JPH0586263A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject new composition having improved heat resistance, electrical characteristics, etc., by blending an epoxy resin with a specific amount of a curable resin composition comprising a polyphenylene ether resin, a polyfunctional maleimide, etc., as essential components. CONSTITUTION:(A) An epoxy resin is blended with (B) 6-<50wt.% curable resin composition comprising (i) a polyphenylene ether resin and (ii) a polyfunctional maleimide of the formula (R1 is aromatic or aliphatic organic group; X1 and X2 are H or lower alkyl; (k) is 2-10 integer) or a polyfunctional cyanuric acid ester of the formula R2=(O-C=N)n (R2 is polyfunctional organic group having <=10 aromatic benzene rings and cyanic acid ester group is directly bonded to aromatic ring of R2; (n) is 2-10 integer) as essential components to give the objective composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a curable resin composition containing a. Polyphenylene ether resin and b-1. Polyfunctional maleimide or b-2. Polyfunctional cyanate ester as essential components.
The present invention relates to a novel epoxy resin composition having improved heat resistance and electrical characteristics by blending (I), and is suitable for, for example, electrical / electronic laminates, paints, molding materials, etc. Is.

[0002]

2. Description of the Related Art There is a strong demand for miniaturization and simplification of mounting methods with the development of electronic and electric devices for consumer use, industrial use, etc., and correspondingly, development of lightweight and high-performance electronic materials is desired. It is rare. In the field of polymer materials as well, research and development are underway to meet this demand. Especially for printed wiring boards, materials with better heat resistance, dimensional stability, or electrical characteristics are required for high-density circuits. Is required. Conventionally, a substrate in which a curable resin such as a phenol resin or an epoxy resin is impregnated is mainly used, but there is a problem that the electrical characteristics, particularly the dielectric constant and the dielectric loss tangent are large. On the other hand, many thermoplastic resins are excellent in electrical characteristics, but have poor heat resistance, solvent resistance, dimensional stability, and the like, and thus have a problem that they cannot be applied particularly to conventional assembly processes. Although the polyphenylene ether resin is a thermoplastic resin having high heat resistance and the like, it has a large temperature dependency of physical properties and also has insufficient solder heat resistance.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
Curable resin composition containing polyphenylene ether resin and b-1. Polyfunctional maleimide represented by formula (1) or b-2. Polyfunctional cyanate ester represented by formula (2) as essential components
By finding (I), it has become possible to manufacture laminated boards with excellent heat resistance and electrical characteristics. As a result of further examination, this composition
The present invention has been completed by discovering that an epoxy resin-based laminate having improved heat resistance and electrical properties can be produced by adding (I) to the epoxy resin (II).

[0004]

Means for Solving the Problems That is, the present invention provides an epoxy resin (I) containing a. Polyphenylene ether resin and b-
1. Polyfunctional maleimide represented by formula (1) or b-2. Formula (2)
A curable resin composition (6) containing 6% by weight or more and less than 50% by weight of a curable resin composition (II) containing a polyfunctional cyanate ester represented by

[Chemical 1] (R ₁ in the formula (1) is an aromatic or aliphatic polyvalent organic, X ₁ , X ₂ is a hydrogen atom or a lower alkyl group, k represents an integer of 2 to 10 , Further, R ₂ in the formula (2) is a polyvalent organic group having 10 or less aromatic benzene rings,
The cyanate ester group is directly bonded to the aromatic ring of R ₂ ,
n represents an integer of 2-10 . )

The present invention will be described below. The epoxy resin (I) of the present invention is a known organic compound containing one or more, preferably two or more epoxy groups in the molecule, and any of them can be used. Epoxy equivalent 60 to 600
0, preferably 160 to 4000, and particularly preferably used for electrical material laminates, copper clad laminates, IC encapsulation materials and the like. Specifically, bisphenol A type epoxy resin, bisphenol A type epoxy resin such as halogenated bisphenol A type epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin, nuclear brominated cresol novolac type epoxy resin Examples thereof include those converted to glycidyl ether. Further, these are also suitably used as a composition with a known curing agent.

Next, the polyphenylene ether resin of the component a of the curable resin (II) of the present invention is known per se and has a heavy chain having a repeating structural unit represented by the following general formula (3) in the skeleton. Collectives are collectively referred to as a homopolymer having the same repeating unit or a copolymer obtained by combining two or more kinds.

[Chemical 2] (In the formula, R ₃ and R ₄ represent a lower alkyl group having 1 to 3 carbon atoms, and R ₅ represents a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms.)

