JP2570138B2 - Laminated board using flame-retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate using a flame-retardant resin composition, and more particularly to a laminate suitable for a multilayer printed circuit board having excellent flame retardancy, heat resistance and electrical properties.

[0002]

2. Description of the Related Art Conventionally, as a laminated material for a multilayer printed circuit board, a laminated plate of a phenol resin, an epoxy resin, a polyimide resin or the like using a brominated modified resin or an additive type flame retardant for imparting flame retardancy is mainly used. Used in In particular, high density is desired for large computers, and polyimide resins having excellent heat resistance and dimensional stability are used. However, in recent years, printed circuit boards having excellent electric characteristics have been demanded in order to improve the signal transmission speed with the high-speed operation processing of large computers. In particular, a printed circuit board having a low dielectric constant is required to reduce the signal transmission delay time and the circuit thickness. As such a low dielectric constant laminate material, an ethylene tetrafluoride resin, a polybutadiene resin laminate, and the like have been developed. As regards this type of laminate, for example, see Procedure D.N.P.C.O.N., (1981), pp. 160-169 (Pr.
oc. NEPCON (1981) pp. 160-169) and JP-A-55-127426.

[0003]

However, the PTFE laminate has a problem that the resin is thermoplastic and the glass transition temperature is low, so that the coefficient of thermal expansion at a high temperature is large and the dimensional stability is not sufficient. When it is applied to a multilayer printed circuit board, the wiring density is almost the same as that of epoxy resin, and there is not much merit as a low dielectric constant material. In addition, since PTFE does not have a suitable solvent, an adhesive method is generally employed by hot-melt compression, but has the disadvantage that the melting temperature is extremely high. In addition, polybutadiene resin has a drawback that it is flammable due to its molecular structure. In order to impart flame retardancy, addition type flame retardants such as decabromodiphenyl ether and triphenyl phosphate, and tribromophenyl methacrylate and tribromophenyl acrylate It is necessary to add a reactive flame retardant such as the above, but there is a problem in that the addition thereof impairs the original electrical properties, heat resistance and dimensional stability of the polybutadiene resin.

An object of the present invention is to provide a low dielectric constant material having a flame-retardant property, capable of high-density wiring comparable to a polyimide laminated material, as a material replacing conventional polyimide-based multilayer printed wiring boards used in large-scale computers. It is intended to provide a laminate using a laminate material.

[0005]

Means for Solving the Problems The first invention relates to a laminated board using a flame-retardant resin composition, and its characteristic is represented by the following general formula (I):

[0006]

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Wherein A is hydrogen, an alkyl group and a halogen group, R is alkenyl or alkenoyl having 2 to 4 carbon atoms, m is a number from 1 to 4, and n is a number from 1 to 100. There is provided a laminate using a thermosetting resin composition containing a prepolymer composed of a poly (P-hydroxystyrene) derivative represented as an essential component.

[0008] The flame retardant resin composition, the following general formula (I)

[0009]

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Wherein A is hydrogen, an alkyl group and a halogen group, R is alkenyl or alkenoyl having 2 to 4 carbon atoms, m is a number of 1 to 4, and n is a number of 1 to 100. A prepolymer comprising a poly (P-hydroxystyrene) derivative represented by the following general formula (II):

[0011]

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[0012] (wherein, B is copolymer of glycidyl ether type epoxy, n is a number of 4 to 100) also Rukoto a thermosetting resin composition obtained by blending an epoxy-modified polybutadiene represented by it can.

The prepolymer which is an essential component of the thermosetting resin composition of the present invention is represented by the general formula (I) as described above. As specific examples, the compounds corresponding to the general formula I include vinyl ether, isobutenyl ether, allyl ether of poly (P-hydroxystyrene), acrylate, methacrylate, epoxy methacrylate and There are bromides. One or more of these may be used as desired.

In the epoxy-modified polybutadiene represented by the general formula (II), which is one of the thermosetting resins of the present invention, specific examples of the glycidyl ether-based epoxy resin used for the modification include diglycidyl. Ether bisphenol A, diglycidyl ether 2,2'-dibromobisphenol A, diglycidyl ether 2,2 ',
4,4'-tetrabromobisphenol A, diglycidyl ether 2,2'-dimethylbisphenol A, diglycidyl ether 2,2 ', 4-trimethylbisphenol A, phenol novolak epoxy resin, and orthocresol novolak epoxy resin . One or more of these may be used as desired. Poly (P-hydroxystyrene) represented by the above general formula (I)
By adding epoxy-modified polybutadiene represented by the general formula (II) to the derivative, flexibility, adhesion to copper foil,
The mechanical properties and the like are improved. Further, by further adding an epoxy curing agent to the resin composition, the above-mentioned various properties can be further improved and the dielectric constant can be reduced. The blending amount of the epoxy-modified polybutadiene is not particularly limited, but as the blending amount increases, the relative permittivity of the thermosetting resin increases, and the flame retardancy, heat resistance, dimensional stability, etc. decrease.

Next, a general method for manufacturing a laminate according to the present invention will be described.

