JP2001081305A - Curable polyphenylene ether resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable polyphenylene ether resin composition having excellent dispersibility of silica capable of forming a metal foil or the like pasted on the resin having excellent flatness free from aggregation of silica by compounding a silica treated with a specific silane coupling agent to a thermosetting polyphenylene ether based resin. SOLUTION: This thermosetting polyphenylene ether based resin composition includes (A) 100 pts.wt of a thermosetting polyphenylene ether based resin, (B) 10-38,000 pts of a silica treated with one or more kind of silane coupling agents selected from silane compounds having structure of formulas I-III (R1 and R2 are each a 1-5C divalent hydrocarbon). The composition preferably includes, (C) 1-1,900 pts of a hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising a polymer block mainly comprising at least a vinyl aromatic compound and a polymer block mainly comprising at least a conjugated diene compound, per 100 pts of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable polyphenylene ether-based resin composition. Furthermore, the present invention
The present invention relates to a composite material comprising the resin composition and a substrate, a film comprising the resin composition, a laminate comprising a film comprising the resin composition and a metal foil, and a cured product thereof.

[0002]

2. Description of the Related Art In recent years, there has been a remarkable trend toward miniaturization and high-density mounting methods in the field of electronic devices for communication, consumer use, industrial use, and the like, and accordingly, materials have become more excellent. Heat resistance, dimensional stability, water absorption resistance and constant dielectric constant and dielectric loss tangent over a wide high frequency range and temperature range, and
Smallness is being demanded. For example, as a printed wiring board, a conventional copper-clad laminate using a thermosetting resin such as a phenol resin or an epoxy resin has been used. Although these have various performances in a well-balanced manner,
It has the drawback of poor electrical properties, especially dielectric properties in the high frequency range.

[0003] Epoxy resins also have problems in heat resistance and water absorption. As a new material for solving this problem, polyphenylene ether-based resins have recently attracted attention and have been applied. However, since the polyphenylene ether-based resin has a higher coefficient of thermal expansion than a polyimide resin or the like, it may be insufficient as a laminated board material in terms of dimensional stability. Further, the fact that the coefficient of thermal expansion is high also has a disadvantage that the difference in the coefficient of thermal expansion between the metal of the metal circuit formed on the surface of the laminate and the like is large.

In order to solve this problem, it has been studied to reduce the coefficient of thermal expansion of a laminate by adding silica having a small coefficient of thermal expansion to a thermosetting polyphenylene ether-based resin. Is a hydrophilic property due to the presence of a large number of silanol groups, and if it is added to a hydrophobic thermosetting polyphenylene ether-based resin as it is, there is no affinity between the two, so that a sufficiently dispersed state cannot be obtained. As a result, when a resin-coated metal foil or film is manufactured using silica, aggregates of silica are generated in the resin composition, and the surface smoothness of the resin-coated metal foil or film is lost, and a cured product is also obtained. In this case, a resin crack may be generated starting from the silica aggregate. In particular, when the thickness of the resin layer is small, it is required to reduce the diameter of the silica to be compounded, and the specific surface area is increased.

[0005]

SUMMARY OF THE INVENTION The present invention provides a polyphenylene ether-based resin having excellent dielectric properties and crack resistance without impairing the excellent chemical resistance after curing.
In addition to heat resistance, to provide a curable polyphenylene ether-based resin composition capable of producing a resin-attached metal foil or film having a low coefficient of thermal expansion and excellent smoothness without silica aggregates on the surface. Aim.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, a thermosetting polyphenylene ether-based resin has the following formulas (1) and (2). ) And a silica treated with at least one silane coupling agent selected from the group consisting of silane compounds having a structure represented by the formula (3), thereby improving the affinity between the two. It has been found that an excellent dispersion state can be obtained, and the present invention has been achieved.

That is, the present invention provides: (A) a thermosetting polyphenylene ether-based resin,
And (b) containing silica treated with at least one silane coupling agent selected from the group consisting of silane compounds having a structure represented by the following formula (1), formula (2) or formula (3): A curable polyphenylene ether-based resin composition comprising 10 to 38000 parts by weight of the component (b) based on 100 parts by weight of the component (a).

