JPH06220226A - Production of prepreg by using polyphenylene ether - Google Patents

Abstract

PURPOSE:To obtain a prepreg having a good surface state without causing solution viscosity rise by dissolving a polyphenylene ether resin composition in xylene above a specified temperature and impregnating a base with the obtained solution. CONSTITUTION:A process for producing a prepreg by dissolving a polyphenylene ether resin composition in xylene and impregnating a base with the obtained solution, wherein the resin composition is dissolved in xylene above a temperature (T deg.C) represented by the formula (wherein T is the dissolution temperature ( deg.C), and G is the ratio of the weight of the polyphenylene ether in the resin composition to the total weight of the xylene and the polyphenylene ether in the resin composition). The prepreg obtained by this process can be used as a dielectric material, a heat-resistant material or the like in the fields of electrical industry, electronic industry, aerospace and aircraft industry, etc. It can be desirably used as especially a prepreg for single-sided, double-sided and multilayer printed circuit boards, semi-rigid circuit boards, metal-base circuit boards and multilayer printed circuit boards.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a prepreg manufacturing method.

[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.

The laminated plate is generally manufactured by laminating a prepreg obtained by impregnating a base material such as paper or glass fiber with a resin solution (varnish) and drying the prepreg. Therefore, the prepreg manufacturing method occupies a very important position. When polyphenylene ether is used as the resin composition for laminates, the solvent used for producing the prepreg is preferably a solvent that dissolves polyphenylene ether. Solvents for dissolving polyphenylene ether include dichloromethane, chloroform,
Examples thereof include halogen-based solvents such as trichlorethylene, aromatic solvents such as benzene, toluene, and xylene, and THF and the like. In the practice, these solvents may be used alone or in combination of two or more.

However, under the present circumstances, halogen-based solvents have a great influence on the human body and are becoming difficult to use. Therefore, it is desired to use an aromatic solvent as a solvent for prepreg production, but when an aromatic solvent is used as a solvent for prepreg impregnation, the viscosity of the solution increases (waxing), which hinders the production of prepreg. The current situation is to come to.

[0005]

The present invention has been made in view of the above circumstances, and provides a method for producing a prepreg of a polyphenylene ether resin composition by using xylene as a solvent without causing wax formation. Is what you are trying to do.

[0006]

[In the formula, T is a melting temperature (° C.), and G is represented by G = (weight of polyphenylene ether in resin composition) / (weight of xylene + weight of polyphenylene ether in resin composition). It is a ratio. ]

 The present invention will be described in detail below.

The polyphenylene ether resin used in the present invention includes a modified product. The polyphenylene ether used in the present invention has the following general formula (1).
It is represented by.

[0008]

[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 group of residues of the compound represented by the four general formulas of Chemical Formula 2 below can be mentioned.

[0011]

[Chemical 2]

Specific examples include residues of the compounds represented by the following chemical formulas 3 and 4.

[0013]

[Chemical 3]

[0014]

[Chemical 4]

In the polyphenylene ether chain represented by J in the general formula (1), in addition to the unit represented by the general formula (A), a unit represented by the general formula of the following chemical formula 5 is included. May be.

[0016]

[Chemical 5]

Preferred examples of the polyphenylene ether resin of the general formula (1) used in the present invention include 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, polyfunctional polyphenylene ether obtained by polymerization in the presence of 2,6-dimethylphenol and a polyfunctional phenol compound represented by the following general formula Examples of the resin include copolymers containing units of the general formulas (A) and (B) as disclosed in JP-A-63-301222 and JP-A-1-297428.

[0018]

[Chemical 6]

Regarding the molecular weight of the polyphenylene ether resin described above, the viscosity number ηsp / c measured with a chloroform solution of 30 g at 0.5 g / dl is 0.1 to 1.0.
Those in the range can be used satisfactorily. 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, JP-A-64-6962
No. 8, JP-A No. 1-113425, and JP-A No. 1-1134.
Examples of the polyphenylene ether resin containing an unsaturated group disclosed in JP-A No. 26, and reaction products 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 cyanic acid. Ester, polyfunctional isocyanate, unsaturated polyester, triallyl isocyanurate, triallyl cyanurate, polybutadiene, crosslinkable polymers such as styrene-butadiene / styrene-butadiene-styrene, various thermoplastic resins, various thermosetting resins Etc. 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 preferred resin compositions include polyphenylene ether and triallyl isocyanurate and / or triallyl cyanurate; polyphenylene ether and epoxy resin; polyphenylene ether, 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, triallyl isocyanurate and / or triallyl cyanurate and epoxy resin Reaction products of polyphenylene ether resins with unsaturated carboxylic acids and / or acid anhydrides and triallyl isocyanurate And / or triallyl cyanurate; reaction product of polyphenylene ether resin with unsaturated carboxylic acid and / or acid anhydride and epoxy resin; reaction product of polyphenylene ether resin with unsaturated carboxylic acid and / or acid anhydride , Triallyl isocyanurate and / or triallyl cyanurate and epoxy resin. The blending amount is determined according to the purpose.

As the substrate used in the present invention, 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; 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.

Further, a radical initiator may be contained for the purpose of lowering the reaction temperature or accelerating the crosslinking reaction of the unsaturated group. Typical 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-butylperoxide, t-butylcumylperoxide,
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- There are, but not limited to, peroxides such as butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, and trimethylsilyltriphenylsilylperoxide. Although not a peroxide, 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.

