JPS63277227A - Resin composition for laminated board - Google Patents

Abstract

PURPOSE:To obtain the titled composition, consisting essentially of a specific compound, butadiene polymer, epoxy resin compound and radical polymerization initiator and having excellent heat resistance and dielectric characteristics. CONSTITUTION:The aimed composition containing (A) a compound having one or more epoxy groups and one or more (meth)acrylamidomethyl groups, (B) butadiene polymer having 1,000-20,000 number-average molecular weight and >=50% butadiene units of the polymer chain consisting of 1,2-bonds, (C) a curing agent for epoxy resins and (D) a radical polymerization initiator as principal components. Furthermore, the component (A) is preferably a glycidyl compound expressed by formula I (Ar<1> is 6-20C aromatic hydrocarbon having one or more glycidyloxy groups; R is H or CH3; n is 1-4) or formula II (Ar<2> is 6-14C aromatic hydrocarbon having one or more N,N-diglycidylamino groups; R is H or CH3; n is 1-3).

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a resin composition for laminates that has excellent heat resistance and dielectric properties.

"Prior Art and Problems" Conventionally, laminates made of a combination of epoxy resin and glass cloth have been mainly used as materials for industrial printed circuit boards.

In recent years, there has been a demand for improved heat resistance and dielectric properties for printed circuit boards used as electronic devices become faster and more densely packaged. There is a limit to the improvement of dielectric properties with the combination of resin and glass cloth.

On the other hand, a substrate obtained by combining polyimide resin and glass cloth is also known, and although the dielectric properties are improved compared to the substrate of epoxy resin and glass cloth, the dielectric constant is 4.
．． It is difficult to reduce the value to 0 or less. 0 Usually used E-
If quartz glass is used instead of glass, the dielectric constant can be lowered, but quartz glass is expensive and has a high hardness, so it has the disadvantage that drilling with a drill is difficult.

In addition, fluororesin is known as a resin with a low dielectric constant, but fluororesin has low heat resistance, and when used as a printed circuit board, it has drawbacks such as not being able to be mounted in high density or multilayered. .

In summary, there is a demand for a resin with excellent heat resistance and a low dielectric constant as a resin for laminates, but the reality is that no resin has yet been provided that fully satisfies this demand.

"Means for Solving the Problems" An object of the present invention is to obtain a resin composition for a laminate that has excellent heat resistance and a low dielectric constant.

The present inventors conducted intensive studies on compositions for achieving the above object, and found that a resin composition in which specific compounds were combined could achieve the object,
We have arrived at the present invention.

That is, the present invention provides the following (A), (B), (C) and (D)
) component as a main component; (A> compound having at least one epoxy group and at least one acrylamide methyl group or methacrylamide methyl group; (B) number average molecular weight is 1000 to 20000,
It contains a butadiene polymer in which 50% or more of the butadiene units in the polymer chain are 1,2-bonds, (C) an epoxy resin curing agent, and (D) a radical polymerization initiator.

The heat resistance number, which is the object of the present invention, is the upper δ self (A).
, (B), (C), and CD) components, and the (B) component G gives a low dielectric constant, but the (A> component and the (B) component i;! The effect of the radical polymerization initiator (D) is due to the cross-linked structure (bonded into an integrated structure) during the polymerization reaction, so that the characteristics of each component are fully exhibited.Epoxy component (C) The resin curing agent performs a crosslinking reaction of the epoxy group in component (A), and provides properties suitable for a resin for lamination, such as adhesion with glass and adhesion with copper foil. A), CB),
By combining components (C) and (D), it is possible to obtain a resin composition that has excellent heat resistance and dielectric properties, and is suitable for a laminate.

The compound having at least one epoxy group and at least one acrylamide methyl or methacrylamide methyl group as component (A) of the present invention is not particularly limited, but is represented by the following general formula (I) or (n). Glycidyl compounds are particularly suitable for the purposes of the present invention.

? (CL"'CCNil CHx+1-Ar' CI
) (wherein, Ar' is an aromatic hydrocarbon group having 6 to 20 carbon atoms having at least one glycidyloxy group,
R represents a hydrogen atom or a methyl group, and n is an integer from 1 to 4)? (CL-C-C-NH-CHa-T-Ar” (II
) (wherein, Ar" represents an aromatic hydrocarbon having 6 to 14 carbon atoms having at least one N,N-diglycidylamino group, R is a hydrogen atom or a methyl group, and n is 1
The glycidyl compound (I) of the present invention is disclosed in Japanese Patent Application Laid-Open No. 60-13
For example, when 2,6-xylenol and N-methylol (meth)acrylamide are used as starting materials, the following structural formula (III) (wherein R is a hydrogen atom or methyl A glycidyl compound represented by the group ) can be obtained.