[0008]

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[0009] 2. (A) a thermosetting polyphenylene ether-based resin; and (b) at least one member selected from the group consisting of silane compounds having a structure represented by the following formula (1), formula (2) or formula (3). A block copolymer comprising silica treated with a silane coupling agent, and (c) 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. It contains a hydrogenated block copolymer obtained by hydrogenating the polymer, and based on 100 parts by weight of the component (a), the component (b) is added in an amount of 10 to 380.
A curable polyphenylene ether-based resin composition, wherein the curable polyphenylene ether-based resin composition contains 1 to 1900 parts by weight of the component (c).

[0010]

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3. The silane coupling agent has the formula (1)
3. The curable polyphenylene ether-based resin composition according to 1 or 2 above, which is a silane compound having a structure represented by 4. a curable composite material comprising the curable polyphenylene ether-based resin composition of 1, 2, or 3, and a base material; 5. A cured composite material obtained by curing the curable composite material of the above item 4, 6. a curable film comprising the curable polyphenylene ether-based resin composition of the above 1, 2 or 3; 7. a cured film obtained by curing the curable film of 6 above; 8. A curable laminate comprising the curable film and the metal foil according to 6 above, 9. a cured laminate obtained by curing the curable laminate of the above item 8, 10. a curable composite comprising the curable composite material of 4 above and / or the curable film of 6 above and / or the curable laminate of 8 above; A cured composite obtained by curing the curable composite of the above item 10.

Hereinafter, the present invention will be described in detail.
The thermosetting polyphenylene ether-based resin used in the present invention contains a polyphenylene ether-based resin (including a modified product) as a component. The content of the polyphenylene ether-based resin (including the modified product) is 40 to 40 parts by weight based on 100 parts by weight of the thermosetting polyphenylene ether-based resin.
98 parts by weight, preferably 43 to 90 parts by weight.

Preferred examples of the above polyphenylene ether resins include poly (2,6-dimethyl-1,4-phenylene ether) obtained by homopolymerization of 2,6-dimethylphenol and poly (2,6-dimethyl -1,4-
Phenylene ether) styrene graft polymer, 2,
Copolymer of 6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and 2-
Methyl-6-phenylphenol copolymer, 2,6-
Polyfunctional polyphenylene ether resin obtained by polymerizing dimethylphenol in the presence of a polyfunctional phenol compound, for example, JP-A-63-301222, JP-A-1
And copolymers containing units of general formulas (A) and (B) as disclosed in JP-297428-A.

The polyphenylene ether-based resin referred to in the present invention includes a modified product. Preferred examples of such a modified product include a polyphenylene ether resin containing an unsaturated group (JP-A-64-69628). JP-A-1-
No. 113425 and JP-A-1-113426), and a reaction product of a polyphenylene ether resin with an unsaturated carboxylic acid and / or acid anhydride. Regarding the molecular weight of the polyphenylene ether resin used in the present invention, 30 ° C., 0.5 gr
/ Dl viscosity number ηsp / c measured with chloroform solution
Is in the range of 0.1 to 1.0 can be used favorably. Preferably, it is in the range of 0.2 to 0.9.

Next, as the resin to be compounded other than the above polyphenylene ether-based resin, any resin may be used as long as the object of the present invention is not impaired. As such a resin, specifically, a phenol resin, an epoxy resin, diallyl phthalate, divinylbenzene, a polyfunctional acryloyl compound, a polyfunctional methacryloyl compound, a polyfunctional maleimide, a polyfunctional cyanate ester,
Polyfunctional isocyanates, unsaturated polyesters, triallyl isocyanurate, triallyl cyanurate, polybutadiene, crosslinkable polymers such as styrene-butadiene / styrene-butadiene-styrene, various thermoplastic resins, various thermosetting resins, etc. No. These are generally blended for the purpose of improving the physical properties of a substrate prepared by laminating a composite material, a resin-attached metal foil and / or a film.

Preferred examples of the thermosetting polyphenylene ether resin used in the present invention include polyphenylene ether, triallyl isocyanurate and / or triallyl cyanurate, polyphenylene ether and epoxy resin, polyphenylene ether containing unsaturated group, and Triallyl isocyanurate and / or triallyl cyanurate, polyphenylene ether containing an unsaturated group, and triallyl isocyanurate and / or triallyl cyanurate with an epoxy resin, polyphenylene ether resin with an unsaturated carboxylic acid and / or acid anhydride. Reaction product of triallyl isocyanurate and / or triallyl cyanurate, reaction product of polyphenylene ether resin with unsaturated carboxylic acid and / or acid anhydride, and epoxy Fat, polyphenylene ether resin and an unsaturated reaction product and triallyl isocyanurate with carboxylic acids and / or acid anhydride and / or triallyl cyanurate and an epoxy resin, and the like. The amount of each component in these systems is selected according to the purpose.

