JPH07242813A - Curable polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition, excellent in dielectric characteristics and chemical and heat resistances and capable of manifesting good preservation stability for a long period and providing a useful laminate by blending a curable polyphenylene ethereal resin with a mixture of a specific peroxyhexyne with a specified benzene. CONSTITUTION:This composition is obtained by blending (A) 99.9-90 pts.wt. curable polyphenylene ethereal resin with 0.1-10 pts.wt. mixture of (B) 2,5- dimethyl-2,5-di-t-butylperoxyhexyne-3 with (C) alpha, alpha'-(tert-butyloxy-m-isopropyl) benzene. The composition is used as a curable composite material comprising the curable resin composition and a substrate, its cured product or a laminate comprising the cured product and a metallic foil. The component (A) is expressed by formula I [(m) is 1-6; J is expressed by formula II; R1 to R4 each is a lower alkyl, an aryl, etc.; Q is H when (m) is 1 and a polyfunctional phenolic compound residue having 2-6 phenolic hydroxyl groups in one molecule and substituent groups inert to the polymerization at the o- and p-positions with respect to the phenolic hydroxyl groups when (m) is >=2] and poly(2,6- dimethy1-1,4-phenylene ether), etc., are preferred.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable resin composition and a cured product obtained by curing the same. Further, the present invention relates to a curable composite material composed of the resin composition and a base material, 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, and heat resistance after curing, and can be used as a dielectric material, an insulating material, and a heat resistant material in the fields of the electronic industry, the space / aircraft industry and the like. .

[0002]

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, and electrical characteristics are being demanded. For example, as a printed wiring board, a copper-clad laminate made of a thermosetting resin such as phenol resin or epoxy resin has been conventionally used. Although these have various performances in a well-balanced manner, they have the drawback of poor electrical properties, especially dielectric properties in the high frequency range. Polyphenylene ether has attracted attention in recent years as a new material for solving this problem, and its application to copper-clad laminates has been attempted.

One of the methods of utilizing polyphenylene ether is a method of blending a curable polymer or monomer. By combining it with a curable polymer or monomer, it is possible to obtain a material which improves the chemical resistance of polyphenylene ether and makes good use of the excellent dielectric properties of polyphenylene ether. Examples of curable polymers and monomers include epoxy resins (Japanese Patent Laid-Open No. 58-690).
46, etc.), 1,2-polybutadiene (JP-A-59-59)
193929), and polyfunctional maleimides (Japanese Patent Laid-Open No. Sho 5)
6-133355), polyfunctional cyanate ester (JP-A-56-141349, etc.), polyfunctional acryloyl or methacryloyl compound (JP-A-57-14).
9317), triallyl isocyanurate and / or triallyl cyanurate (JP-A-61-218).
No. 652) and isocyanate compounds.

[0004] These curable polymers and monomers are blended with polyphenylene ether to cause a crosslinking reaction to cure, but generally, for the purpose of lowering the reaction temperature at that time or accelerating the crosslinking reaction of the unsaturated group. A radical initiator is used. In general, the behavior at the time of curing (meaning curing temperature, that is, moldability) and the performance of the resin after curing are largely dependent on the performance of the radical initiator used. For example, when 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, which is a peroxide having a relatively high decomposition initiation temperature, is used, it has good substrate properties, particularly good electrical properties. However, since the decomposition initiation temperature is high, a high temperature is required during molding.

On the other hand, 2,5-dimethyl-2,5-di (t
Α-α'-bis (tert-butyloxy-m-, whose decomposition initiation temperature is lower than that of -butylperoxy) hexyne-3
When isopropyl) benzene is used, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-
It is possible to mold the substrate at a lower temperature than the case of using 3, but the electric characteristics are better than those of using 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3. Will be inferior.

That is, in a resin composition for a printed circuit board, which requires a wide variety of performances, it has been difficult to prepare a printed circuit board which can sufficiently satisfy the requirements with one kind of radical initiator.

