JPH07247414A - Tough and curable polyphenylene ethereal resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, comprising a polyphenylene ether resin, triallyl (iso)cyanurate, silica and a specific hydrogenated block copolymer and capable of manifesting low thermal expansion coefficient characteristics and excellent toughness and dielectric and mechanical characteristics after curing. CONSTITUTION:This resin composition comprises (A) 98-40 pts.wt. polyphenylene ether resin containing unsaturated groups, (B) 2-60 pts.wt. triallyl isocyanurate and/or triallyl cyanurate, (C) 10-400 pts.wt. silica and (D) 1-50 pts.wt. hydrogenated block copolymer prepared by hydrogenating a block copolymer comprising at least one polymer block (a) consisting essentially of a vinyl aromatic compound and at least one polymer block (b) consisting essentially of a conjugated diene compound based on 100 pts.wt. total amount of the components (A) and (B).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable polyphenylene ether resin composition and a cured product obtained by curing the same. Furthermore, the present invention relates to a curable composite material composed of the resin composition and a substrate, a cured product thereof, and a laminate composed of the cured product and a metal foil.

The resin composition of the present invention exhibits excellent chemical resistance, dielectric properties, heat resistance, dimensional stability, and toughness after curing, and is used as a dielectric material or an insulating material in the fields of the electronic industry, space / aircraft industry and the like. It can be used as a material and a heat resistant material.

[0003]

2. Description of the Related Art In recent years, there has been a remarkable trend toward miniaturization and high density of mounting methods in the field of electronic devices for communication, consumer use, industrial use, etc. Heat resistance, dimensional stability, electrical characteristics, and moldability are being demanded. For example, as a printed wiring board, a copper-clad laminate having a thermosetting resin such as a phenol resin or an epoxy resin as a base material has been used. Although these have various performances in a well-balanced manner, they have the drawback of poor electrical characteristics, especially dielectric characteristics in the high frequency region. As a new material for solving this problem, polyphenylene ether has been attracting attention in recent years and its application to copper-clad laminates has been attempted.

Polyphenylene ether is an engineering plastic excellent in mechanical properties and electrical properties and has relatively high heat resistance. However, when it is intended to be used as a printed circuit board material, extremely high heat resistance of solder is required, so that the heat resistance inherent to polyphenylene ether is by no means sufficient. That is, the polyphenylene ether is deformed when exposed to a high temperature of 200 ° C. or higher, causing a significant decrease in mechanical strength and peeling of the copper foil formed on the resin surface for a circuit. Further, polyphenylene ether has strong resistance to acids, alkalis and hot water, but has extremely weak resistance to aromatic hydrocarbon compounds and halogen-substituted hydrocarbon compounds and is soluble in these solvents.

As one method for improving the heat resistance and chemical resistance of polyphenylene ether, a crosslinkable functional group is introduced into the chain of polyphenylene ether and further cured to be used as a cured polyphenylene ether. A method has been proposed. As a specific example, a polymer of 2-allyl-6-methylphenol or 2,6-diallylphenol is a Journal of Polymer Science.
Ce magazine, Vol. 49, p. 267 (1961). U.S. Pat. Nos. 3,281,393 and 34220
No. 62 discloses a copolymer of 2,6-dimethylphenol and 2-allyl-6-methylphenol or 2,6-diallylphenol. US Patent No. 4
No. 634,742 includes vinyl group-substituted polyphenylene ether.
Tell is disclosed. Furthermore, the present inventors previously invented a polyphenylene ether substituted with a propargyl group or an allyl group, and a polyphenylene ether containing a triple bond or a double bond, and that these are curable, and It has been found that the cured product obtained is insoluble in aromatic hydrocarbon solvents and halogen-substituted hydrocarbon solvents and has excellent dielectric properties (JP-A-1-69628,
1-69629, 1-113425, 1-1
13426).

However, any of the above-mentioned curable polyphenylene ethers has a high coefficient of thermal expansion as compared with conventional polyimide resins and the like, so that it is unsatisfactory in terms of dimensional stability as a material for laminates and sealing materials. There were enough cases. Further, when it is hardened, it becomes brittle and may be vulnerable to mechanical shock or thermal shock.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it does not impair the excellent dielectric properties and mechanical properties of the curable polyphenylene ether resin, and has a thermal expansion after curing. It is intended to provide a novel curable polyphenylene ether resin composition having a low coefficient and toughness.

The above parts have been described with reference to a laminated board for a printed wiring board and an encapsulant. However, since the resin composition of the present invention gives a cured product having good dimensional stability and toughness, It goes without saying that the resin composition can be suitably used for the production of other molded products.

[0009]

The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, (a) unsaturated group-containing polyphenylene ether resin, (b) triallyl isocyanurate and By mixing // or triallyl cyanurate, (c) silica, and (d) hydrogenated block copolymer, a cured polyphenylene ether resin composition having excellent low thermal expansion characteristics and toughness after curing can be obtained. The present invention has been completed by finding out what can be obtained. The present invention comprises the following five inventions.

That is, the first aspect of the present invention is (a), (a)
98 parts by weight based on 100 parts by weight of the sum of the components and the component (b)
To 40 parts by weight of a polyphenylene ether resin containing an unsaturated group, (b), based on 100 parts by weight of the sum of the components (a) and (b), 2 to 60 parts by weight of the triallyl isocyanurate and / or triacetate. Allyl cyanurate,
10 to 400 parts by weight of silica, based on 100 parts by weight of the sum of components (c), (a) and (b), (d),
Based on 100 parts by weight of the sum of the components (a) and (b), 1 to 50 parts by weight of a polymer block A containing at least one vinyl aromatic compound as a main component and at least one conjugated diene compound as a main component. A curable polyphenylene ether-based resin composition comprising a hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising the polymer block B.