In addition to the above-mentioned radical initiator, 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 ammonium compounds.
Known compounds such as secondary phosphonium compounds can be used. For details of the technology related to the curing accelerator, see, for example, “Recent Advances in Epoxy Resins” by Hiroshi Kakiuchi, Shokoido (19
90) See Chapter 4 and references cited therein.

In addition to the above, polyamine is used as a suitable curing agent for polyfunctional maleimod, 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 catalysts and curing agents for polyfunctional isocyanates are the phosphoric acid esters, etc., of Polyurethane Resin Handbook, edited by Keiji Iwata, Nikkan Kogyo Shimbun (198).
7) P. Amines, organometallics, polyhydric alcohols, etc., as taught in 118-123, respectively.

The above catalyst, initiator, curing agent, etc. are appropriately selected and used according to the type of resin composition. In the present invention, the resin composition may be used by blending an amount of a filler or an additive in a range that does not impair the original properties for the purpose of imparting desired performance depending on the application. The filler may be fibrous or powdered, silica, alumina,
Examples thereof include 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. For the purpose of further improving flame retardancy, chlorine-based,
Bromine- and phosphorus-based flame retardants, Sb ₂ O ₃ , Sb ₂ O ₅ ,
A flame retardant aid such as NbSbO ₃ .1 / 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.

The above polyphenylene ether resin composition is prepared and dissolved in a solvent. In the present invention, xylene is used as the solvent. Next, the temperature at which the resin composition of the present invention is dissolved in xylene will be described. It is an essential condition that the melting temperature is equal to or higher than the temperature (T ° C.) shown below. T = 136.8 G + 59.6 (I) [In the formula, T is the melting temperature (° C.), and G is G = (weight of polyphenylene ether in the resin composition) / (weight of xylene + It is the ratio represented by the weight of the polyphenylene ether in the resin composition). ] In the present invention, polyphenylene ether (including modified products)
Is preferably dissolved at a temperature equal to or higher than the temperature represented by the above formula at least until the dissolution is completed. Further, it is desirable that the melting temperature is within a range in which denaturation and decomposition of the resin composition and boiling of the solution do not occur. Insufficient dissolution may accelerate the wax formation of the solution. Further, in the present invention, the melting temperature when the polyphenylene ether resin composition is dissolved is determined only by the weight fraction of polyphenylene ether and xylene.

When the substrate is impregnated, the impregnation temperature can be adjusted by the concentration of the solution, but is preferably 40.
C. or higher, more preferably 45.degree. C. or higher, even more preferably 50.degree. C. or higher. Temperatures below 40 ° C. may accelerate the waxing of the solution. 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.

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

[0030]

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.

[0031]

[Synthesis Example 1] Poly (2,3) 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.

[0032]

[Synthesis example 2] Viscosity number η measured by the same method as in synthesis example 1
Poly (2,6-dimethyl-1,4) with sp / c of 0.60
-Phenylene ether) (100 parts by weight) and maleic anhydride (1.5 parts by weight) 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.

[0033]

[Synthesis Example 3] Polyphenylene ether resin containing an unsaturated group Average substitution ratio 14%, η measured by the same method as in Synthesis Example 1
An allyl group-substituted polyphenylene ether with sp / c = 0.62 was prepared according to a known method disclosed in Japanese Patent Laid-Open No. 64-69629, and poly (2,6-) with ηsp / C = 0.56.
Dimethyl-1,4-phenylene ether). This allyl-substituted polyphenylene ether is designated as C.

[0034]

Examples 1 to 5 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 Synthesis Example 1 (hereinafter referred to as D). Was mixed with various compositions in the composition shown in Table 1 and dissolved in xylene at the temperature shown in Table 2 for 1 hour. The dissolution was carried out promptly, and all the resins were uniformly dissolved in xylene.

These solutions were cooled to the temperatures shown in Table 2, and one hour after reaching the predetermined temperature, glass cloth (made of E glass, basis weight 48 g / m ² or 105 g /
m ² ) was dipped for impregnation and then dried in an air oven to prepare a prepreg. Any of the solutions could be impregnated without causing wax formation, and the surface condition of the prepreg was good.

[0036]

Comparative Examples 1 to 3 A and D having the same composition as in Examples 2 and 3 were dissolved in xylene. The melting temperature was as shown in Table 2 for 1 hour. These solutions were cooled to the temperatures shown in Table 2 and the same operations as in Examples 1 to 5 were performed to prepare prepregs. The solution waxed when cooled. The surface of the obtained prepreg was cracked.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

The prepreg manufacturing method of the present invention is a process that does not use a halogen-based solvent, and is a process that has less influence on the human body. Further, this is a process in which wax formation is suppressed, and the obtained prepreg has a good surface condition. Therefore, the prepreg obtained by the manufacturing method 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. Particularly, it is suitably used as a single-sided, double-sided, multi-layer printed circuit board, semi-rigid substrate, metal base substrate, and prepreg for multi-layer printed circuit board.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area B29K 105: 06

Claims (1)

[Claims] 1. A method for producing a prepreg in which a polyphenylene ether-based resin composition is dissolved in xylene to impregnate a base material, wherein the resin composition is dissolved at a temperature (T ° C.) or higher represented by the following formula (I). A method for producing a prepreg using a polyphenylene ether, which comprises: T = 136.8 G + 59.6 (I) [In the formula, T is the melting temperature (° C.), and G is G = (weight of polyphenylene ether in the resin composition) / (weight of xylene + It is the ratio represented by the weight of the polyphenylene ether in the resin composition). ]