[0007]

The present invention has been made in view of the above circumstances, and uses two different types of peroxides to formability at low temperatures, dielectric properties, heat resistance, and resistance to heat. It is an object of the present invention to provide a curable resin composition having both chemical properties.

[0008]

That is, the present invention provides 99.9 to 90 parts by weight of a curable polyphenylene ether resin composition and 2,5-dimethyl-2,5-di-t-butylperoxyhexyne-. A mixture of 3 and α, α′-bis (tert-butyloxy-m-isopropyl) benzene.
1 to 10 parts by weight of a resin composition, a composite material and a laminate.

The polyphenylene ether resin used in the present invention includes a modified product and will be described in detail below. The polyphenylene ether used in the present invention is represented by the following general formula (1).

[0010]

[Chemical 1]

Examples of the lower alkyl group represented by R _{1 to} R ₄ in the general formula (A) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group. A phenyl group etc. are mentioned as an example of an aryl group. Examples of the haloalkyl group include a bromomethyl group and a chloromethyl group. Examples of halogen atoms include bromine and chlorine.

As a typical example of Q in the general formula (1),
A compound group represented by the following four kinds of general formula (2) can be given.

[0013]

[Chemical 2]

As specific examples, the following general formulas (3) and (4)
Etc.

[0015]

[Chemical 3]

[0016]

[Chemical 4]

The polyphenylene ether chain represented by J in the general formula (1) contains a unit represented by the following general formula (5) in addition to the unit represented by the general formula (A). May be.

[0018]

[Chemical 5]

A preferred example of the polyphenylene ether resin of the general formula (1) used in the present invention is poly (2,6) obtained by homopolymerization of 2,6-dimethylphenol.
-Dimethyl-1,4-phenylene ether), styrene graft polymer of poly (2,6-dimethyl-1,4-phenylene ether), copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,
Copolymer of 6-dimethylphenol and 2-methyl-6-phenylphenol, 2,6-dimethylphenol and polyfunctional phenol compound

[0020]

[Chemical 6]

A polyfunctional polyphenylene ether resin obtained by polymerization in the presence of, for example, JP-A-63-3012.
For example, a copolymer containing the units of the general formulas (A) and (B) as disclosed in JP-A No. 22 and JP-A No. 1-297428 can be used. The molecular weight of the above-mentioned polyphenylene ether resin is 30 ° C., 0.5 g / dl
The viscosity number ηsp / c measured with the chloroform solution of 0.1 is 0.
Those in the range of 1 to 1.0 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, for example, a prepreg for a multilayer wiring board.

The polyphenylene ether used in the present invention also includes modified products. Specifically, a polyphenylene ether resin containing an unsaturated group (JP-A-64)
-69628, JP-A-1-113425, JP-A-1
-113426), and a reaction product of a polyphenylene ether resin with an unsaturated carboxylic acid and / or an acid anhydride, and the like.

Next, the polyphenylene resin composition of the present invention will be described. The polyphenylene ether-based resin composition is a resin composition containing the above-mentioned polyphenylene ether (including modified products). Resins other than polyphenylene ether can be used as a material for a printed circuit board, which is an object of the present invention. Any material may be used as long as it does not damage it.

Specifically, phenol resin, epoxy resin, diallyl phthalate, divinylbenzene, polyfunctional acryloyl compound, polyfunctional methacryloyl compound,
Polyfunctional maleimide, polyfunctional methacryloyl compound,
Polyfunctional maleimide, polyfunctional cyanate ester, polyfunctional isocyanate, unsaturated polyester, triallyl isocyanurate, triallyl cyanurate, polybutadiene, styrene-butadiene / styrene-butadiene-styrene, etc. A thermosetting resin or the like. These are generally compounded for the purpose of improving the physical properties of a substrate produced by laminating and molding a prepreg.