The silica used as the component (b) of the present invention is blended for the purpose of imparting dimensional stability to the cured product of the curable polyphenylene ether-based resin composition of the present invention. In order to reduce the hydrophilicity of untreated silica (SiO ₂ ), the following formula (1):
It has been treated with at least one silane coupling agent selected from the group consisting of silane compounds having the structure represented by the formula (2) or (3).

That is, untreated silica is treated with a silane coupling agent, and the silanol group on the silica surface is replaced with a hydrophobic group represented by the following formula (1), (2) or (3). Substitution reduces its hydrophilicity.
As a result, the affinity with the hydrophobic thermosetting polyphenylene ether-based resin is improved, and a good dispersion state is formed between the two. Thus, the following equations (1) and (2)
Alternatively, silica treated with a silane coupling agent selected from silane compounds having a structure represented by the formula (3) is well dispersed in a thermosetting polyphenylene ether-based resin, and therefore, the curable polyphenylene ether-based resin of the present invention is used. Metal foil and film with resin created using the composition,
It has a smooth surface without silica agglomerates. Furthermore, in the case of a cured product, it is possible to avoid the occurrence of resin cracks originating from the silica aggregate.

[0019]

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When the silane compound having the structure represented by the above formula (1), (2) or (3) has an alkoxy group such as a methoxy group and an ethoxy group, these are untreated. It is preferable because it reacts with a silanol group on the silica surface and is easily replaced with a group having a structure represented by the above formula (1), formula (2) or formula (3). Examples of such a silane coupling agent include γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane; -Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane and the like. Can be

Among the silane coupling agents having the structures represented by the above formulas (1), (2) and (3), the silane coupling agent having the structure of the formula (1) is not yet available. When the silanol group of the treated silica is substituted with a group having a structure represented by the formula (1), the hydrophilicity of the untreated silica is greatly reduced, and the silica is particularly well dispersed in the thermosetting polyphenylene ether-based resin. Is preferred. Particularly preferred silane coupling agents used in the present invention include γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane And the like.

The silane coupling agent treatment is
Another object is to improve the adhesion at the interface between the silica and the resin. The treatment amount of the silane coupling agent is not particularly limited, and although it depends on the specific surface area of the untreated silica, 0.1 to 5 wt. %. This processing amount is 0.1 wt. %, Sufficient dispersibility cannot be obtained, and 5 wt. %, It is unfavorable because aggregation of silica occurs on the contrary. A more preferable range of the processing amount is 0.3 to 2 w.
t. %.

The shape of the silica may be spherical, crushed, or a mixture thereof, and is not particularly limited. The average particle size is not particularly limited as long as it is not more than the thickness of the cured product formed by the curable polyphenylene ether-based resin composition of the present invention, but is preferably 0.1 to 3 μm.
The hydrogenated block copolymer of the component (c) preferably used in the curable polyphenylene ether-based resin composition of the present invention comprises at least one polymer block A mainly composed of a vinyl aromatic compound and a conjugated diene compound. It is obtained by hydrogenating a block copolymer composed of at least one of the main polymer blocks B, and is, for example, a vinyl aromatic compound-conjugated diene compound having a block structure or the like represented by the following chemical formula 6. It is a hydrogenated block copolymer. The hydrogenated block copolymer contains 5 to 85% by weight, preferably 10 to 70% by weight of a vinyl aromatic compound.

[0024]

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Still referring to the block structure,
The hydrogenated polymer block A mainly composed of a vinyl aromatic compound contains more than 50% by weight, preferably 70% by weight or more of a polymer block composed of only a vinyl aromatic compound or a vinyl aromatic compound. Having a structure of a copolymer block of an aromatic compound and a hydrogenated conjugated diene compound, and further comprising a hydrogenated polymer block B mainly composed of a conjugated diene compound
Is a polymer block consisting of only a hydrogenated conjugated diene compound, or a hydrogenated conjugated diene compound containing more than 50% by weight, preferably 70% by weight or more, of a hydrogenated conjugated diene compound and vinyl aromatic. It has a structure of a copolymer block with a compound.

