JPH06316642A - Laminated sheet using flame retardant resin composition - Google Patents

Abstract

PURPOSE:To provide a laminated sheet, consisting essentially of a prepolymer composed of a specific derivative as a synthetic resin, excellent in flame retardancy, heat resistance and electrical characteristics and suitable as multilayered printed circuit boards. CONSTITUTION:The laminated sheet is obtained by using a prepolymer composed of a poly(p-hydroxystyrene) derivative expressed by formula I [A is H, an alkyl or halogen; R is a 2-4C alkenyl or alkenoyl; (m) is 1-4; (n) is 1-100] as an essential component as a synthetic resin, impregnating substrates with the synthetic resin, drying the prepared sheets of prepreg, laminating and bonding the resultant sheets of the prepreg. Furthermore, an epoxy-modified polybutadiene expressed by formula II [B is a copolymer of glycidyl ethereal epoxy; (n) is 4-100] is preferably blended.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, as a laminated material for a multilayer printed circuit board, a laminated board 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 has been mainly used. Is used for. In particular, a large computer is required to have a high density, and a polyimide resin having excellent heat resistance and dimensional stability is used. However, in recent years, with the increase in the speed of arithmetic processing of large-scale computers, a printed circuit board having excellent electrical characteristics has been required to improve the signal transmission speed. In particular, a printed circuit board having a low dielectric constant is required to shorten the signal transmission delay time and the circuit thickness. As such a low dielectric constant laminated material, tetrafluoroethylene resin, polybutadiene resin laminated plate, etc. have been developed. Examples of such laminated sheets include, for example, Proceeding N.N.P.C.O.N., (1981), pages 160 to 169 (Pr.
oc. NEPCON (1981) pp. 160-169) and JP-A-55-127426.

[0003]

However, since the resin is thermoplastic and the glass transition temperature is low, the PTFE laminated plate has a problem that the coefficient of thermal expansion is large at a high temperature and the dimensional stability is not sufficient. There is a concern about the reliability of through holes after chemical bonding, and when applied to a multilayer printed circuit board, the wiring density is about the same as that of epoxy resin, and there is not much advantage as a low dielectric constant material. Further, since PTFE does not have an appropriate solvent, a bonding method by heating, melting and compression is generally used, but it has a drawback that the melting temperature is very high. Polybutadiene resin has a drawback that it is flammable in terms of its molecular structure. In order to impart flame retardancy, addition type flame retardants such as decabromodiphenyl ether and triphenyl phosphate, tribromophenyl methacrylate and tribromophenyl acrylate are added. Although it is necessary to add reactive flame retardants such as the above, there is a problem that addition of these impairs the electrical characteristics, heat resistance, and dimensional stability inherent in the polybutadiene resin.

The object of the present invention is to replace the polyimide-based multi-layer printed wiring board that has been used in large-scale computers in the past with a low dielectric constant having flame retardancy and capable of high-density wiring equivalent to that of a polyimide laminated material. A laminated board using a laminated material is provided.

[0005]

The first invention relates to a laminated board using a flame-retardant resin composition, which is characterized by the following general formula (I):

[0006]

[Chemical 4]

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

The second invention relates to a laminated board using a flame-retardant resin composition, which is characterized by the following general formula (I):

[0009]

[Chemical 5]

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

[0011]

[Chemical 6]

A laminate using a thermosetting resin composition containing an epoxy-modified polybutadiene represented by the formula (wherein B is a glycidyl ether epoxy copolymer and n is a number from 4 to 100). It is in.

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. Specific examples thereof include vinyl ethers, isobutenyl ethers, allyl ethers of poly (P-hydroxystyrene), acrylic acid esters, methacrylic acid esters, epoxy methacrylic acid esters, and compounds corresponding to the general formula I. There is that bromide. These may be used alone or in combination of two or more as desired.