Although not particularly limited, examples of preferable resin composition include polyphenylene ether and triallyl isocyanurate and / or triallyl cyanurate, polyphenylene ether and epoxy resin, polyphenylene ether and styrene butadiene block copolymer and triallyl isocyanurate. And / or triallyl cyanurate, polyphenylene ether containing unsaturated group and triallyl isocyanurate and / or triallyl cyanurate, polyphenylene ether containing unsaturated group and triallyl isocyanurate and / or triallyl cyanurate and epoxy resin Reaction product of polyphenylene ether resin with unsaturated carboxylic acid and / or acid anhydride and triallyl isocyanate And / or triallyl cyanurate, a reaction product of a polyphenylene ether resin with an unsaturated carboxylic acid and / or acid anhydride, and an epoxy resin, a reaction product of a polyphenylene ether resin with an unsaturated carboxylic acid and / or acid anhydride And triallyl isocyanurate and / or triallyl cyanurate and epoxy resin. The blending amount is determined according to the purpose.

Various thermoplastic resins may be added to the polyphenylene ether resin composition of the present invention as long as the characteristics are not impaired. Specifically, a hydrogenated block copolymer obtained by hydrogenating a polymer block containing one vinyl polymer as a main component and a block copolymer containing at least one polymer containing a conjugated diene compound as a main component. Examples thereof include polymers.

Next, the radical initiator used in the resin composition of the present invention is two different peroxides, specifically 2,5-dimethyl-2,5-di-t-butylperoxyhexyne-. 3 and α, α′-bis (tert-butyloxy-m-isopropyl) benzene. By using both of them in combination, it is possible to provide a resin composition having both advantages.

That is, 2,5-dimethyl-2,5-di-
By using t-butylperoxyhexyne-3 and α, α'-bis (tert-butyloxy-m-isopropyl) benzene together, the moldability at low temperature is good, and the heat resistance, chemical resistance, and dielectric properties are good. It becomes possible to obtain an excellent resin composition. In the present invention, the amount of the radical initiator used in the resin composition is 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, particularly preferably 1 to 6 parts by weight, based on 100 parts by weight of the resin composition. It is a department.

The amount ratio of each initiator in both initiators is not particularly limited and can be appropriately selected. If the amount of both initiators exceeds 10 parts by weight, the dielectric properties deteriorate, which is not preferable.
Further, if it is less than 0.1 parts by weight, the improvement of chemical resistance is insufficient, which is not preferable. In addition to the radical initiator described above,
A curing accelerator may be used for the purpose of reacting the epoxy resin. Examples of the curing accelerator include amine compounds, imidazole compounds, nitrogen-containing heterocyclic compounds such as diazabicycloundecene, organic phosphine compounds, organic phosphine / organic boron complexes, quaternary ammonium compounds, and quaternary compounds. Known compounds such as phosphonium compounds can be used. For details of the technology related to curing accelerators, see "Recent Advances in Epoxy Resins," edited by Hiroshi Kakiuchi.
(Shokoido, 1990), Chapter 4 and references cited therein.

In addition to the above, polyamine is used as a curing agent suitable for polyfunctional maleimide, and as a catalyst suitable for polyfunctional cyanate ester, mineral acid, Lewis acid, salts such as sodium carbonate or lithium chloride, tributylphosphine, etc. Examples of suitable phosphoric acid esters and catalysts and curing agents for polyfunctional isocyanates are, for example, edited by Keiji Iwata,
"Polyurethane resin handbook" (Nikkan Kogyo Shimbun,
1987) pp. 118-123, amines, organic metals, polyhydric alcohols and the like, respectively. The above catalyst, initiator, curing agent, etc. are appropriately selected and used according to the type of the resin composition.

As the substrate used in the present invention, various glass cloths 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; natural fiber cloth such as cotton cloth, linen cloth and felt; carbon fiber cloth; kraft paper, cotton paper, Natural cellulosic cloth such as paper-glass mixed fiber paper may be used alone or in combination of two or more kinds.