A second aspect of the present invention provides a cured polyphenylene ether resin composition obtained by curing the curable polyphenylene ether resin composition of the first aspect.
The third aspect of the present invention is (a), a polyphenylene ether resin containing 98 to 40 parts by weight of an unsaturated group, based on 100 parts by weight of the sum of the components (a) and (b), (b), (a). )
Based on 100 parts by weight of the sum of the component and the component (b), 2 to
10-100 based on 60 parts by weight of triallyl isocyanurate and / or triallyl cyanurate, 100 parts by weight of the sum of components (c), (a) and (b).
1 to 50 parts by weight of at least one vinyl aromatic compound-based polymer block A based on 100 parts by weight of silica, 100 parts by weight of the components (d), (a) and (b), and A hydrogenated block copolymer obtained by hydrogenating a block copolymer consisting of at least one polymer block B mainly composed of a conjugated diene compound, and components (e), (a) to (e) A curable composite material comprising 5 to 90 parts by weight of a base material, based on 100 parts by weight of the above.

A fourth aspect of the present invention provides a cured composite material obtained by curing the curable composite material of the third aspect. A fifth aspect of the present invention provides a laminate comprising the cured composite material of the fourth aspect and a metal foil. These inventions will be described in detail below.

First, the curable polyphenylene ether resin composition and the cured product thereof, which are the first and second aspects of the present invention, will be described. The unsaturated group-containing polyphenylene ether resin used as the component (a) of the curable polyphenylene ether-based resin composition means a carbon-carbon double bond and / or a carbon-carbon triple bond as a side chain with respect to the polyphenylene ethers. Refers to the one in which an unsaturated group containing is introduced. An example thereof is a resin comprising a reaction product of a polyphenylene ether resin represented by the following general formula (I), an alkenyl halide of the general formula (III) and / or an alkynyl halide of the general formula (IV):

[0014]

[Chemical 1]

[0015]

[Chemical 2]

A resin in which X and / or Y and the following alkenyl group and / or alkynyl group are covalently bonded to the polyphenylene ether resin can be mentioned.

[0017]

[Chemical 3]

Explaining the polyphenylene ether resin of the general formula (I), typical examples of Q include compounds represented by the following four general formulas.

[0019]

[Chemical 4]

As a concrete example,

[0021]

[Chemical 5]

[0022]

[Chemical 6]

Etc. In the polyphenylene ether chain represented by J in the general formula (I), one or two or more of the units or terminal groups described below are contained unless the heat resistance and heat stability of the polyphenylene ether resin are reduced. May be included. i) a unit represented by the following general formula other than (II),

[0024]

[Chemical 7]

Ii) a unit represented by the following general formula,

[0026]

[Chemical 8]

Iii) an end group represented by the following general formula:

[0028]

[Chemical 9]

Iv) The above formula (II) and general formula (V)
Units or terminal groups obtained by graft-polymerizing a polymerizable monomer having an unsaturated bond such as styrene or methyl methacrylate to the units or terminal groups of (VII). As an example of the unit of the general formula (V),

[0030]

[Chemical 10]

And the like. Examples of the unit of general formula (VI) include:

[0032]

[Chemical 11]

And the like. Examples of the terminal group of the general formula (VII) include:

[0034]

[Chemical 12]

And the like. Next, specific examples of the alkenyl halide of the general formula (III) will be listed below: allyl chloride, allyl bromide, allyl iodide, 4
-Bromo-1-butene, trans- and / or cis-1-bromo-2-butene, trans- and / or cis-1-chloro-2-butene, 1-chloro-2-methyl-2-propene, 5 -Bromo-1-pentene, 4-bromo-2-methyl-2-butene, 6-bromo-1-hexene, 5-bromo-2-methyl-2-pentene and the like.

Specific examples of the alkynyl halide of the general formula (IV) include propargyl chloride, propargyl bromide, propargyl iodide, 4-bromo-1-butyne, 4-bromo-2-butyne, 5-bromo-1. -Pentyne, 5-bromo-2-pentyne, 1-iodo-2-pentyne, 1-iodo-3-hexyne, 6-bromo-1-hexyne and the like.

These alkenyl halides and alkynyl halides can be used alone or in combination of two or more. The unsaturated group-introduced polyphenylene ether resin used in the component (a) of the present invention is
For example, JP-A-64-69628 and 64-69629.
No. 1,113,425, and No. 1-113426.
No. 2-232260, No. 2-233759, the polyphenylene ether resin of the general formula (I) is metallized with an organic metal, and subsequently alkenyl halide (III) and / or alkenyl halide (IV). ) It is possible to produce by substitution reaction. The polyphenylene ether resin containing an unsaturated group produced according to the present method is at least the following two or three types.
It is composed of units represented by the structural formula of the species.

[0038]

[Chemical 13]

In addition to the above, the following units may be included.

[0040]

[Chemical 14]

The content of halogen derived from the above general formula (VIII) is in the range of 0 or more (when M is a hydrogen atom) 30% by weight or less, more preferably 0 or more and 20% by weight, based on the polyphenylene ether resin. % Or less. The unsaturated group-introduced polyphenylene ether resin used in the present invention does not necessarily need to contain halogen. However, when the halogen is chlorine or bromine, there is an effect that flame retardancy can be imparted to the curable polyphenylene ether resin composition of the present invention. When imparting flame retardancy, the preferred halogen content is 1
It is more than weight%. However, if it exceeds 30% by weight, the thermal stability of the polyphenylene ether resin itself is deteriorated, which is not preferable.