In the epoxy-modified polybutadiene, which is one of the thermosetting resins of the present invention represented by the general formula (II), a specific example of the glycidyl ether type epoxy resin used for modification is diglycidyl. Ether bisphenol A, diglycidyl ether 2,2'-dibromobisphenol A, diglycidyl ether 2,2 ',
There are 4,4'-tetrabromobisphenol A, diglycidyl ether 2,2'-dimethylbisphenol A, diglycidyl ether 2,2 ', 4-trimethylbisphenol A, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin. . These may be used alone or in combination of two or more, if desired. Poly (P-hydroxystyrene) represented by the above general formula (I)
Addition of epoxy-modified polybutadiene represented by general formula (II) to the derivative makes it flexible, adhesive to copper foil,
Mechanical properties etc. are improved. Further, by further adding an epoxy curing agent to the above resin composition, it is possible to further improve the various characteristics and reduce the dielectric constant. The compounding amount of the epoxy-modified polybutadiene is not particularly limited, but when the compounding amount is large, the relative dielectric constant of the thermosetting resin becomes high, and the flame retardancy, heat resistance, dimensional stability, etc. are reduced.

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

First, a poly (P-hydroxystyrene) derivative and an epoxy-modified polybutadiene are dissolved in an organic solvent to prepare a varnish. As the organic solvent, for example,
Toluene, xylene, acetone, methyl ethyl ketone,
N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, trichloroethylene, trichloroethane, methylene chloride, dioxane, ethyl acetate and the like can be used without limitation as long as they are solvents capable of uniformly dissolving the resin composition. A radical polymerization initiator and an epoxy curing agent are added to this varnish thus prepared to obtain a varnish for impregnation.

Typical examples of the radical polymerization agent include benzoyl peroxide, dicumyl peroxide,
Methyl ethyl ketone peroxide, t-butyl peroxylavate, 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) hexyne (3), diisopropylbenzene hydroperoxide, p-methane hydroperoxide, pinan hydroxide, 2,5-dimethyl Examples include hexane-2,5-dihydroperoxide and cumene hydroperoxide. These are preferably added in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin composition.

Typical examples of epoxy curing agents include 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, pyro-anhydrous Mellitic acid, bonzophenone tetracarboxylic acid 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 or more kinds thereof are used. It is suitable to use the compounding amount 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 sheet-like base material is impregnated and coated with the obtained impregnating varnish and dried at room temperature to 170 ° C. to obtain a prepreg having no tackiness. The setting of the drying temperature at this time depends on the solvent and the initiator used. The required number of prepregs obtained at the end are piled up at 1 to 100 kgf / cm at 100 to 250 ° C.
^A heat curing reaction is performed under a pressure of ² to obtain a laminated plate.

As the sheet-shaped substrate, almost all those generally used for laminated materials can be used. As the inorganic fiber, E glass, C glass, A glass, S glass, D glass, YM containing SiO ₂ , Al ₂ O _3, etc. as components
There are various glass fibers such as Q-glass using 31-A glass and quartz. Examples of the organic fibers include aramid fibers containing a polymer compound having an aromatic polyamideimide skeleton as a component.

[Reference Example] Reference Examples 1 to 4 250 g of brominated poly (P-hydroxystyrene) was dissolved in 500 g of chloroform, and sodium hydroxide 120 was added.
500 g of an aqueous solution was added with stirring, and the mixture was stirred at 25 ° C for 1
After reacting for a time, a sodium salt is obtained. Next, 200 g of a chloroform solution of 120 g of methacrylic acid chloride was gradually added and reacted at 25 ° C. for 2 hours, then the chloroform solution and the aqueous solution were separated, and the chloroform solution was concentrated to obtain a reaction product. Furthermore, this reaction product was dissolved in acetone, and the solution was added dropwise to methanol for purification.

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

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 the mixture was 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 was gradually added and reacted at 25 ° C. for 2 hours, then the chloroform solution and the aqueous solution were separated, and the chloroform solution was concentrated to obtain a reaction product. Furthermore, 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) methacrylic acid ester obtained in Reference Example 1 is dissolved in methyl ethyl ketone by heating to obtain a varnish having a solid content of 40 to 50% by weight.
Further, 3 parts by weight of dicumyl peroxide was added as a radical weight initiator to 100 parts by weight of the resin, and then the varnish was impregnated and coated on a glass cloth (thickness: 0.1 mm) at 60 to 80 ° C. It was dried for 10 to 20 minutes to obtain a tack-free prepreg. Next, the prepreg
A laminated sheet was obtained by heating the sheet at a stacking pressure of 30 kgf / cm ² and a temperature of 130 ° C. for 30 minutes and further pressing at 170 ° C. for 1 hour.