Examples of the metal foil used in the present invention include copper foil and aluminum foil. The thickness is not particularly limited, but is 5 to 200 μm, more preferably 5
˜100 μm. In the present invention, the resin composition,
For the purpose of imparting desired performance depending on the application, fillers and additives can be blended and used in an amount within a range that does not impair the original properties. The filler may be fibrous or powdery, and examples thereof include silica, alumina, talc, mica, glass beads, and glass hollow spheres. Examples of the additives include antioxidants, heat stabilizers, antistatic agents, plasticizers, pigments, dyes, colorants and the like. The chlorine in order to further improve the flame retardancy, bromine, and flame retardant _{phosphorus-based, Sb 2 O 3, Sb 2} O 5, NbSbO 3 · 1 /
A flame retardant aid such as 4H ₂ O can also be used in combination. Furthermore, it is also possible to mix one or more kinds of other thermoplastic resins or thermosetting resins.

As a method of mixing the above components, a solution mixing method of uniformly dissolving or dispersing the above components in a solvent, a melt blending method of heating with an extruder or the like can be used. As the solvent used for the solution mixing, a halogen-based solvent such as dichloromethane, chloroform and trichloroethylene; an aromatic solvent such as benzene, toluene and xylene; a ketone solvent such as acetone, methyl ethyl ketone and methyl isobutyl ketone; tetrahydrofuran alone or Used in combination of two or more.

The resin composition of the present invention may be molded and cured in advance depending on its use. The molding method is not particularly limited. Usually, a casting method in which the resin composition is dissolved in the above-mentioned solvent and molded into a desired shape, or a heating and 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.

As the method for producing the curable composite material of the present invention, for example, the components of the present invention and, if necessary, other components are added in the above-mentioned halogen-based, aromatic-based, ketone-based solvent or a mixed solvent thereof. A method in which the base material is uniformly dissolved or dispersed, the base material is impregnated, and then dried. Impregnation is performed 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.

In the curable 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. A combination of brominated diphenyl ether and antimony oxide is preferably used as the flame retardant for the composite material including the base material.

The cured polyphenylene ether resin composition of the present invention is obtained by curing the curable polyphenylene ether resin cured product 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 is 80 to 300 ° C, more preferably 120 ° C to
It is selected in the range of 250 ° C. The time is selected in the range of 1 minute to 10 hours, more preferably 1 minute to 5 hours.
Further, the pressure is selected in the range of 1 to 100 kg / cm ² .

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. The cured composite material of the present invention can be used in the form of a film, or a form in which at least one kind of metal foil is laminated on at least one side.

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 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.

When curing is carried out by heating, it may be carried out under the same curing conditions as for the curable resin composition. The laminate of the present invention is composed of the cured composite material of the present invention and a metal foil. As a method for producing the laminate of the present invention, for example, a method in which the curable composite material of the present invention and a metal foil are laminated in a layered structure according to the purpose, and each layer is adhered under heat and pressure and at the same time thermoset Can be mentioned.

For example, in the laminated body, the curable composite material and the metal foil are laminated in an arbitrary layer structure. The metal foil can be used as both the surface layer and the intermediate layer. In the laminated plate, a curable composite material is laminated on one side or both sides of a metal plate as a base. 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. Examples of the adhesive include epoxy-based, acrylic-based, phenol-based, and cyanoacrylate-based adhesives, but are not particularly limited thereto. The above-mentioned lamination molding and curing can be performed under the same conditions as for the cured composite material of the present invention.

[0043]

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.

[0044]

Reference Example 1 Poly (2, having a viscosity number ηsp / c of 0.54 measured at 30 ° C. in a chloroform solution of 0.5 g / dl.
100 parts by weight of 6-dimethyl-1,4-phenylene ether, 1.5 parts by weight of maleic anhydride, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (Perhexa 25B manufactured by NOF Corporation) ) After 1.0 parts by weight dry blending at room temperature, the cylinder temperature is 30.
Extrusion was carried out by a twin-screw extruder under the conditions of 0 ° C. and screw rotation speed of 230 rpm. This reaction product is designated as A.