Preferred examples of the unsaturated group-introduced polyphenylene ether resin obtained by the above method include:
The resin which consists of the reaction product of polyphenylene ether-type resin and allyl bromide, allyl chloride, propargyl bromide, and propargyl chloride described below can be mentioned. Examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene ether) and poly (2,6-dimethyl-1,4-phenylene ether) obtained by homopolymerization of 2,6-dimethylphenol. Polystyrene graft copolymer of 2,6
-Copolymer of dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and 2,6
-Dimethyl-3-phenylphenol copolymer, 2,
6-Dimethylphenol is a polyfunctional phenol compound

[0043]

[Chemical 15]

A polyfunctional polyphenylene ether resin obtained by polymerization in the presence of, for example, JP-A-63-3012.
No. 22, a copolymer containing units of the general formulas (V) and (VI) as disclosed in JP-A-1-29748,
For example, a resin containing a unit of general formula (V) and an end group of general formula (VII) as disclosed in Japanese Patent Application No. 1-135763 can be mentioned.

Another example of the polyphenylene ether resin containing an unsaturated group used in the curable polyphenylene ether resin composition of the present invention is a resin containing the following repeating units.

[0046]

[Chemical 16]

A specific example is US Pat. No. 3,422.
Copolymers of 2-allyl-6-methylphenol with 2,6-dimethylphenol as disclosed in 062, 2,6-Diallyl-4- as disclosed in U.S. Pat. No. 3,281,393. Bromophenol and 2,6-
Copolymer of dimethyl-4-bromophenol, Japanese Patent Publication No. 6
A copolymer of 2,6-diprenylphenol and 2,6-dimethylphenol as disclosed in 3-47733, also of 2,6-bis (2-butenyl) phenol and 2,6-dimethylphenol. Copolymer, also 2,
A copolymer of 6-dicinnamylphenol and 2,6-dimethylphenol, a homopolymer of 2-prenyl-6-methylphenol as disclosed in JP-A-58-27719, and also 2-prenyl-6. -A copolymer of methylphenol and 2,6-dimethylphenol, also 2-
A homopolymer of (2-butenyl) -6-methylphenol, a copolymer of 2- (2-butenyl) -6-methylphenol and 2,6-dimethylphenol, and a homopolymer of 2
-Cinnamyl-6-methylphenol homopolymer, also 2-cinnamyl-6-methylphenol and 2,6-
Examples thereof include a dimethylphenol copolymer.

A resin obtained by converting the methyl group at the 2,6-position of poly (2,6-dimethyl-1,4-phenylene ether) disclosed in US Pat. No. 4,634,742 into a vinyl group, also poly (2 A resin obtained by introducing a vinyl group into the 3,5-position of the phenyl group of (2,6-dimethyl-1,4-phenylene ether) is also a preferable example of the polyphenylene ether resin containing an unsaturated group used in the present invention. Is one.

The range of the unsaturated group content of the polyphenylene ether resin containing an unsaturated group used in the present invention is 0.1 mol% or more and 100 mol% or less, more preferably 0. 5 mol% or more and 50 mol%
The following are preferred:

[0050]

[Equation 1]

If the unsaturated group content is less than 0.1 mol%, the chemical resistance after curing is insufficiently improved, which is not preferable. On the contrary, if it exceeds 100 mol%, it becomes very brittle after curing, which is not preferable. Regarding the molecular weight of the unsaturated group-introduced polyphenylene ether resin used in the present invention, the viscosity number ηsp / c measured with a chloroform solution at 30 ° C. and 0.5 g / dl is 0.1 to 1.
Those in the range of 0 can be used favorably. A resin having a low viscosity number is preferable for a curable resin composition that places importance on molten resin flow, such as a sealing material or a prepreg for a multilayer wiring board.

The triallyl isocyanurate and / or triallyl cyanurate used as the component (b) of the polyphenylene ether resin composition of the present invention is
Each is a trifunctional monomer represented by the following structural formula.

[0053]

[Chemical 17]

In practicing the present invention, triallyl isocyanurate and triallyl cyanurate may be used alone, or both may be mixed and used at an arbitrary ratio. In the present invention,
Triallyl isocyanurate and triallyl cyanurate act as a plasticizer and a crosslinking agent. That is, it improves the flow of resin during pressing and the crosslink density.

The silica used as the component (c) of the polyphenylene ether resin composition of the present invention is chemically silicon dioxide (SiO ₂ ). Hereinafter, commonly used commonly used silica is used. The component (c) of the polyphenylene ether-based resin composition of the present invention is characterized in that it contributes to the improvement of the dimensional stability of the resin composition after curing, and adversely affects the mechanical properties and dielectric properties of the cured composition. Don't give.

In the polyphenylene ether resin composition of the present invention, a component (c) which has been previously treated with a coupling agent is used for the purpose of improving the adhesiveness at the interface between the component (c) and the resin, if necessary. be able to. As the coupling agent, silane coupling agents, titanate coupling agents, aluminum-based coupling agents, zircoaluminate coupling agents and the like can be used.
Further, the above coupling agent may be added when the resin composition is prepared.