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 laminated board 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 The same as Example 1 except that quartz glass cloth (thickness: 0.075 mm) was used as a sheet substrate in the brominated poly (P-hydroxystyrene) epoxymethacrylate obtained in Reference Example 4. A laminated plate 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, 2-ethyl-4-metalimidazole as an epoxy curing agent 0.6
A laminated board was obtained in the same manner as in Example 1 except that parts by weight were used.

Example 6 60 parts by weight of the poly (P-hydroxystyrene) methacrylic acid ester obtained in Reference Example 5 and 40 parts by weight of polybutadiene modified with diglycidyl ether 2,2 ', 4,4'-tetrabromobisphenol A. Parts, and 1.0 parts by weight of 2-ethyl-4-methylimidazole as an epoxy curing agent were used to obtain a laminated plate in the same manner as in Example 1.

Comparative Examples 1 and 2 Comparative examples 1 and 2 are an epoxy resin laminated plate and a polyimide resin laminated plate.

Comparative Example 3 50 parts by weight of 1,2-polybutadiene prepolymer and 50 parts by weight of phenol novolac type epoxy-modified polybutadiene are 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 as an epoxy curing agent.
Add 1 part by weight of -ethyl-4-methylimidazole,
A laminated board was obtained in the same manner as in Example 1.

Table 2 shows the main characteristics of the laminates according to the above-mentioned Examples and Comparative Examples.

[0034]

[Table 2]

The laminated plate of the present invention has a low dielectric constant characteristic similar to a laminated plate using a polybutadiene-based material generally known as a low dielectric constant material, and is currently applied to a multilayer printed board of a large computer. Compared with the epoxy resin laminates and polyimide resin laminates that are used, the relative permittivity is 4.7 to 3.
Since it can be 5 or less, the signal transmission delay time can be reduced by 15%. Furthermore, the characteristics of heat resistance and linear expansion coefficient indicated by glass transition temperature, thermal decomposition temperature, solder heat resistance, etc. are more attractive than those of epoxy resin laminates and polybutadiene resin laminates, and are equivalent to polyimide resin laminates. It has the characteristics of. Flame retardance is UL standard V-without addition of flame retardants.
Conforms to O class.

[0036]

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

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI technical display location C08L 63/08 NJN 8830-4J (72) Inventor Akio Takahashi 4026 Kuji Town, Hitachi City, Ibaraki Prefecture Co., Ltd. Hitachi Research Laboratory, Hitachi, Ltd. (72) Motoyo Wajima, 4026 Kujimachi, Hitachi City, Ibaraki Prefecture Hitachi Research Institute, Ltd., Hitachi Research Institute, Ltd. (72) Toshikazu Narahara 4026, Kuji Town, Hitachi City, Ibaraki, Japan Hitachi Research Laboratory

Claims (2)

[Claims] 1. A laminated board having a prepreg obtained by impregnating a base material with a synthetic resin and drying the laminated prepreg, wherein the synthetic resin has the general formula (I): (Wherein A is hydrogen, an alkyl group and a halogen group, R is an alkenyl or alkenoyl having 2 to 4 carbon atoms, m is 1 to 4 and n is a number of 1 to 100). A laminated board using a flame-retardant resin composition, which comprises a prepolymer composed of a (P-hydroxystyrene) derivative as an essential component. 2. The following general formula (I): (Wherein A is hydrogen, an alkyl group and a halogen group, R is an alkenyl or alkenoyl having 2 to 4 carbon atoms, m is 1 to 4 and n is a number of 1 to 100). A prepolymer composed of a (P-hydroxystyrene) derivative is added to the following general formula (II): (In the formula, B is a copolymer of glycidyl ether type epoxy, and n is a number of 4 to 100), and a flame-retardant resin composition is used. Laminated board.