The hydrogenated polymer block A mainly composed of a vinyl aromatic compound and the polymer block B mainly composed of a hydrogenated conjugated diene compound are used.
The distribution of the hydrogenated conjugated diene compound or vinyl aromatic compound in the molecular chain in each polymer block is random, tapered (one in which the monomer component increases or decreases along the molecular chain), and some blocks. Or any combination of these,
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.

The vinyl aromatic compound constituting the hydrogenated block copolymer is, for example, one or two of styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, p-tert-butylstyrene, and the like. The above can be selected, and among them, styrene is preferable. Further, as the conjugated diene compound before hydrogenation constituting the hydrogenated conjugated diene compound, for example, butadiene, isoprene,
One or more of 1,3-pentadiene, 1,3-dimethyl-1,3-butadiene and the like are selected, and among them, butadiene, isoprene and a combination thereof are preferable.

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

As a method for producing these block copolymers, any production method having the above-mentioned structure may be used. For example, Japanese Patent Publication No. 40-2379
No. 8, a vinyl aromatic compound-conjugated diene compound block copolymer is synthesized in an inert solvent using a lithium catalyst or the like, and then, for example, disclosed in JP-B-42-8704. JP-B-43-6636, JP-B-59-133203 and JP-B-60.
Hydrogenation in an inert solvent in the presence of a hydrogenation catalyst by a method described in JP-A-79005, particularly preferably a method described in JP-B-59-133203 and JP-B-60-79005. By the addition, the hydrogenated block copolymer used in the present invention can be synthesized.

At this time, at least 80% by weight of the aliphatic double bond based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer is hydrogenated, and the copolymer block mainly composed of the conjugated diene compound is hydrogenated. Can be morphologically converted to an olefinic compound polymer block. Further, hydrogen of an aromatic double bond based on a vinyl aromatic compound copolymerized with a polymer block A mainly composed of a vinyl aromatic compound and, if necessary, a polymer block B mainly composed of a conjugated diene compound. Although the addition ratio is not particularly limited, the hydrogenation ratio is preferably set to 20% by weight or less. The blending ratio of the component (b)
10 to 38000 based on 100 parts by weight of component (a)
Parts by weight, preferably 20 to 10000 parts by weight, more preferably 40 to 1000 parts by weight. (B) component is 10
If the amount is less than part by weight, the improvement of the thermal expansion characteristics of the curable polyphenylene ether-based resin composition of the present invention is insufficient, which is not preferable. On the other hand, if it exceeds 38,000 parts by weight, the fluidity of the resin composition is lost, and the adhesion to the metal foil when a laminate with the metal foil is formed is undesirably reduced.

The compounding ratio of the component (c) preferably used in the curable polyphenylene ether resin composition of the present invention is from 1 to 1 based on 100 parts by weight of the component (a).
900 parts by weight, preferably 1 to 1000 parts by weight,
More preferably, it is 1 to 500 parts by weight. The compounding ratio of the component (c) is 1 to 1 based on 100 parts by weight of the component (a).
When the content is in the range of 900 parts by weight, the toughness of the cured product is sufficiently improved, and the fluidity of the resin composition is also satisfied.

As a method of mixing the components (a) and (b), a solution mixing method of uniformly dissolving / dispersing the two components in a solvent is employed, but the dispersibility of the component (b) is further improved. For this purpose, it is preferable to use a dispersing machine such as a planetary system, a ball mill or a bead mill system, or a three-roll mill system. As the solvent used in the solution mixing method,
Aromatic hydrocarbons such as benzene, toluene and xylene,
Halogen-based solvents such as dichloromethane, chloroform and trichloroethylene, and THF and the like can be mentioned, and these can be used alone or in combination.
In the case of the three components (a), (b) and (c),
Mixing can be performed in a similar manner.

The curable polyphenylene ether-based resin composition of the present invention is cured by causing a cross-linking reaction by means of heating or the like, as will be described later. For the purpose of accelerating, a radical initiator may be contained and used. The amount of the radical initiator used in the curable polyphenylene ether-based resin composition of the present invention is 0.1% based on 100 parts by weight of the component (a).
It is 1 to 10 parts by weight, preferably 0.1 to 8 parts by weight.