The particle shape and particle size of the component (c) are not particularly limited, but preferably a crush type particle shape having a wide particle size distribution with an average particle size of 4 to 10 μm. further,
You may mix and use a crushing type and a spherical type. The hydrogenated block copolymer used as the component (d) of the polyphenylene ether-based resin composition of the present invention is at least one polymer block A containing a vinyl aromatic compound as a main component and at least one conjugated diene compound. Is obtained by hydrogenating a block copolymer consisting of a polymer block B mainly composed of

[0058]

[Chemical 18]

It is a hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as. The hydrogenated block copolymer contains a vinyl aromatic compound in an amount of 5 to 85% by weight, preferably 10 to 70% by weight. Further referring to the block structure, a polymer block A mainly composed of a vinyl aromatic compound
Is a polymer block consisting of a vinyl aromatic compound alone 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. And a polymer block B mainly composed of a hydrogenated conjugated diene compound, wherein the polymer block B is composed only of the hydrogenated conjugated diene compound, or a hydrogenated conjugated diene compound Of 50% by weight or more, preferably 70% by weight or more, has a structure of a copolymer block of a hydrogenated conjugated diene compound and a vinyl aromatic compound. Further, the polymer block A mainly composed of these vinyl aromatic compounds and the polymer block B mainly composed of the hydrogenated conjugated diene compound are the hydrogenated conjugated diene in the molecular chain of each polymer block. The distribution of the compound or the vinyl aromatic compound may be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially block-shaped, or any combination thereof. When there are two or more polymer blocks mainly composed of a compound and polymer blocks mainly composed of the hydrogenated conjugated diene compound, the respective polymer blocks may have the same structure or different structures. May be

Examples of the vinyl aromatic compound constituting the hydrogenated block copolymer include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene and p-third.
One or more of butyl styrene and the like can be selected, and styrene is preferable among them. Examples of the conjugated diene compound before hydrogenation that constitutes the hydrogenated conjugated diene compound include, for example, butadiene, isoprene, and 1,3-
One kind or two 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.

The number average molecular weight of the hydrogenated block copolymer of the present invention having the above structure is not particularly limited, but the number average molecular weight is 5,000 to 1,000,000, preferably 10,000 to 500,000, more preferably 30.
It can be used in the range of 000 to 300,000. Further, the molecular structure of the hydrogenated block copolymer may be linear, branched, radial or any combination thereof.

Any method of producing these block copolymers may be used as long as it has the above-mentioned structure. For example, Japanese Patent Publication No. 40-23
A vinyl aromatic compound-conjugated diene compound block copolymer was synthesized in an inert solvent using a lithium catalyst or the like by the method described in JP-A-798-8. The method described in JP-A-43-6636, particularly preferably JP-A-59-13
Hydrogenation is carried out in the presence of a hydrogenation catalyst in an inert solvent by the method described in JP-A No. 3203 and JP-A No. 60-79005 to synthesize the hydrogenated block copolymer used in the present invention. be able to. At that time, the aliphatic double bond based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer is at least 80%.
Can be hydrogenated to morphologically convert the polymer block mainly composed of the conjugated diene compound into the olefin compound polymer block. Further, a polymer block A mainly composed of a vinyl aromatic compound and, if necessary,
The hydrogenation rate of the aromatic double bond based on the vinyl aromatic compound copolymerized with the polymer block B mainly containing the conjugated diene compound is not particularly limited, but the hydrogenation rate should be 20% or less. Is preferred.

The block copolymer also includes a modified block copolymer to which a molecular unit containing a dicarboxylic acid group or a derivative thereof is bound, as long as its characteristics are not impaired. The molecular unit containing a dicarboxylic acid group or a derivative thereof can be used usually in the range of 0.05 to 5 parts by weight with respect to the basic block copolymer. Examples of the modifier containing a dicarboxylic acid group or a derivative thereof include maleic acid, fumaric acid, chloromaleic acid, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid and anhydrides and esters of these dicarboxylic acids. Examples include amide and imide. Specific examples of preferable modifiers include maleic anhydride, maleic acid, and fumaric acid.

The method for producing the modified block copolymer is not particularly limited, but usually, the block copolymer and the modifier are melted by an extruder or the like and reacted with or without a radical initiator. A method is used. The component (d) of the polyphenylene ether resin composition of the present invention improves the toughness of the cured resin composition and does not adversely affect other mechanical properties and dielectric properties of the cured composition.

Of the four components (a) to (d) described above, the mixing ratio of the components (a) and (b) is 98 to 40 for the component (a) based on 100 parts by weight of the sum of the two components. Parts by weight, 2 to 60 parts by weight of the component (b), more preferably 95 to 50 parts by weight of the component (a) and 5 to 5 parts of the component (b).
It is in the range of 0 parts by weight. When the amount of the component (b) is less than 2 parts by weight, the chemical resistance is not sufficiently improved, which is not preferable. Conversely, 60
If it exceeds 5 parts by weight, the dielectric properties and hygroscopic properties deteriorate, and it becomes a very brittle material after curing, which is not preferable.

The mixing ratio of the component (c) used in the resin composition of the present invention is 10 to 400 parts by weight, preferably 10 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b).
The amount is 0 to 300 parts by weight, more preferably 150 to 200 parts by weight. When the amount of the component (c) is less than 10 parts by weight, the thermal expansion characteristics of the resin composition after curing are insufficiently improved, which is not preferable. On the other hand, if it exceeds 400 parts by weight, the fluidity of the resin during melt molding and the adhesion to the metal foil when a laminate with the metal foil is produced are unfavorable.

The blending ratio of the component (d) is 1 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 5 to 2 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b).
0 parts by weight. When the amount of the component (d) is less than 1 part by weight, the toughness of the cured product is not sufficiently improved, which is not preferable. On the other hand, if the amount exceeds 50 parts by weight, the fluidity of the resin at the time of melt molding is lowered, which is not preferable.

As a method for mixing the above-mentioned components (a) to (d), there are a solution mixing method in which the three components are uniformly dissolved or dispersed in a solvent, or a melt blending method in which heating is performed by an extruder or the like. Available. As the solvent used for the solution mixing, halogen-based solvents such as dichloromethane, chloroform and trichloroethylene; aromatic-based solvents such as benzene, toluene and xylene; and tetrahydrofuran are used alone or in combination of two or more.

