JPH0653786B2 - Thermosetting resin composition - Google Patents

Description

The present invention relates to a thermosetting resin composition, and more particularly to a thermosetting resin composition having excellent processability, heat resistance and adhesiveness.

Thermosetting resins are used as various electrical insulating materials, structural materials, etc. as casting, impregnating, laminating, and molding materials. In recent years, the usage conditions of materials have tended to be severe in each of these applications, and the heat resistance of materials has become an important characteristic. In addition, in laminated plates and the like, heat resistance as well as adhesiveness to a base material have become important characteristics.

Conventionally, a thermosetting polyimide resin has been used for this purpose, but it requires heating at a high temperature for a long time until the curing, and further, the adhesiveness to a substrate is insufficient.

Further, although the epoxy resin having improved heat resistance is excellent in workability and adhesiveness, its high heat resistance such as mechanical properties at high temperature, electrical properties and long-term heat deterioration resistance is insufficient.

As one of the alternative materials, for example, polyimide,
Thermosetting mixture comprising an alkali group-containing epoxy compound having a specific production and a curing agent (JP-A-52-154897)
However, the allylic group-containing epoxy compound used here is an epoxidized Claisen transfer product of an allyl ether compound, in which the nucleus-substituted allyl group and the epoxy group have the same aromatic ring ortho position. It is difficult to obtain a uniform cured product because it is located at, especially in the case of the novolac type, there is a problem in cured physical properties, heat resistance property, etc., because either group is likely to remain unreacted .

From such a background, as a result of intensive investigations by the present inventors on a resin composition having excellent heat resistance properties, it was found that a resin composition containing a specific resin, a maleimide compound and an optional curing agent is suitable for the above purpose. Heading The present invention has been completed.

That is, the present invention provides (A) a phenol novolac resin in which a phenolic hydroxyl group is epoxidized and allyl etherified, (B) a polymaleimide compound having two or more maleimide groups in the molecule, and (C) ) A thermosetting resin composition containing a curing agent is provided.

The component (A) used in the present invention is an alkyl group, an aryl group, an aralkyl group, an arenyl group or a halogen atom-substituted or unsubstituted phenol, specifically, phenol, cresol, ethylphenol, isopropyl. Phenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, phenylphenol, penzylphenol, chlorophenol, promphenol, xylenol, methylbutylphenol, methoxyphenol,
Ethoxyphenol, α-methylbenzylphenol,
Obtained by condensation reaction of one or more phenols such as β-phenylethylphenol, dihydroxybenzene (including isomers) and bisphenol A with aldehydes such as formaldehyde, furfural, acrolein and glyoxal by a known method. A novolak resin having an average number of nuclides of usually 2 to 15 and an allyl etherified phenolic novolak resin obtained by reacting an allyl halide such as allyl chloride, allyl bromide and allyl iodide in the presence of an alkali. It is obtained by epoxidation.

As a method of partially epoxidizing, in order to obtain a desired allyl etherification ratio of phenol novolac resin,
After partial allyl etherification, the residual hydroxyl group is reacted with epihalohydrin such as epichlorohydrin, epipromohydrin, and methyl epichlorohydrin in the presence of alkali, or after almost complete allyl etherification, hydrogen peroxide is added. There is a method of partially epoxidizing so as to obtain a desired epoxidation rate with a peroxide such as peracid.

Here, the ratio of the allyl etherified hydroxyl groups to the epoxidized hydroxyl groups should preferably be 0.5 to 9.0, and more preferably 0.7 to 4.0.

When the ratio of allyl ether groups is high, the adhesiveness is lowered, while when the ratio is low, the heat resistance is lowered.

The component (B) used in the present invention is a compound containing two or more maleimide groups represented by the general formula (I) in the molecule.

(In the formula, R represents a hydrogen atom or a lower alkyl group.) Specific examples thereof include N, N'-diphenylmethane bismaleimide and N, N'-phenylene bismaleimide. , N, N'-
Diphenyl ether bismaleimide, N, N'-diphenylsulfone bismaleimide, N, N'-dicyclohexylmethane bismaleimide, N, N'-xylene bismaleimide, N, N'-tolylene bismaleimide, N,
N'-xylylene bismaleimide, N, N'-diphenylcyclohexane bismaleimide, N, N'-dichloro-diphenylmethane bismaleimide, N, N'-diphenylcyclohexane bismaleimide, N, N'-diphenylmethane bismethyl maleimide, N , N'-diphenylether bismethylmaleimide, N, N'-diphenylsulfone bismethylmaleimide (including each isomer), N, N'-ethylene bismaleimide, N, N'-
Hexamethylenebismaleimide, N, N'-hexamethylenebismethylmaleimide, and prepolymer having N, N'-bismaleimide skeleton at the end obtained by adding these N, N'-bismaleimide compounds and diamines , And a maleimide compound or a methylmaleimide compound of an aniline / formalin polycondensate. In particular, N, N'-diphenylmethane bismaleimide, N, N '
-Diphenyl ether bismaleimide is preferred.