Specifically, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-)
Homopolymers represented by phenylene) ether and poly (2,6-diethyl-1,4-phenylene) ether; copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol and 2 -A copolymer of methyl-6-ethylphenol and 2,3,6-trimethylphenol is exemplified, and poly (2,6-
Copolymers of dimethyl-1,4-phenylene) ether, 2,6-dimethylphenol and 2,3,6-trimethylphenol are practical. The number average molecular weight is 1000 to 3
A low molecular weight product has a good solubility and good workability, and a high molecular weight product improves mechanical properties.

The polyfunctional maleimide of the component b-1. Of the curable resin composition (II) of the present invention is a compound represented by the formula (1). This polyfunctional maleimide is prepared by a known method of reacting maleic anhydrides with a polyamine containing 2 to 10, preferably 2 to 5 amino groups to prepare maleamic acid, and then dehydrating and cyclizing the maleamic acid. It can be manufactured.

The polyamines used are meta or paraphenylenediamine, 1,4- or 1,3-cyclohexanediamine, hexahydroxylylenediamine, 4,4'-diaminobiphenyl, bis (4-aminophenyl) methane,
Bis (4-aminophenyl) ether, bis (4-aminophenyl) sulfone, bis (4-amino-3-methylphenyl) methane, bis (4-amino-3,5-dimethylphenyl)
Methane, bis (4-amino-3-chlorophenyl) methane,
Bis (4-aminophenyl) cyclohexane, 2,2-bis (4
-Aminophenyl) propane, 2,2-bis (4-amino-3-
Methylphenyl) propane, 2,2-bis (4-amino-3,5-
Dibromophenyl) propane, bis (4-aminophenyl) -phenylmethane, 3,4-diaminophenyl-4'-aminophenylmethane, 1,1-bis (4-aminophenyl) -1-phenylethane, s-triazine Examples thereof include a melamine having a ring, a polynuclear polyamine in which an aniline and formalin are reacted to bond a benzene ring with a methylene bond, and an aromatic one is particularly preferable from the viewpoint of heat resistance. It can also be used as an oligomer (prepolymer) or a prepolymer with the polyamines exemplified above.

The polyfunctional cyanate ester as the component b-2. Is a compound represented by the above formula (3). Specifically, 1,3- or 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-, 1,4-, 1,6-, 1,8-, 2,6-or 2,
7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4′-dicyanatobiphenyl, bis (4-cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) propane, 2 , 2-bis (3,5-dichloro-4-cyanatophenyl)
Propane, 2,2-bis (3,5-dibromo-4-cyanatophenyl) propane, bis (4-cyanatophenyl) ether,
Bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, tris (4-cyanatophenyl) phosphite, tris (4-cyanatophenyl) phosphate, and polycarbonate oligomer containing a terminal OH group and halogen Cyanate obtained by reaction with cyanide (USP-4026913), Cyanate obtained by reaction with novolac and cyanogen halide (USP-4026913)
P-4022755, USP-3448079) and the like. In addition to these, Japanese Examined Japanese Patent Publications 41-1928, 43-18468, 44-4791, 45-1171
2, the same 46-41112, the same 47-26853, JP-A-51-63149, USP-355
3244, 3755402, 3740348, 3595900, 3694410 and 41
Cyanate esters described in 16946 and the like can also be used.

The polyfunctional cyanate ester described above was polymerized in the presence or absence of a catalyst to form a sym-triazine ring in the molecule, which was formed by trimerizing a part of the cyanato group. It can be used as a prepolymer. The polyfunctional cyanate ester and its prepolymer can be used alone or in the form of a mixture, and the number average molecular weight of the individual and the mixture is preferably 1,700 or less, particularly preferably in the range of 500 to 1,500.

The composition ratio of the components in the curable resin (II) of the present invention is 2 to 99% by weight of component a and 98 to 1% by weight of component b.
b-1. Component: 95% by weight or less, b-2: Component: 97% by weight or less.
It is preferably used in an amount of not less than 50% by weight, particularly 50 to 80% by weight. Also, curable resin (II) for epoxy resin (I)
The compounding amount of less than 50% by weight to 6% by weight, preferably
A range of less than 50% by weight and up to 25% by weight is preferable. If the blending amount is too small, the effect of improving heat resistance and electric properties will be insufficient.