First, a varnish is prepared by dissolving a poly (P-hydroxystyrene) derivative and an epoxy-modified polybutadiene in an organic solvent. As an organic solvent, for example,
Toluene, xylene, acetone, methyl ethyl ketone,
Examples thereof include N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, trichloroethylene, trichloroethane, methylene chloride, dioxane, and ethyl acetate. Any solvent that can uniformly dissolve the resin composition can be used without limitation. A varnish for impregnation is obtained by adding a radical polymerization initiator and an epoxy curing agent to the prepared varnish.

Typical examples of the radical polymerization agent include benzoyl peroxide, dicumyl peroxide,
Methyl ethyl ketone peroxide, t-butyl peroxylaurate, di-t-butyl peroxyphthalate,
Dibenzyl oxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, t-butylhydroperoxide, di-
t-butylperoxy 2,5-dimethyl-2,5-di (t-butylperoxy) hexine (3), diisopropylbenzene hydroperoxide, p-methane hydroperoxide, pinane hydroxide, 2,5-dimethyl Hexane-2,5-dihydroperoxide, cumene hydroperoxide and the like. These are preferably added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the resin composition.

Typical examples of epoxy curing agents include 4,4
4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, m-
Phenylenediamine, p-phenylenediamine, 4,
4'-diaminodiphenylmethane, 2,2'-bis (4
-Aminophenyl) propane, benzine, 4,4'-diaminophenyloxide, 4,4'-diaminophenylsulfone, bis (4-aminophenyl) methylphosphine oxide, bis (4-aminophenyl) phenylphosphine oxide, bis ( 4-aminophenyl) methylamine, 1,5-diaminonaphthalene, m-xylylenediamine, 1,1'-bis (p-aminophenyl) furatan, p-xylylenediamine, hexamethylenediamine, 6,6'- Diamino-2,2'-dipyridyl, 4,
4'-diaminobenzophenone, 4,4'-diaminoazobenzene, bis (4-aminophenyl) phenylmethane, 1,1'-bis (4-aminophenyl) cyclohexane, 1,1'-bis (4-amino-3 -Methylphenyl) cyclohexane, 2,5-bis (m-aminophenyl) -1,3,4-oxadiazole, 2,5-bis (p-aminophenyl) -1,3,4-oxadiazole, 2,5-bis (m-aminophenyl) thiazolo (4,5-d) thiazole, 5,5′-di (m-aminophenyl)-(2,2 ′) bis (1,3,4-oxadiazolyl) 4,4'-diaminodiphenyl ether,
4,4'-bis (b-aminophenyl) -2,2'-dithiazole, m-bis (4-p-aminophenyl-2-
Thiazolyl) benzene, 4,4'-diaminobenzanilide, 4,4'-diaminophenylbenzoate, N,
N'-bis (4-aminobenzyl) -p-phenylenediamine, 4,4'-methylenebis (2-dichloroaniline), benzoquanamine, methylguanamine, tetramethylbutanediamine, phthalic anhydride, trimellitic anhydride, pyromethylene anhydride Melitic acid, bonzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate), maleic anhydride, 2-methylimidazole,
There are 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole and the like, and at least one kind is used. The compounding amount is suitably in the range of 0.1 to 30 parts by weight, preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the epoxy-modified polybutadiene. Next, the obtained varnish for impregnation is applied to a sheet-like substrate by impregnation and dried at room temperature to 170 ° C. to obtain a prepreg having no tackiness. The setting of the drying temperature at this time is determined by the solvent and the initiator used. The required number of prepregs obtained at the end are piled up in a necessary number, and 100 to 250 ° C and 1 to 100 kgf / cm
^A heat curing reaction is performed under the pressure of ² to obtain a laminate.

As the sheet-like substrate, almost all of those generally used for laminated materials can be used. Examples of the inorganic fiber include E glass, C glass, A glass, S glass, D glass, and YM having SiO ₂ , Al ₂ O _{3, and the} like as components.
There are various glass fibers such as 31-A glass and Q glass using quartz. Examples of the organic fiber include an aramid fiber containing a polymer compound having an aromatic polyamideimide skeleton.

REFERENCE EXAMPLES Reference Examples 1 to 4 250 g of brominated poly (P-hydroxystyrene) was dissolved in 500 g of chloroform.
g of an aqueous solution (500 g) is added thereto with stirring.
The reaction is carried out for a time to obtain a sodium salt. Next, 200 g of a chloroform solution of 120 g of methacrylic acid chloride is gradually added, and the mixture is reacted at 25 ° C. for 2 hours. Thereafter, the chloroform solution and the aqueous solution are separated, and the chloroform solution is concentrated to obtain a reaction product. Further, this reaction product was dissolved in acetone, and the solution was added dropwise to methanol for purification.

Acrylic acid chloride, allyl chloride, and epoxy methacrylic acid chloride were reacted in the same manner as described above to obtain the reaction products of Reference Examples 2 to 4.

Table 1 shows each characteristic.