Representative examples of the radical initiator include:
Benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-
Butylperoxy) hexyne-3, di-t-butyl peroxide, t-butylcumyl 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-butylperoxy) octane, 2,5-dimethyl-2, Peroxides such as 5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide and trimethylsilyltriphenylsilyl peroxide;

The curable polyphenylene ether-based resin composition of the present invention may be used by adding a filler or an additive in an amount that does not impair the original performance for the purpose of imparting desired performance according to its use. Can be. The filler may be fibrous or powdery, and examples thereof include carbon black, alumina, talc, mica, glass beads, and glass hollow spheres. As additives, antioxidants,
Examples include a heat stabilizer, an antistatic agent, a plasticizer, a pigment, a dye, and a colorant. For the purpose of further improving the flame retardancy, chlorine-based, bromine-based, phosphorus-based flame retardants, Sb ₂ O ₃ , NbSb
A flame retardant auxiliary such as O ₃ .1 / 4H ₂ O can be used in combination.

A cured product of a curable composite material comprising the curable polyphenylene ether-based resin composition of the present invention and a substrate,
The cured product of the curable film composed of the resin composition, the cured product of the curable laminate composed of the curable film composed of the resin composition and the metal foil are obtained by curing the composition described above. Things. The method of curing is arbitrary, and a method using heat, light, an electron beam, or the like can be employed. In the case where curing is performed by heating, the curing temperature is selected in the range of 80 to 300 ° C., more preferably 120 to 250 ° C., depending on the type of the radical initiator. The curing time is 1 minute to 10 hours, more preferably 1 minute to 5 hours.

Next, the curable composite material of the present invention and its cured product will be described. The curable composite material of the present invention,
(A) thermosetting polyphenylene ether-based resin, (b)
Silica treated with at least one silane coupling agent selected from the group consisting of silane compounds having a structure represented by the following formula (1), formula (2) or formula (3):
(D) a base material and / or (c) a hydrogenated block copolymer.

[0038]

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As the base material of the component (d), various glass cloths such as roving cloth, cloth, chopped mat, surfing mat, asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloths; polyvinyl alcohol fiber, Woven or nonwoven fabric obtained from liquid crystal fiber such as polyester fiber, acrylic fiber, wholly aromatic polyamide fiber, aromatic polyester fiber, polybenzazole fiber, or synthetic fiber such as polytetrafluoroethylene fiber; cotton cloth, linen cloth, felt, etc. Natural fiber; carbon fiber cloth; cellulosic natural cellulosic cloth such as kraft paper, cotton paper, paper-glass mixed paper, etc. are used alone or in combination of two or more.

When the component (c) is not used, the proportion of the component (d) in the curable composite material of the present invention is based on 100 parts by weight of the sum of the components (a) and (b). When used, the amount is 5 to 90 parts by weight, more preferably 20 to 70 parts by weight, based on 100 parts by weight of the sum of the components (a), (b) and (c). (D) Component is 5
If the amount is less than 10 parts by weight, the dimensional stability and strength of the curable composite material after curing are insufficient, and if the amount is more than 90 parts by weight, the dielectric properties of the cured body of the curable composite material are inferior, which is not preferable.

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 composition layer and the substrate. As the coupling agent, those usually used such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, and a zircoaluminate coupling agent can be used. Examples of the method for producing the curable composite material of the present invention include a method of uniformly dissolving / dispersing the curable polyphenylene ether-based resin composition of the present invention in a solvent, impregnating the substrate, and then drying. As the solvent used herein, in addition to the aromatic hydrocarbon solvent and the halogen solvent used in the production of the resin composition of the present invention, a ketone solvent, dimethylformamide,
Dimethyl sulfoxide and the like are used, and these are used alone or as a mixture.

The impregnation is performed by dipping (dipping), coating or the like. The impregnation can be repeated a plurality of times as necessary.At this time, it is also possible to repeat the impregnation using a plurality of solutions having different compositions and concentrations, and to use a plurality of solutions having different compositions and concentrations. It is also possible to repeat the impregnation to finally adjust the desired resin composition and resin amount.

The cured product of the curable 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, and for example, a plurality of curable composite materials are stacked, and the respective layers are adhered under heat and pressure, and simultaneously thermoset to obtain a cured body having a desired thickness. . Further, it is also possible to obtain a cured body having a new layer structure by combining the cured body once bonded and cured and the cured body.

The lamination molding and curing are usually performed using a hot press or the like.
It is done at the same time, but both may be done independently
No. That is, the uncured body obtained by lamination molding in advance
Alternatively, the semi-cured curable composite is heat treated or
It can also be cured by treating it with a method.
Lamination molding and curing are performed at a temperature of 80 to 300 ° C. and a pressure of 0.
1-500kg / cm ^Two, Time range from 1 minute to 10 hours,
More preferably, the temperature is 150 to 250 ° C. and the pressure is 1 to 10
0kg / cm^TwoCan be performed in a time range of 1 minute to 5 hours
it can.

