-1,3-benzoxazine type compound> 6,6 '-(1-methylethylidene) bis (3,4-
Dihydro-3-phenyl-2H-1,3-benzoxazine) Number average molecular weight (in terms of polystyrene) = 1000 A 37% aqueous formaldehyde solution was added dropwise to an aniline solution diluted with dioxane at 10 ° C or lower. After stirring at room temperature for 30 minutes, bisphenol A dissolved in dioxane was added dropwise at room temperature. After the mixture was heated and refluxed for about 6 hours, the dioxane solvent was distilled off to obtain a pale yellow residue. These were dissolved in diethyl ether, washed with water, and the ether solution was distilled off to obtain a compound having a number average molecular weight of 1,000. In addition, the molar ratio of aniline, formaldehyde, and bisphenol A was set at a charging ratio of 1: 2: 4.

<Silica> Huze Rex E-2 (shape crushed type, average particle size 7 μm, manufactured by Tatsumori Co., Ltd.) Huze Rex silane coupling treatment E-2
(Shape crush type, average particle size 7μm, manufactured by Tatsumori Co., Ltd.) ・ Grassrain CUS-85K (shape spherical type
Average particle size 15 μm, manufactured by Toshiba Ceramics Co., Ltd. <Hydrogenated block copolymer> H1041 (Styrene-butadiene copolymer number average molecular weight 48,000 Styrene content 32% Hydrogenation rate 98%
H1051 (styrene-butadiene copolymer number average molecular weight 53,000 styrene content 42% hydrogenation rate 98%
Asahi Kasei Kogyo Co., Ltd.)

<Flame retardant> (Flame retardant E) Decabromodiphenyl ether (Asahi Glass AFR102)
1) (flame retardant F) phosphoric acid ester (manufactured by Daihachi Chemical PX-200) <Flame retardant aid> Sb ₂ O ₃ (Nihonseiko PATOX-M) <glass cloth> E glass, weight per unit area 48 g / m ²

Examples 1 to 14 Curable polyphenylene ether resin composition and cured polyphenylene ether resin composition Polyphenylene ether resin, 3,4-dihydro-3-substituted-1,3-benzoxazine type compound, silica and hydrogenated The block copolymer was mixed with the composition shown in Table 1 using a Henschel mixer, and the mixture was heated at 240 ° C. in a vacuum press.
It was molded and cured over time to obtain a cured product having a thickness of about 1 mm. These cured products were cut into 7 mm squares, and the coefficient of thermal expansion in the thickness direction was measured by a thermomechanical analyzer at a heating rate of 20 ° C./min. The coefficient of thermal expansion here is from 30 ° C to 1
The rate of increase of the sample thickness when the temperature of the sample is raised to 50 ° C is 120 ° C (150 ° C-30 ° C), which is the change in temperature.
Divided by In each of the examples, a cured product having a small coefficient of thermal expansion, toughness and resin fluidity was obtained. The results are shown in Table 1.

Comparative Example 1 A cured product was prepared in the same manner as in Example 1, except that silica and the hydrogenated block copolymer were not added. The coefficient of thermal expansion was much larger than that of Example 1. (Comparative Example 2) A cured product was prepared in the same manner as in Example 12, except that silica was not added, in the same manner.
The coefficient of thermal expansion was extremely large as compared with Example 12. Comparative Example 3 A cured product was prepared with the same composition as in Example 12 except that 900 parts of silica was used. The cured product was brittle and had an uneven surface. The results of the above comparative examples are shown in Examples 1 to
The results are shown in Table 1 together with No. 14.

(Examples 15 to 28) Curable composite materials Each component having the composition shown in Table 2 was dissolved or dispersed in toluene. A glass cloth was immersed in this solution for impregnation, and dried in an air oven. Each of the obtained curable composite materials had no stickiness on the surface and was excellent in handleability. Laminate Next, a plurality of the above-described curable composite materials are laminated so that the thickness after curing becomes about 0.8 mm, and a thickness of 35
A copper foil of μm was placed and molded and cured by a press molding machine to obtain a laminate. Table 3 shows the curing conditions of each example.
The pressure was all 40 kg / cm ² . In each of the examples, the resin flow during pressing was good. The physical properties of the thus obtained laminate were measured by the following methods, and good results as shown in Table 3 were obtained.