[0023]

[Table 1]

Reference Example 5 250 g of poly (P-hydroxystyrene) was dissolved in 500 g of chloroform, 500 g of an aqueous solution of 120 g of sodium hydroxide was added with stirring, and reacted at 250 ° C. for 1 hour to obtain a sodium salt. Next, 200 g of a chloroform solution of 120 g of methacrylic acid chloride is gradually added, and the mixture is reacted at 25 ° C. for 2 hours. Thereafter, the chloroform solution and the aqueous solution are separated, and the chloroform solution is concentrated to obtain a reaction product. Further, this reaction product was dissolved in acetone, and the solution was added dropwise to methanol for purification.

[0025]

【Example】

Example 1 The brominated poly (P-hydroxystyrene) methacrylate obtained in Reference Example 1 is heated and dissolved in methyl ethyl ketone to obtain a varnish having a solid content of 40 to 50% by weight.
Further, 3 parts by weight of dicumyl peroxide as a radical weight initiator was added to 100 parts by weight of the resin, and then the varnish was impregnated and coated on a glass cloth (0.1 mm thick). After drying for 10 to 20 minutes, a tack-free prepreg was obtained. Next, the prepreg was added to 10
The laminate was heated at a stacking pressure of 30 kgf / cm ^{2 at} a temperature of 130 ° C. for 30 minutes, and further pressed at 170 ° C. for 1 hour to obtain a laminate.

Example 2 A laminated board was obtained in the same manner as in Example 1 except that the brominated poly (P-hydroxystyrene) acrylate obtained in Reference Example 2 was used.

Example 3 A laminate was obtained in the same manner as in Example 1 except that the brominated poly (P-hydroxystyrene) allyl ether obtained in Reference Example 3 was used.

Example 4 Example 4 was repeated except that quartz glass cloth (0.075 mm thick) was used as the sheet base for the brominated poly (P-hydroxystyrene) epoxy methacrylate obtained in Reference Example 4. A laminate was obtained in the same manner.

Example 5 70 parts by weight of brominated poly (P-hydroxystyrene) methacrylate, 30 parts by weight of polybutadiene modified with diglycidyl ether bisphenol A, 0.6 of 2-ethyl-4-metalimidazole as an epoxy curing agent
A laminate was obtained in the same manner as in Example 1 except that parts by weight were used.

Example 6 60 parts by weight of poly (P-hydroxystyrene) methacrylate obtained in Reference Example 5 and 40 parts by weight of polybutadiene modified with diglycidyl ether 2,2 ', 4,4'-tetrabromobisphenol A Parts, and a laminated board was obtained in the same manner as in Example 1, except that 1.0 parts by weight of 2-ethyl-4-methylimidazole was used as an epoxy curing agent.

Comparative Examples 1 and 2 Epoxy resin laminates and polyimide resin laminates are referred to as Comparative Examples 1 and 2.

Comparative Example 3 50 parts by weight of a 1,2-polybutadiene prepolymer and 50 parts by weight of a phenol novolak type epoxy-modified polybutadiene were dissolved in xylene to obtain a varnish having a solid content of 20 to 30% by weight. Further, 5 parts by weight of dicumyl peroxide as a radical polymerization initiator and 2 parts by weight as an epoxy curing agent
1 part by weight of -ethyl-4-methylimidazole is added,
A laminate was obtained in the same manner as in Example 1.

Table 2 shows the main characteristics of the laminates according to the examples and comparative examples.

[0034]

[Table 2]

The laminate according to the present invention has a low dielectric constant characteristic similarly to a laminate using a polybutadiene-based material generally known as a low dielectric constant material, and is currently applicable to a multilayer printed board of a large computer. Relative dielectric constant from 4.7 to 3.
Since it can be set to 5 or less, the signal transmission delay time can be reduced by 15%. In addition, the properties of heat resistance and linear expansion coefficient, such as glass transition temperature, thermal decomposition temperature, and solder heat resistance, show characteristics that are more attractive than epoxy resin laminates and polybutadiene resin laminates, and are equivalent to polyimide resin laminates. It has the following characteristics. Flame retardancy is UL standard V- without adding flame retardant etc.
Complies with O class.

[0036]

According to the present invention, it is possible to manufacture a low dielectric constant laminated material having both heat resistance and flame retardancy.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C08L 63/08 NJN C08L 63/08 NJN (72) Inventor Akio Takahashi 4026 Kuji-cho, Hitachi City, Ibaraki Prefecture Hitachi, Ltd.Hitachi Laboratory (72) Inventor Motoyo Wajima 4026 Kuji-cho, Hitachi City, Ibaraki Prefecture Hitachi, Ltd. In the laboratory (56) References JP-A-50-103599 (JP, A)

Claims (1)

(57) [Claims] 1. A laminate in which a prepreg obtained by impregnating a synthetic resin into a base material and drying is laminated and bonded, wherein the synthetic resin is represented by * Wherein A is hydrogen, an alkyl group and a halogen group, R is alkenyl or alkenoyl having 2 to 4 carbon atoms, m is a number from 1 to 4, and n is a number from 1 to 100. A laminate using a flame-retardant resin composition, comprising a prepolymer comprising a (P-hydroxystyrene) derivative as an essential component.