Next, a method for producing a curable laminate in which a film of the curable polyphenylene ether-based resin composition of the present invention is a metal foil with a resin formed on the surface of a metal foil will be described. Any method may be used to form a film of the curable polyphenylene ether-based resin composition, but a preferable method is, for example, to apply a varnish obtained by dissolving / dispersing the resin composition in a solvent to a metal foil. After drying, a method of drying is used. A suitable solvent is selected according to the selection of the resin composition.

Examples of the solvent used for preparing the varnish of the curable polyphenylene ether resin composition include aromatic hydrocarbons such as benzene, toluene, and xylene; halogen solvents such as dichloromethane, chloroform, and trichloroethylene; and THF. These can be used alone or as a mixture. As a method of applying a varnish comprising a curable polyphenylene ether-based resin composition and a solvent, an aired coater, a blade coater,
Examples include a method using an apparatus such as a rod coater, a knife coater, a gravure coater, a reverse coater, and a cast coater. As a method of drying the coating film, hot air drying,
Examples include methods using devices such as roll heating drying, infrared drying, and far infrared drying. These devices may be used alone or in combination of two or more.

Any metal foil can be used as the metal foil of the present invention. For example, copper foil, aluminum foil, tin foil,
Gold leaf and the like. Copper foil and aluminum foil are preferred because they are easily available and can be etched, and copper foil is most preferred. The thickness of the metal foil is not particularly limited, but is preferably 5 to 200 μm, more preferably 5 to 100 μm from the viewpoint of ease of handling.
It is in the range of μm. The surface of the metal foil on which the film of the curable polyphenylene ether-based resin composition is formed may be roughened and / or subjected to a coupling treatment for the purpose of enhancing the adhesion to the resin.

The roughened electrolytic copper foil manufactured and sold for manufacturing a wiring board can be used as it is for manufacturing the resin-coated copper foil for a multilayer wiring board of the present invention. The metal foil is mainly used as a conductor of the multilayer wiring board of the present invention, but may be used for heat radiation. The metal foil is also selected according to the purpose. The thickness of the film of the curable polyphenylene ether-based resin composition is not particularly limited.
To 100 μm, more preferably 20 to 100 μm, and most preferably 30 to 100 μm. When the film thickness is extremely small, it becomes difficult to perform the lamination build-up method.

The curable film of the present invention has a coating substrate of P
It is obtained by changing to an ET film or the like and manufacturing the same as the above-mentioned metal foil with resin, and then peeling off the PET film. In the curable composite of the present invention, the above-described composite material, film, and resin-attached metal foil are laminated in an arbitrary layer configuration. As a method for producing the cured composite of the present invention, for example, the curable composite material of the present invention and / or the curable film of the present invention and / or the curable laminate of the present invention are laminated in a layer configuration according to the purpose. And a method in which each layer is adhered to each other under heat and pressure, and simultaneously cured by heat. Lamination molding and curing can be performed under the same conditions as in the case of the cured body of the curable composite material of the present invention.

The curable polyphenylene ether resin composition of the present invention exhibits excellent chemical resistance, dielectric properties, heat resistance, dimensional stability, and toughness after curing, and is useful in the fields of the electronics industry, space and aircraft industries. Dielectric materials, insulating materials,
It can be used for heat-resistant materials.