Moreover, the glycidyl compound (II) of the present invention is
It can be produced by the method described in No. 1-88456. In particular, when using compounds represented by as raw material amines, glycidyl represented by the following general formula (■) (wherein R is a hydrogen atom or a methyl group, and m is an integer of 0 to 2) compound can be obtained.

The number average molecular weight of the butadiene polymer which is component (B) of the present invention is in the range of 1,000 to 20,000. 1000
If it is less than 20,000, the heat resistance will be insufficient, and if it is more than 20,000 (
It is preferable that 50% or more of the butadiene units in the polymer chain are 1,2-bonds, which makes it difficult to mix with component A), and if it is less than 50%, the heat resistance will be insufficient. Preferably 85
The ratio of components (A) and (B) used in the present invention is 20% by weight.
j80-8.0: 20, more preferably 40
:60-60 :40.

As the epoxy resin curing agent which is the component (C) used in the present invention, various commonly known curing agents can be used, but examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride. 4. acids, acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, chlorendifucic anhydride, benzophenonetetracarboxylic anhydride;
Aromatic diamines such as 4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, metaphenylenediamine, paraphenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, bis(hexamethylene)triamine, menthendiamine, Aliphatic polyamines such as isophorone diamine and metaxylylene diamine, imidazole, 2-ethyl-
4-methylimidazole, 2-phenylimidazole,
Examples include imidazoles such as 1-benzyl-2-methylimidazole and 2-undecylimidazole, dicyandiamide, and amine complexes of boron trifluoride.

The amount of curing agent used varies depending on the type of curing agent, but for example, in the case of an acid anhydride, it is preferably 0.5 to 1.5 equivalents relative to the epoxy group.

In the present invention, a curing accelerator for the epoxy resin may be added as required. As the Vl conversion accelerator, any commonly known one can be used. Examples include benzyl dimethylamine, 2 4. Tertiary amines such as 6-tris(dimethylaminomethyl)phenol, imidazoles such as 2-ethyl-4-methylimidazole and N-benzylimidazole, boron trifluoride-amine complexes, ureas, phosphine metal salts, etc.

The amount of curing accelerator used should be adjusted to obtain the desired curing rate, but typically 0.01
~5% by weight is added.

As the radical polymerization initiator which is component (D) of the present invention, any initiator generally known as a radical polymerization initiator can be used, but among them, organic peroxides are particularly suitable. Examples include t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, peroxide, and [-butyl peroxybenzoate. The amount of the radical polymerization initiator used is not particularly limited, but is usually 0.1 to 2
It is used in a range of 0% by weight.

The composition of the present invention can be prepared by mixing components (A), (B), (C), and (D), impregnating glass cloth, laminating the mixture, and heat-curing the mixture. It is also possible to impregnate glass cloth, heat it to B-stage it, make it into a prepreg, and then laminate it and mold it by heat pressing. In addition, if necessary, a resin composition may be prepared by mixing the components (A>, (B), and (I)), heating them to cause a partial reaction, and then adding and mixing the component (C). This method is particularly effective when the compatibility between components (A) and (B) is low.

The glass cloth laminate obtained using the resin composition of the present invention has a low dielectric constant even when E-glass is used, has excellent heat resistance, and has excellent adhesion to glass cloth and copper foil. Therefore, it is suitable as a substrate material for electronic devices operating at high frequencies and a substrate material for microcommunications.

"Examples" The present invention will be specifically explained based on Examples below.
The present invention is not limited only to these examples.
In addition, in the following, "parts" represent "parts by weight".

Example I N-(4-glycidyloxy-3,5-dimethylphenylmethyl)acrylamide (R
is a hydrogen atom), 75 parts of 1,2-polybutadiene (B-3000, manufactured by Nippon Soda Co., Ltd., 1.2-polybutadiene with a bonding rate of 90%), and 0.3 parts of t-butyl perbenzoate. The parts were mixed and allowed to react partially with stirring at 100°C for 1 hour. Make this into a mixture.

66.7 parts of the mixture A, 1 part of N-(4-glycidyloxy-3,5-dimethylphenylmethyl)acrylamide
5.8 parts of methylnadic anhydride, 17.5 parts of methylnadic anhydride, 0.33 parts of 1-benzyl-2-methylimidazole, and 2.48 parts of dicumyl peroxide were mixed, poured between glass plates, and heated at 130°C for 3 hours. Thereafter, the mixture was cured by heating at 160° C. for 2 hours to prepare a cast plate. The heating deformation temperature, Tg, dielectric constant, and dielectric loss tangent of the obtained cast plate were measured. The results are shown in Table 1.