The resin composition of the present invention may be preliminarily molded into a desired shape depending on its use. The molding method is not particularly limited, and usually, a casting method in which the resin composition is dissolved in the above-mentioned 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 independently. Moreover, you may carry out combining each.
For example, it is possible to obtain a sheet of the present resin composition by laminating several to several tens of films of the present resin composition prepared by a casting method and heating and melting the film by a heating and melting method, for example, using a press molding machine.

The curable resin composition of the present invention and the curable composite material thereof undergo a crosslinking reaction by means of heating or the like to be cured as described later, but the reaction temperature at that time is lowered or crosslinking of unsaturated groups is carried out. A radical initiator may be incorporated for use to accelerate the reaction. The amount of the radical initiator used in the resin composition of the present invention is 0.1 to 10 parts by weight, preferably 0.1 to 8 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b). . Typical examples of the radical initiator include benzoyl peroxide, cumene hydroperoxide, and 2,5-dimethylhexane-
2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,
Di-t-butyl peroxide, t-butyl cumyl peroxide, α, α′-bis (t-butylperoxy-
m-isopropyl) benzene, 2,5-dimethyl-2,
5-di (t-butylperoxy) hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2, 2-bis (t-
Butyl peroxy) octane, 2,5-dimethyl-2,
There are peroxides such as, but not limited to, 5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, and trimethylsilyltriphenylsilylperoxide. Also, it is not a peroxide, but 2,3-
Dimethyl-2,3-diphenylbutane can also be used as a radical initiator. However, the initiator used for curing the resin composition is not limited to these examples.

The resin composition of the present invention can be used by blending an amount of a filler or an additive within a range that does not impair the original properties for the purpose of imparting desired performance depending on its use. The filler may be fibrous or powdery,
Examples thereof include carbon black, alumina, talc, mica, glass beads and glass hollow spheres. As additives, antioxidants, heat stabilizers, antistatic agents, plasticizers,
Examples include pigments, dyes, colorants, and the like. For the purpose of further improving flame retardancy, chlorine-based, bromine-based, phosphorus-based flame retardants, Sb ₂ O ₃ , Sb ₂ O ₅ , NbSbO ₃ · 1 / 4H
A flame retardant aid such as ₂ O can also be used in combination.

Further, it is possible to blend one kind or two or more kinds of other thermoplastic resins or thermosetting resins. Examples of thermoplastic resins include polyolefins such as polyethylene, polypropylene, polybutene, ethylene / propylene copolymer, poly (4-methyl-pentene), and their derivatives, nylon 4, nylon 6, nylon 6,
Polyamides such as 6, nylon 6/10 and nylon 12 and their derivatives, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyesters such as polyethylene terephthalate / polyethylene glycol block copolymers and their derivatives, polyphenylene ether, modified polyphenylene Ether, polycarbonate, polyacetal, polysulfone, polyvinyl chloride and its copolymer, polyvinylidene chloride and its copolymer, polymethylmethacrylates, acrylic acid (or methacrylic acid) ester copolymers, polystyrenes, acrylonitrile styrene Polystyrenes such as copolymers, acrylonitrile styrene butadiene-based copolymers and their copolymers, polyvinyl acetates, polyethylene Vinyl formal, polyvinyl acetal, polyvinyl butyral, ethylene vinyl acetate copolymers and hydrolysates thereof, polyvinyl alcohols, styrene butadiene block copolymers, rubbers such as polybutadiene and polyisoprene, polymethoxyethylene, polyethoxy Polyvinyl ethers such as ethylene, polyacrylic amide, polyphosphazenes,
Examples thereof include liquid crystal polymers such as polyether sulfone, polyether ketone, polyether imide, polyphenylene sulfide, polyamide imide, thermoplastic polyimide and aromatic polyester, and side chain type liquid crystal polymers containing a liquid crystal component in the side chain. Examples of the thermosetting resin include epoxy resin and polyimide precursor.

The cured polyphenylene ether resin composition of the present invention is obtained by curing the curable polyphenylene ether resin cured composition described above. The curing method is arbitrary, and a method using heat, light, an electron beam or the like can be adopted. When curing is performed by heating, the temperature varies depending on the type of radical initiator, but it is 80 to 300 ° C., and more preferably 120 to 2 ° C.
It is selected in the range of 50 ° C. The time is about 1 minute to 10 hours, more preferably 1 minute to 5 hours.

The resin composition of the obtained cured polyphenylene ether resin composition can be analyzed by methods such as infrared absorption spectroscopy, high resolution solid state nuclear magnetic resonance spectroscopy and pyrolysis gas chromatography. Also, this curable polyphenylene ether resin composition can be used by laminating it with a metal foil and / or a metal plate, as in the case of the cured composite material described below as the fourth invention.

Next, the third and fourth curable composite materials of the present invention and their cured products will be described. Third of the present invention
Is a polyphenylene ether resin containing an unsaturated group, (b) triallyl isocyanurate and / or triallyl cyanurate, (c) silica, (d) hydrogenated block copolymer and (E) base material,
It is characterized by consisting of.

As the base material of the component (e), various kinds of glass cloth such as roving cloth, cloth, chopped mat, surfacing mat, asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloth; polyvinyl alcohol fiber, Woven or non-woven fabric obtained from synthetic fibers such as polyester fiber, acrylic fiber, wholly aromatic polyamide fiber, polytetrafluoroethylene fiber; cotton cloth,
Natural fiber cloths such as linen cloth and felt; carbon fiber cloths; natural cellulosic cloths such as kraft paper, cotton paper, paper-glass mixed fiber paper, etc. may be used alone or in combination.