[0045]

Reference Example 2 Viscosity number η measured by the same method as in Reference Example 1
Poly (2,6-dimethyl-1,4) with sp / c of 0.54
-Phenylene ether) and 1.5 parts by weight of maleic anhydride were dry-blended at room temperature, and then extruded by a twin-screw extruder under the conditions of a cylinder temperature of 300 ° C. and a screw rotation speed of 230 rpm. This reaction product is designated as B.

[0046]

Reference Example 3 Polyphenylene ether resin containing unsaturated group Average substitution ratio 14%, η measured by the same method as Reference Example 1
An allyl group-substituted polyphenylene ether with sp / c = 0.62 was prepared according to the known method disclosed in JP-A-64-69629 by poly (2,6-dimethyl-1,4-phenylene) with ηsp / C = 0.56. Ether). This allyl-substituted polyphenylene ether is designated as C.

[0047]

Examples 1 to 4 Poly (2,6-dimethyl-1,4-phenylene ether) having ηsp / c = 0.56 measured in the same manner as in A, B and C and Reference Example 1 (hereinafter referred to as D). Was mixed with various compositions in the compositions shown in Table 1 and dissolved or dispersed in trichlorethylene. To this solution, glass cloth (made of E glass, basis weight 48 g / m ² or 10
5 g / m ² ) was dipped to impregnate and dried in an air oven.

A plurality of the above-mentioned curable composite materials are superposed so that the thickness after molding is about 0.8 mm, and a copper foil having a thickness of 35 μm is placed on both surfaces thereof, and is molded and cured by a press molding machine to obtain a laminate. Got The curing was performed at 170 ° C. for 30 minutes for molding. 20 kg / cm ^{2 for} all pressures
And The physical properties of the laminate thus obtained 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.

All the curable composite materials had good resin flowability even after being left at 23 ° C. for 3 months, and no change with time in physical properties of the curable composite material was observed. The curing is 170 ° C, which is 180 ° C or less that can be steam-pressed,
It was possible in 30 minutes. Also, the obtained laminate does not warp or swell even if it is boiled in trichlorethylene for 5 minutes,
The electrical characteristics were also good.

[0050]

[Comparative Examples 1 and 2] Various compositions shown in the table and the compositions shown in Table 1 were blended in the same manner as in Example 1, and a substrate was prepared in the same manner as in Example 1. The obtained substrate had poor chemical resistance and heat resistance and was insufficiently cured (Comparative Example 1) or poor electrical properties (Comparative Example 2).

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

The laminate, laminate, and metal-clad laminate obtained by using the curable resin composition of the present invention are materials that can be molded at low temperature and have good chemical resistance and excellent dielectric properties. Is. In addition, it exhibits well-balanced properties in various physical properties such as heat resistance, adhesiveness with metals, and dimensional stability.

Therefore, the material of the present invention can be used as a dielectric material, an insulating material, or a heat-resistant material in the fields of electrical machinery industry, electronic industry, space / aircraft industry and the like. Especially on one side,
It is preferably used as a double-sided, multi-layer printed circuit board, semi-rigid substrate, metal base substrate, and prepreg for multi-layer printed circuit board. Further, the material of the present invention can be favorably used 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 and moisture resistant insulation property.

Claims (5)

[Claims] 1. A curable polyphenylene ether resin composition 99.9 to 90 parts by weight and 2,5-dimethyl-
2,5-di-t-butylperoxyhexyne-3 and α,
A curable resin composition comprising 0.1 to 10 parts by weight of a mixture of α'-bis (tert-butyloxy-m-isopropyl) benzene. 2. A cured resin composition obtained by curing the curable resin composition according to claim 1. 3. A curable polyphenylene ether resin composition 99.9 to 90 parts by weight and 2,5-dimethyl-
2,5-di-t-butylperoxyhexyne-3 and α,
A curable composite material comprising a base material and a curable resin composition comprising 0.1 to 10 parts by weight of a mixture of α'-bis (tert-butyloxy-m-isopropyl) benzene. 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.