[0051]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments. In the following examples, the following were used as each component. <Modified polyphenylene ether resin> 30 ° C, 0.5g
r / dl viscosity number ηsp /
After dry-blending 100 parts by weight of poly (2,6-dimethyl-1,4-diphenylene ether) having a c of 0.40 and 1.5 parts by weight of maleic anhydride at room temperature, the cylinder temperature is 300 ° C. and the screw is rotated. It was extruded by a twin screw extruder under the condition of several 230 rpm. 30 ° C, 0.5 gr /
The viscosity number ηsp / c of the reaction product measured with a dl chloroform solution was 0.43. <Polymerization initiator> 2,5-dimethyl-2,5-di (t-butylperoxy) hexine-3 (Perhexin 25B manufactured by NOF Corporation) <Silica>-Spherical silica (average particle size: 0.9 μm) Using Admafine SO-C3) manufactured by Admatechs as a raw material,
Γ-methacryloxypropyltrimethoxysilane which is a silane coupling agent (KBM manufactured by Shin-Etsu Chemical Co., Ltd.)
503) (treatment amount 0.8 wt.%) (This surface-treated silica is referred to as A). Spherical silica (average particle size: 0.5 μm; Admafine SO-C2 manufactured by Admatechs Co., Ltd.) as a raw material,
Γ-methacryloxypropyltrimethoxysilane which is a silane coupling agent (KBM manufactured by Shin-Etsu Chemical Co., Ltd.)
503) (a treatment amount of 0.8 wt.%) (This surface-treated silica is referred to as B). Using spherical silica (average particle size: 0.9 μm; Admafine SO-C3 manufactured by Admatechs Co., Ltd.) as a raw material,
Γ-glycidoxypropyltrimethoxysilane which is a silane coupling agent (KBM4 manufactured by Shin-Etsu Chemical Co., Ltd.)
03) (treatment amount: 0.8 wt.%) (This surface-treated silica is referred to as C). Using spherical silica (average particle size: 0.9 μm; Admafine SO-C3 manufactured by Admatechs Co., Ltd.) as a raw material,
A material treated with 0.8% by weight of vinyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM1003) as a silane coupling agent (this surface-treated silica is referred to as D). Using spherical silica (average particle size: 0.9 μm; Admafine SO-C3 manufactured by Admatechs Co., Ltd.) as a raw material,
N-phenyl-γ-aminopropyltrimethoxysilane which is a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM573) (treatment amount 0.8 wt.%) (This surface-treated silica is referred to as E). Using spherical silica (average particle size: 0.9 μm; Admafine SO-C3 manufactured by Admatechs Co., Ltd.) as a raw material,
Γ-mercaptopropyltrimethoxysilane which is a silane coupling agent (KBM80 manufactured by Shin-Etsu Chemical Co., Ltd.)
3) (the surface-treated silica is referred to as F) (treatment is 0.8 wt.%). <Hydrogenated block copolymer> Hydrogenated styrene-butadiene-styrene block copolymer (Tuftec H1041 manufactured by Asahi Kasei Kogyo Co., Ltd.) <Flame retardant> Brominated flame retardant (Albemar Asano Co., Ltd. SAYTE)
X 8010)

[0052]

Examples 1 to 4 The above-mentioned modified polyphenylene ether resin, triallyl isocyanurate and hydrogenated block copolymer were added to toluene at a composition ratio shown in Table 1 at 80 ° C. and stirred for 1 hour. Silicas A and B and a flame retardant were added thereto at the composition ratios shown in Table 1, and dispersed at 80 ° C. for 1 hour using a wet bead mill (SC mill manufactured by Mitsui Mining Co., Ltd.). Finally, a polymerization initiator was added at the composition ratio shown in Table 1 to prepare a varnish. Then, after coating with a blade coater on the electrolytic copper foil for printed wiring boards having a thickness of 12 μm,
It was dried in an air oven at 50 ° C. for 30 minutes to obtain a resin-coated copper foil. The obtained resin-coated copper foil had a resin thickness of 60 μm, and showed no silica aggregates on the resin surface, and had excellent smoothness.

The obtained copper foil with resin was laminated and cured by a vacuum press molding machine to produce a cured product having a thickness of about 120 μm.
The curing conditions were as follows: the temperature was raised at 3 ° C./min, and the temperature was maintained at 200 ° C. for 1 hour. The pressure was 30 kg / cm ² . When the cross section of this cured product was observed with a scanning electron microscope (SEM),
No silica aggregate was found, indicating a good dispersion. Various physical properties of the cured product obtained as described above were measured by the following methods. 1. Methylene chloride resistance: 60 cured products from which copper foil has been removed
It was cut into a square mm, boiled in methylene chloride for 5 minutes, and the change in appearance was visually observed. 2. Dielectric constant, dielectric loss tangent: Measurement was performed at 1 MHz. The measuring device is an impedance analyzer 4192AL
F (manufactured by Yokogawa Hewlett-Packard Co., Ltd.) was used. 3. Solder heat resistance: 60mm of cured product from which copper foil is removed
It was cut into corners, floated in a 260 ° C. solder bath for 120 seconds, and visually observed for changes in appearance. 4. Glass transition temperature and coefficient of thermal expansion: A sample cut from the cured product from which the copper foil had been removed was measured by the TMA method. Further, an inner layer circuit was formed on a thermosetting polyphenylene ether double-sided copper-clad laminate having a thickness of 0.6 mm in which copper foil of 12 μm was stretched on both sides, and a diameter of about 10 mm was formed at a necessary portion by a carbon dioxide laser.
The copper foil with resin was laminated and cured on both sides of the substrate on which the plated through hole of 0 μm was formed so that the copper foil was on the surface. Observation of the cross section and the surface of the laminated plate with an optical microscope showed no occurrence of resin cracks. Table 4 shows the above results.