The blending ratio of the component (a) and the component (b) is 98 to 4 for the component (a) based on 100 parts by weight of the sum of both.
0 parts by weight, 2 to 60 parts by weight of the component (b), more preferably 95 to 50 parts by weight of the component (a) and 5 to 50 parts by weight of the component (b). When the amount of the component (b) is less than 2 parts by weight, the chemical resistance is not sufficiently improved, which is not preferable. On the other hand, if it exceeds 60 parts by weight, the dielectric properties and moisture absorption properties will deteriorate,
Further, it is not preferable because it becomes a very brittle material after curing.

The mixing ratio of the component (c) is 10 to 100 based on 100 parts by weight of the sum of the components (a) and (b).
Parts by weight, preferably 20 to 70 parts by weight, more preferably 30 to 50 parts by weight. When the amount of the component (c) is less than 10 parts by weight, the thermal expansion characteristics of the resin composition after curing are insufficiently improved, which is not preferable. Further, if it exceeds 100 parts by weight, the adhesive force with a metal decreases, which is not preferable.

The mixing ratio of the component (d) is 1 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 5 to 2 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b).
0 parts by weight. When the amount of the component (d) is less than 1 part by weight, the toughness of the cured product is not sufficiently improved, which is not preferable. On the other hand, if the amount exceeds 50 parts by weight, the fluidity of the resin at the time of melt molding is lowered, which is not preferable.

The proportion of component (e) 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.
Parts by weight. If the component (e) is less than 5 parts by weight, the dimensional stability and strength of the composite material after curing will be insufficient,
If the amount of the base material is more than 90 parts by weight, the dielectric properties of the composite material are inferior, which is not preferable.

In the composite material of the present invention, a coupling agent can be used if necessary for the purpose of improving the adhesiveness at the interface between the resin and the substrate. As the coupling agent, silane coupling agents, titanate coupling agents, aluminum-based coupling agents, zircoaluminate coupling agents and the like can be used. The method for producing the composite material of the present invention includes, for example, the first method of the present invention.
The components (a) to (d) described in the section (1) and, if necessary, other components are uniformly dissolved or dispersed in the aforementioned halogen-based, aromatic, ketone-based solvent or a mixed solvent thereof,
A method of impregnating the base material and then drying the base material may be mentioned.

Impregnation is carried out by dipping, coating or the like. Impregnation can be repeated multiple times as needed, and in this case it is also possible to repeat impregnation using multiple solutions with different compositions and concentrations to finally adjust the desired resin composition and amount. Is. The fourth curable composite material of the present invention is obtained by curing the curable composite material thus obtained by a method such as heating. The manufacturing method is not particularly limited, and for example, a plurality of the curable composite materials are stacked, and each layer is adhered under heat and pressure, and at the same time heat cured to obtain a cured composite material having a desired thickness. You can It is also possible to obtain a cured composite material having a new layer structure by combining the cured composite material that has been adhesively cured once and the curable composite material. The lamination molding and curing are usually performed simultaneously by using a hot press or the like, but both may be performed independently. That is, an uncured or semi-cured composite material obtained by laminating in advance can be cured by heat treatment or another method.

Molding and curing are carried out at a temperature of 80 to 300 ° C.
Pressure 0.1-1000Kg / cm² , 1 minute to 10 o'clock
Range, more preferably, the temperature of 150 ~ 250 ℃, pressure
Force 1-500Kg / cm², In the range of 1 minute to 5 hours
It can be carried out. Finally, in the laminated body which is the fifth of the present invention
explain about. The laminated body of the present invention is the fourth of the present invention.
And composed of the cured composite material and metal foil described above
It is a thing. Examples of the metal foil used here include
Examples include copper foil and aluminum foil. Especially its thickness
Although not limited, 5-200 μm, more preferably 5-
It is in the range of 105 μm.

As the method for producing the laminate of the present invention,
For example, a method in which the curable composite material described above as the third aspect of the present invention and a metal foil and / or a metal plate are laminated in a layered structure according to the purpose, and each layer is adhered under heat and pressure and at the same time heat cured. Can be mentioned. In the laminate of the present invention, the curable composite material and the metal foil are laminated in any layer structure. The metal foil can be used as both the surface layer and the intermediate layer.

In addition to the above, it is also possible to repeat lamination and curing a plurality of times to form a multilayer. An adhesive may be used to bond the metal foil. As an adhesive, epoxy type,
Examples thereof include acrylic type, phenol type, and cyanoacrylate type, but are not particularly limited thereto. The lamination molding and curing described above can be performed under the same conditions as in the fourth aspect of the present invention.

[0086]

EXAMPLES Hereinafter, the present invention will be described with reference to examples in order to further clarify the present invention, but the scope of the present invention is not limited to these examples. In the examples below, the following components were used. Polymerization initiator: 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3 (NOF Corporation Perhexin 25B; abbreviated as PH25B) Silica: Fuze Rex E-2 (Tatsumori Co., Ltd.) FUUSELEX silane coupling treatment E-2 (manufactured by Tatsumori Co., Ltd.) Glass Rain CUS-85K (manufactured by Toshiba Ceramics Co., Ltd.) Hydrogenated block copolymer: H1041 (Asahi Kasei Co., Ltd.)
H1051 (manufactured by Asahi Chemical Industry Co., Ltd.) Flame retardant: Decabromodiphenyl ether (Asahi Glass A
FR-1021) flame retardant agent: Sb ₂ O ₃ (Nippon Seiko PATOX-M) glass cloth: E glass, a basis weight of 48g / m ²

[0087]

Reference Example 1 Polyphenylene ether resin containing an unsaturated group, average substitution ratio 14%, ηsp / C = 0.62 (30 ° C.,
An allyl group-substituted polyphenylene ether (abbreviated as A-PPE) (0.5 g / dl, chloroform solution) was used.
According to known methods disclosed in US Pat.
It was synthesized from poly (2,6-dimethyl-1,4-phenylene ether) with /C=0.56. This polymer is designated as A.