Example 2 53.3 parts of mixture A of Example 1, 25.7 parts of N-(4-glycidyloxy-3,5-dimethylphenylmethyl)acrylamide, 21.0 parts of methylnadic anhydride,
A casting plate was prepared in the same manner as in Example 1 by mixing 0.39 parts of 1-benzyl-2-methylimidazole and 2.37 parts of dicumyl peroxide. The heating deformation temperature, Tg, lWt ratio, and dielectric loss tangent of the obtained cast plate were measured. The results are shown in Table 1.

Example 3 66.7 parts of mixture A of Example 1, 33.3 parts of N-(4-glycidyloxy-3,5-dimethylphenylmethyl)acrylamide, 2.0 parts of dicyandiamide, 3-
2.0 parts of (3,4-dichlorophenyl)-1°1-dimethylurea and 3.0 parts of dicumyl peroxide were mixed and a casting plate was prepared in the same manner as in Example 1. The heating deformation temperature, Tg, dielectric constant, and dielectric loss tangent of the obtained cast plate were measured.

The results are shown in Table 1.

Comparative Example 1 100 parts of Epibis type epoxy resin (trade name Epicote 828, manufactured by Yuka Shell C Co., Ltd.), 7 parts of methylnadic anhydride
A cast plate was prepared by mixing 9.6 parts of N,N-dimethylbenzylamine and 0.7 parts of N,N-dimethylbenzylamine, pouring the mixture between glass plates, heating at 140°C for 1 hour, and then heating at 150°C for 15 hours to harden. The heating deformation temperature, Tg,
The dielectric constant and dielectric loss tangent were measured. The results are shown in Table 4.

Table 1 Example 4 N-(4-glycidyloxy-3,5-dimethylphenylmethyl)acrylamide (R in the above structural formula (III)
is a hydrogen atom) and 25 parts of 1゜2-polybutadiene (+3-3000, Nippon Soda Co., Ltd.!> 75
part, 0.3 part of t-butyl perbenzoate,
Partial reaction was allowed to proceed at 100° C. with stirring for 1 hour. This is called mixture A.

66.7 parts of the mixture A, 1 part of N-(4-glycidyloxy-3,5-dimethylphenylmethyl)acrylamide
5.8 parts of methylnadic anhydride, 17.5 parts of methylnadic anhydride, 0.33 parts of 1-benzyl-2-methylimidazole, and 2.48 parts of dicumyl peroxide were mixed, and the mixture was heated with a glass cloth ( E-glass, WE116E1
04BZ (manufactured by Nippon Boseki Co., Ltd.) and laminated, 1
Press molding was performed at 40° C. for 2 hours, and after-curing was performed at 160° C. for 2 hours to obtain a single-sided copper-clad laminate with a resin content of 50% by weight. The copper foil, beer strength, Tg, dielectric constant, and dielectric loss tangent of the obtained laminate were measured. The results are shown in Table 2.

Polyimide laminates (
The results of measuring the properties of commercial product A) and epoxy laminate (commercial product B) are shown in Table 2 for reference.

Table 1 "Operations and Effects" As described above, the present invention can provide a resin suitable for use in laminates that has excellent heat resistance and low electrical conductivity.

Claims (1)

[Claims] 1. A resin composition for a laminate comprising the following components (A), (B), (C) and (D) as main components; (A) at least one epoxy group; and a compound having at least one acrylamide methyl group or methacrylamide methyl group, (B) a number average molecular weight of 1000 to 20000,
A butadiene polymer in which 50% or more of the butadiene units in the polymer chain are 1,2-bonds, (C) an epoxy resin curing agent, and (D) a radical polymerization initiator. 2. (A) component is the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, Ar^1 represents at least one glycidyloxy group.
Claim 1 is a glycidyl compound having an aromatic hydrocarbon group having 6 to 20 carbon atoms, R represents a hydrogen atom or a methyl group, and n is an integer of 1 to 4. Compositions as described. 3. Compound A has the following general formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, Ar^2 has at least one N,N-diglycidylamino group and has a carbon number of 6 to 6) 14 aromatic hydrocarbons, R is a hydrogen atom or a methyl group, and n is 1
The composition according to claim 1, which is a glycidyl compound represented by: 4. Claims that the glycidyl compound is a glycidyl compound represented by the following structural formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) (wherein R is a hydrogen atom or a methyl group) The composition according to item 2. 5. The glycidyl compound has the following structural formula (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) (In the formula, R is a hydrogen atom or a methyl group, and m is 0 to
The composition according to claim 3, which is a glycidyl compound represented by: 6. A patent claim in which component (C) is at least one selected from acid anhydride-based epoxy resin curing agents, aromatic diamine-based epoxy resin curing agents, aliphatic polyamine-based epoxy resin curing agents, imidazoles, and dicyandiamide. The composition according to each item of the range 1 to 5. 7. The composition according to each of claims 1 to 6, wherein component (D) is an organic peroxide.