The curable resin composition of the present invention contains the above-mentioned components as essential components, but known amines, novolacs, imidazoles, organic metal salts, metal chelate compounds, organic peroxides, etc. in each component. Catalyst or curing agent :; known organic or inorganic fibers such as glass fiber, carbon fiber, quartz fiber, wholly aromatic polyamide fiber and aluminum nitride,
Various forms such as graphite, wollastonite, mica, silica, glass, titanium oxide, copper, iron, stainless steel, aluminum, polyimide resin, and other powders, fibers, and scales can be blended. The method for preparing the curable resin composition of the present invention is a method of blending the above components in powder form and mixing with a Henshol mixer,
Examples of the method include a method of preparing without solvent such as a method of melting and mixing by heating for a preliminary reaction at the time of mixing, a method of preparing as a solution using a solvent, particularly a solvent of component (I) a, and the like. In case of solution, resin impregnated base material (prepreg)
The powder mixture is suitable for the preparation of the molding material, and is appropriately selected according to the purpose.

[0014]

EXAMPLES The present invention will be described in more detail with reference to the following examples. Examples 1 to 5 and Comparative Example 1 As the epoxy resin, a cresol novolac type epoxy resin (manufactured by Ciba Geigy, trade name; ECN 1273, hydroxyl equivalent)
0.007 meq / g, epoxy equivalent 225, softening point 73
℃, hereinafter referred to as “ECN 1273”), nuclear brominated novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name; BREN, hydroxyl equivalent 0.007 meq / g, epoxy equivalent 275, softening point 85 ° C, Br included) Amount of 36%, hereinafter referred to as "BREN"), and diaminodiphenylmethane (hereinafter referred to as "DDM") as its curing agent.
)) Was added to the polyphenylene ether copolymer (intrinsic viscosity 0.34 dl / g; 25 ° C, chloroform solvent, 2,6-dimethylphenol / 2,3,6-trimethylphenol = 95/5 (molar ratio), (Hereinafter referred to as "C-PPE"), screws
(4-aminophenyl) methane (hereinafter referred to as "BM"), 2,
2-bis (4-cyanatophenyl) propane (hereinafter referred to as "BPA-C
N)) and 2-ethyl-4-methylimidazole (hereinafter referred to as "2E4MI") powders were mixed in the respective ratios shown in Table 1 and uniformly mixed with a Henschel mixer.
The obtained mixture was uniformly put between electrolytic copper foils having a thickness of 35 μm, and compression-molded at a temperature of 225 ° C. and a pressure of 100 kg / cm ² for 1 hour to obtain a double-sided copper clad plate having a thickness of about 1.5 mm. The test results of this double-sided copper clad plate are shown in Table 1 below.

[0015]

[Table 1] Table-1 (Resin composition and physical properties) Test species & No .: Ratio 1 Actual 1 Actual 2 Actual 3 Actual 4 Actual 5 Resin component ECN 1273: 100 75 60 BREN: 55 55 55 C-PPE: 20 20 20 20 20 BM: 5 20 20 5 BPA-CN: 25 5 20 Curing agent or catalyst DDM: 25 18.8 15.0 2E4MI: 0.2 0.2 Physical properties / glass transition point (℃): 192 201 220 223 241 228 ・ Peel strength (kg / cm ): 1.3 1.6 1.4 1.8 1.4 1.8 ・ Dielectric constant (at1MHz): 4.1 3.8 3.5 3.3 3.4 3.3 ・ Dielectric loss tangent (〃): 0.020 0.012 0.008 0.005 0.004 0.005

[0016]

As described above, the curable resin composition of the present invention has heat resistance of epoxy resin (ratio 1), copper foil peeling strength (= Peel strength), and electrical characteristics (especially low dielectric loss tangent). It can be improved. As a result, it is possible to easily meet this requirement even when heat resistance and the like are further required as an improved electrical property for the same application as the epoxy resin. It can be suitably used for molded products, paints and the like.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08L 71/12 LQM 9167-4J LQP 9167-4J

Claims (1)

[Claims] 1. An epoxy resin (I) containing a polyphenylene ether resin and b-1. A polyfunctional maleimide represented by the formula (1) or b-2. A polyfunctional represented by the formula (2). A curable resin composition (6) containing 6% by weight or more and less than 50% by weight of a curable resin composition (II) containing a cyanate ester as an essential component. (R ₁ in the formula (1) is an aromatic or aliphatic polyvalent organic, X ₁ , X ₂ is a hydrogen atom or a lower alkyl group, k represents an integer of 2 to 10 , Further, R ₂ in the formula (2) is a polyvalent organic group having 10 or less aromatic benzene rings,
The cyanate ester group is directly bonded to the aromatic ring of R ₂ ,
n represents an integer of 2-10 . )