[0088]

[Reference Example 2] Polyphenylene ether resin containing an unsaturated group In the same manner as in Reference Example 1, an average substitution rate of 14%, ηsp /
Ηsp of C = 0.44 (30 ° C., 0.5 g / dl, chloroform solution) allyl group-substituted polyphenylene ether
It was synthesized from poly (2,6-dimethyl-1,4-phenylene ether) with /C=0.40.

This polymer is designated as B.

[0090]

Examples 1 to 9 Curable polyphenylene ether resin composition and curing
Polyphenylene ether resin composition The polyphenylene ether resin A or B containing an unsaturated group synthesized in Reference Examples 1 and 2, triallyl (iso) cyanurate, silica and hydrogenated block copolymer having the composition shown in Table 1 are used in a Henschel mixer. Was mixed and molded by a press molding machine at 200 ° C. for 30 minutes and cured to prepare a cured product having a thickness of about 1 mm.

This cured product was cut into a 7 mm square and the coefficient of thermal expansion in the thickness direction was measured by a thermomechanical analyzer at a rate of temperature rise of 20 ° C./min. The coefficient of thermal expansion referred to here is the rate of increase in the sample thickness when the temperature of the sample is increased from 30 ° C to 150 ° C, which is the change in temperature of 120 ° C (150 ° C-30
The value is divided by (° C). In any 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.

[0092]

[Reference Example 3] Polyphenylene ether and unsaturated carboxylic acid or no acid
Product 30 ° C. obtained by modifying reaction anhydride, poly (2,6-dimethyl-1,4-phenylene ether) having a viscosity number .eta.sp / c measured in chloroform solution of 0.5 g / dl is 0.54 to 100 parts by weight And 1.5 parts by weight of maleic anhydride and 2,5-dimethyl-
After dry blending 1.0 part by weight of 2,5-di (t-butylperoxy) hexane (Perhexa25B, manufactured by NOF CORPORATION) at room temperature, 2 under the conditions of a cylinder temperature of 300 ° C. and a screw rotation speed of 230 rpm. A reaction product was obtained by extrusion with a shaft extruder. Ηs of this reaction product
p / c was 0.48. Hereinafter, this reaction product is abbreviated as maleated PPE. This reaction product is thermoplastic and can be added to the resin composition of the present invention.

[0093]

Example 10 In Example 3, 55 parts of polyphenylene ether resin containing an unsaturated group was made into 44 parts, and 11 parts of the maleated PPE synthesized in Reference Example 3 was added in the form of replacing this. As in Example 3, a cured product having a small coefficient of thermal expansion, toughness, and resin fluidity was obtained.
The results are shown in Table 1.

[0094]

Comparative Example 1 A cured product was prepared in the same manner as in Example 1 except that silica and hydrogenated block copolymer were not added. The coefficient of thermal expansion was extremely larger than that in Example 1.

[0095]

Comparative Example 2 A cured product was prepared with the same composition as in Example 8 except that silica was not added. The coefficient of thermal expansion was extremely higher than that in Example 8.

[0096]

Comparative Example 3 A cured product was prepared with the same composition as in Example 6 except that the hydrogenated block copolymer was not added. The cured product cracked when rubbed with a file.

[0097]

Comparative Example 4 A cured product was prepared with the same composition as in Example 8 except that the silica was 500 parts. The cured product is brittle,
There was unevenness on the surface.

[0098]

Comparative Example 5 A cured product was prepared with the same composition as in Example 9 except that the hydrogenated block copolymer was changed to 60 parts. The coefficient of thermal expansion was extremely higher than that in Example 8. The results of the above comparative examples are shown in Table 1 together with Examples 1 to 10.

[0099]

[Table 1]

[0100]

Examples 11 to 18 Curable composite material For each composition shown in Table 2, a total amount of 200 g of the composition was 8
It was dissolved or dispersed in 1000 ml of toluene at 0 ° C. This solution is cooled to 50 ° C., glass cloth is immersed at 50 ° C. for impregnation, and the solution is placed in an air oven at 50 ° C. for 3 days.
It was dried for 0 minutes to obtain a curable composite material.

A plurality of the above-mentioned curable composite materials were superposed so that the thickness of the laminated body after molding was about 0.8 mm, and the thickness was 35 μm on both sides.
The copper foil of was placed and cured by a press molding machine to obtain a laminate. The curing conditions of each example are shown in Table 3. The pressure was 20 kg / cm ^{2 in} all cases.

Various physical properties of the thus obtained laminate were measured by the following methods. 1. Trichloroethylene resistance The laminate from which the copper foil was removed was cut into 25 mm square pieces, boiled in trichlorethylene for 5 minutes, and the change in appearance was visually observed. 2. The dielectric constant and the dielectric loss tangent were measured at 1 MHz. 3. Solder heat resistance Cut the laminate from which the copper foil was removed into 25 mm square pieces, 260
Floating in a solder bath at ℃ for 120 seconds, 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 made on the copper foil surface, and then a speed of 50 mm / min in a direction perpendicular to the surface. Then, the copper foil was continuously peeled off, and the stress at that time was measured by a tensile tester, and the minimum value of the stress was shown. 5. Thermal expansion characteristics The laminate from which the copper foil was removed was cut into a 7 mm square, and the thermal expansion amount in the thickness direction was measured by a thermomechanical analyzer at a rate of temperature increase of 20 ° C / min. 6. Resin Flowability Three curable composite materials are stacked and pressed at 170 ° C. for 10 minutes by a press molding machine at a surface pressure of 22 kg / cm ² , and the resin composition protruding is weighed to determine the volume of the resin composition. A value obtained by dividing this by the volume of only the resin composition in the curable composite material before pressing was shown. 7. Cracks In order to investigate the toughness of the resin, a multilayer printed wiring board was prepared and subjected to a thermal shock of 100 times between -65 ° C and 125 ° C to see if resin cracks were generated inside the wiring board.