[0054]

Example 5 The same operation as in Example 1 was repeated except that the content of the hydrogenated block copolymer was changed as shown in Table 2, and each evaluation was performed. Table 5 shows the results.

[0055]

Examples 6 and 7 Table 2 shows the content of the hydrogenated block copolymer.
Each evaluation was performed by repeating the same operation as in Example 4 except that the conditions were changed as shown in FIG. Table 5 shows the results.

[0056]

Examples 8 to 9 The same operation as in Example 1 was repeated except that silicas C and D were used alone as shown in Table 3, and each evaluation was performed. Some white silica aggregates were found on the resin surface of the obtained resin-coated copper foil, and some silica aggregates were also confirmed in the cross-sectional photograph of the cured product. However, when the cross section and the surface of the laminated plate were observed, no resin crack originating from the silica aggregate was found. Table 6 shows the results
Shown in

[0057]

Comparative Examples 1 and 2 Each evaluation was repeated by repeating the same operation as in Example 1 except that silicas E and F were used alone as shown in Table 3. Aggregates of white silica are seen on the resin surface of the obtained resin-coated copper foil, and even in the cross-sectional photograph of the cured body,
An aggregate of silica was confirmed. When the cross section of the laminate was observed, resin cracks originating from silica aggregates were observed. Table 6 shows the results.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

[0062]

[Table 5]

[0063]

[Table 6]

[0064]

According to the curable polyphenylene ether-based resin composition of the present invention, it is possible to obtain a resin-coated metal foil or film having excellent silica dispersibility and excellent smoothness without silica aggregates on the surface. Can be. In addition, it has a low coefficient of thermal expansion after curing, and is excellent in chemical resistance, heat resistance, and dielectric properties. In a laminate obtained using such a resin-attached metal foil or film, a resin crack originating from an aggregate of silica does not occur.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4F071 AA12 AA12X AA22 AA22X AA42 AA51 AA75 AA78 AB26 AC12 AE02 AG12 AH19 BA02 BA03 BB02 BC02 BC12 4J002 AA02W AA05W BP01X CD00W CH07W DJ017 EU196 FB097FD 017

Claims (11)

[Claims] 1. A group consisting of (a) a thermosetting polyphenylene ether-based resin and (b) a silane compound having a structure represented by the following formula (1), (2) or (3): A curable polyphenylene ether containing silica treated with at least one selected silane coupling agent and containing 10 to 38000 parts by weight of component (b) based on 100 parts by weight of component (a) -Based resin composition. Embedded image 2. A compound selected from the group consisting of (a) a thermosetting polyphenylene ether-based resin and (b) a silane compound having a structure represented by the following formula (1), (2) or (3). (C) a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block B mainly composed of at least one conjugated diene compound
A hydrogenated block copolymer obtained by hydrogenating a block copolymer consisting of: (b) 10 to 38000 parts by weight of component (b) based on 100 parts by weight of component (a); and (c) (1) A curable polyphenylene ether-based resin composition comprising 1 to 1900 parts by weight of a component. Embedded image 3. The curable polyphenylene ether-based resin composition according to claim 1, wherein the silane coupling agent is a silane compound having a structure represented by the formula (1). 4. A curable composite material comprising the curable polyphenylene ether-based resin composition according to claim 1, 2 or 3, and a substrate. 5. A cured composite material obtained by curing the curable composite material according to claim 4. 6. A curable film comprising the curable polyphenylene ether-based resin composition according to claim 1, 2 or 3. 7. A cured film obtained by curing the curable film according to claim 6. 8. A curable laminate comprising the curable film according to claim 6 and a metal foil. 9. A cured laminate obtained by curing the curable laminate according to claim 8. 10. The curable composite material according to claim 4, and / or
Or the curable film according to claim 6 and / or claim 8.
A curable composite comprising the curable laminate according to the above. 11. A cured composite obtained by curing the curable composite according to claim 10.