[Evaluation of Physical Properties of Laminate] Trichlorethylene resistance The laminate from which the copper foil had been removed was cut into 25 mm squares, boiled in trichlorethylene for 5 minutes, and visually observed for changes in appearance. 2. The dielectric constant and the dielectric loss tangent were measured at 1 MHz. 3. Solder heat resistance The laminate from which the copper foil has been removed is cut into 25 mm squares,
The sample was floated in a solder bath at 120 ° C. for 120 seconds, and the change in appearance was visually observed. 4. Copper foil peeling strength A test piece having a width of 20 mm and a length of 100 mm was cut out from the laminate, and a parallel cut having a width of 10 mm was formed in the copper foil surface, and then a speed of 50 mm / min in a direction perpendicular to the surface. , The copper foil was continuously peeled off, and the stress at that time was measured with a tensile tester, and the lowest value of the stress was shown.

5. Thermal expansion characteristics The laminate from which the copper foil had been removed was cut into a 7 mm square, and the coefficient of thermal expansion in the thickness direction was measured at a heating rate of 20 ° C./min using a thermomechanical analyzer. 6. Flame retardant 127 mm long and 12.7 width from the laminate from which the copper foil was removed
A test piece of mm was cut out and performed according to the UL-94 test method. 7. Resin Flowability Three curable composite materials were stacked and pressed at 170 ° C. for 10 minutes with a press molding machine at a surface thickness of 22 kg / cm ² , and the protruding resin composition was weighed to determine the volume of the resin composition.
The value obtained by dividing this by the volume of only the resin composition in the curable composite material before pressing was shown. 8. Cracks In order to examine the toughness of the resin, a multilayer printed wiring board was prepared and subjected to 100 thermal shocks between −65 ° C. and 125 ° C. 100 times to determine whether resin cracks occur inside the wiring board.

Comparative Example 4 A cured product was prepared in the same manner as in Example 15, except that silica and the hydrogenated block copolymer were not added. The coefficient of thermal expansion was larger than that of Example 15, and cracks occurred. (Comparative Example 5) A cured product was prepared in the same manner as in Example 27, except that silica was not added, in the same manner.
The coefficient of thermal expansion was larger than that of Example 27, and cracks occurred. Comparative Example 6 A cured product was prepared with the same composition as in Example 27 except that 900 parts of silica was used. The resin flowability was poor, and the copper foil peel strength decreased.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

[0063]

EFFECTS OF THE INVENTION By using the curable polyphenylene ether composition of the present invention, excellent dielectric properties, mechanical properties,
A curable polyphenylene ether composition having flame retardancy, chemical resistance, and heat resistance and having an unprecedented low coefficient of thermal expansion can be obtained. Therefore, the material of the present invention is a dielectric material, an insulating material,
It can be used as a heat-resistant material, a structural material, and the like. In particular, it is suitably used as a prepreg for single-sided, double-sided, multi-layer printed boards, semi-rigid boards, metal base boards, and multi-layer printed boards.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3:36 5: 357) F term (Reference) 4F100 AA00A AA00H AA20A AA20H AB01B AB33B AK54A AK80A AL05A BA02 BA10A BA10B DE01A DE01H GB31 GB41 GB48 JA02 JB01 JB13A JG05 JJ07 YY00A 4J002 CH07W CM01X DJ006 DJ016 DJ046 FD016

Claims (7)

[Claims] (A) a polyphenylene ether resin,
(B) a 3,4-dihydro-3-substituted-1,3-benzoxazine type compound or a mixture of the compound and a ring-opening polymer thereof, and (c) a curable polyphenylene ether resin composition comprising an inorganic powder. Component (a) is 98 to 20 parts by weight, component (b) is 2 to 80 parts by weight, and component (c) is 1 to 100 parts by weight based on 100 parts by weight of the sum of components (a) and (b).
A curable polyphenylene ether resin composition, wherein the composition is 800 parts by weight. 2. A curable polyphenylene ether resin composition, wherein the inorganic powder according to claim 1 is silica. 3. A cured polyphenylene ether resin composition obtained by curing the curable polyphenylene ether resin composition according to claim 1 or 2. (A) a polyphenylene ether resin,
(B) a 3,4-dihydro-3-substituted-1,3-benzoxazine-type compound or a mixture of the compound and a ring-opening polymer thereof, (c) an inorganic powder, and (d) a base material. 98 to 20 parts by weight of the component (a), 2 to 80 parts by weight of the component (b), based on 100 parts by weight of the sum of the components and the component (b);
Component (c) is 1 to 800 parts by weight and component (d) is 5 to 5 parts by weight based on 100 parts by weight of the sum of components (a) to (d).
A curable composite material comprising 90 parts by weight. 5. A curable composite material, wherein the inorganic powder according to claim 4 is silica. 6. A cured composite material obtained by curing the curable composite material according to claim 4. 7. A laminate comprising the cured composite material according to claim 6 and a metal foil.