In each of the examples, a cured product having a small coefficient of thermal expansion, toughness, resin fluidity, and excellent dielectric properties was obtained. The physical properties are shown in Table 3.

[0104]

Example 19 The maleated PPE synthesized in Reference Example 3 was prepared in the same manner as in Example 13 except that the polyphenylene ether resin containing 55 parts of the unsaturated group was replaced by 44 parts.
11 parts were added. Similar to Example 13, a cured product having a small coefficient of thermal expansion, toughness, and resin fluidity was obtained. Table 3 shows the physical properties.

[0105]

[Example 20] The maleated PPE prepared in Reference Example 3 in the same manner as in Example 14 except that the polyphenylene ether resin containing 55 parts of unsaturated groups was replaced by 44 parts.
11 parts were added. Similar to Example 14, a cured product having a small coefficient of thermal expansion, toughness, and resin fluidity was obtained. Table 3 shows the physical properties.

[0106]

Comparative Example 6 A cured product was prepared in the same manner as in Example 11 except that silica and hydrogenated block copolymer were not added. The coefficient of thermal expansion was larger than that in Example 11, and cracks were generated.

[0107]

Comparative Example 7 A cured product was prepared in the same manner as in Example 18, except that silica was not added.
The coefficient of thermal expansion was larger than that in Example 18, and cracks were generated.

[0108]

Comparative Example 8 A cured product was prepared in the same manner as in Example 16, except that the hydrogenated block copolymer was not added. A crack has occurred.

[0109]

[Comparative Example 9] A cured product was prepared in the same manner as in Example 18, except that 125 parts of silica was used. The resin flowability was poor, and the copper foil peeling strength decreased.

[0110]

Comparative Example 10 A cured product was prepared in the same manner as in Example 18, except that the hydrogenated block copolymer was changed to 60 parts. The resin flowability was poor and the coefficient of thermal expansion was large. Various physical properties of the above comparative examples are shown in Table 3 together with Examples 11 to 20.

[0111]

[Table 2]

[0112]

[Table 3]

[0113]

The resin composition of the present invention can be preformed into a film, sheet or curable composite material having a good appearance before curing. By using the curable polyphenylene ether-based resin composition of the present invention, a cured polyphenylene ether-based resin composition having excellent dielectric properties, mechanical properties, chemical resistance, and heat resistance and having unprecedented low coefficient of thermal expansion and toughness. The thing is obtained.

The curable composite material of the present invention has excellent adhesion to metal. Further, the cured composite material and the laminate obtained by using the curable composite material of the present invention have heat resistance, chemical resistance and excellent dielectric properties, and have an unprecedentedly low coefficient of thermal expansion and toughness. It is a good material. Therefore, the material of the present invention can be used as a dielectric material, an insulating material, a heat-resistant material, etc. in the fields of electric industry, electronic industry, space / aircraft industry and the like. In particular, the curable composite material of the present invention is a single-sided, double-sided, multilayer printed circuit board, semi-rigid substrate,
It is preferably used as a prepreg for metal base substrates and multilayer printed circuit boards.

Further, the material of the present invention is excellent as an adhesive for a high-density circuit board having a line spacing of 100 μm or less, a multilayer circuit board having an interlayer insulating layer thickness of 200 μm or less, and a mounting circuit board because of its heat resistance and moisture absorption resistance Can be used for

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/3477 C08L 53/02 LLZ

Claims (5)

[Claims] 1. A sum of (a), (a) component and (b) component 1
Based on 100 parts by weight, 98 to 40 parts by weight of a polyphenylene ether resin containing an unsaturated group, (b), 2 to 6 based on 100 parts by weight of the sum of the components (a) and (b).
0 parts by weight of triallyl isocyanurate and / or triallyl cyanurate, components (c), (a) and (b)
10 to 400 parts by weight of silica based on 100 parts by weight of the components, and 100 of the components (d), (a) and (b).
A block copolymer comprising 1 to 50 parts by weight, based on parts by weight, of at least one vinyl aromatic compound-based polymer block A and at least one conjugated diene compound-based polymer block B. A curable polyphenylene ether resin composition comprising a hydrogenated block copolymer obtained by hydrogenating 2. A cured polyphenylene ether-based resin composition obtained by curing the curable polyphenylene ether-based resin composition according to claim 1. 3. The sum 1 of the components (a), (a) and (b).
Based on 100 parts by weight, 98 to 40 parts by weight of a polyphenylene ether resin containing an unsaturated group, (b), 2 to 6 based on 100 parts by weight of the sum of the components (a) and (b).
0 parts by weight of triallyl isocyanurate and / or triallyl cyanurate, components (c), (a) and (b)
10 to 100 parts by weight of silica based on 100 parts by weight of the components, and 100 of the components (d), (a) and (b).
A block copolymer comprising 1 to 50 parts by weight, based on parts by weight, of at least one vinyl aromatic compound-based polymer block A and at least one conjugated diene compound-based polymer block B. Hydrogenated block copolymer obtained by hydrogenating, and (e),
5 based on 100 parts by weight of the sum of components (a) to (e)
A curable composite material comprising 90 parts by weight of a base material. 4. A cured composite material obtained by curing the curable composite material according to claim 3. 5. A laminate comprising the cured composite material according to claim 4 and a metal foil.