Examples of the component (C) used as necessary in the present invention include bisphenol A, tetrapromobisphenol A,
Bisphenol F, bisphenol S, bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenylethane, 1,3,3-trimethyl-1-m-
Hydroxyphenylindan-5 or 7-ol,
1,3,3-trimethyl-1-p-hydroxyphenylindan-6-ol, resorcin, hydroquinone,
Catechol, polyphenol compounds such as phenols novolac as a raw material of the above-mentioned component (A), maleic acid,
Polycarboxylic acids such as phthalic acid, nadic acid, methyl-tetrahydrophthalic acid, methyl nadic acid and their anhydrides, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl ether, phenylenediamine, diaminodicyclohexylmethane, xylylenediamine, toluenediamine, xylenediamine. , Diaminodiphenylcyclohexane, dichloro-diaminodiphenylmethane (including isomers), ethylenediamine,
Polyamine compounds such as hexamethylenediamine, boron trifluoride ethylamine complex, boron trifluoride amine complex such as boron trifluoride piperidine complex, imidazole derivative,
Examples thereof include tertiary amines, quaternary ammonium salts, and active hydrogen-containing compounds capable of reacting with an epoxy group such as dicyandiamide and tetramethylguanidine.

In the resin composition according to the present invention, the quantitative ratio of each component can be appropriately selected depending on the application, the desired heat resistance, etc., but generally the (B) component to the double bond of the (A) component is The ratio of double bonds is 0.5 to 3, (A) when using the component of (C)
The ratio of active hydrogen of component (C) to the epoxy group of component is 3
It is preferable to select the following.

In the present invention, each component can be preliminarily reacted to the extent that gelation does not occur, but when three components are used, first the components (A) and (C) are reacted and then the component (B) is used. Is preferable in terms of cured physical properties.

The resin composition according to the present invention can be easily cured by heat. In this case, curing is accelerated by adding an azo compound, a radical polymerization initiator such as an organic peroxide, a tertiary amine, a quaternary ammonium salt, an imidazole, an ion catalyst such as boron trifluoride / amine salt. You can also

The resin composition of the present invention is blended with various fillers and reinforcing materials using a mixer, a kneader, a roll, etc. at a relatively low temperature,
It is possible to prepare casting or molding materials,
It can also be used as a laminated material by dissolving it in a solvent and coating it on various fibers such as glass fiber and carbon fiber. Further, other known thermosetting resins such as other acrylic resins, epoxy resins, unsaturated polyester resins, phenol resins, silicone resins, triazine resins, etc. may be added depending on the purpose.

Thus, the resin composition of the present invention is useful as a thermosetting resin composition having excellent processability, heat resistance and adhesiveness for casting, impregnation, lamination and molding materials.

Next, reference examples and examples will be shown in order to explain the present invention in detail, but the present invention is not limited thereto. In the examples, "part" means "weight unit".

Reference Example 1 (Partial Allyl Etherification) o-Cresol novolac resin 2 having a softening point of 90 ° C. in a reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser.
Charge 36 parts (2 equivalents) and 840 parts of dimethylformamide as a reaction solvent, and after completely dissolving the resin,
Add 62 parts (1.5 equivalents) of 7% caustic soda and stir well. Allyl chloride 1 while keeping the temperature of the reaction system at 40 ° C
After 20 parts (1.58 equivalents) was added dropwise over 1 hour, the temperature was raised to 50 ° C. and the temperature was maintained for 5 hours. Then, dimethylformamide was distilled off, 300 parts of toluene was charged to dissolve the resin, and the inorganic salt was removed by washing with water and filtration,
By concentrating the liquid, 282 parts of a reddish-orange viscous liquid resin having an allyl etherification rate of 75% having no nuclear-substituted allyl group and an OH equivalent of 592 g / eq was obtained.

(Epoxidation) In a reactor equipped with a thermometer, a stirrer, a dropping funnel, and a reaction water recovery device, 236.8 parts (0.4 equivalent) of the partially allyl ether compound and 370 parts (4.0 parts) of epichlorohydrin were added.
(Equivalent), the reaction system pressure was adjusted to 150 mmHg, and while gradually heating the system to boiling, 35 parts of 48% caustic soda aqueous solution (0.42 equivalent) was maintained at a reaction temperature of 62 ° C. gradually over 2 hours. Add. During the reaction, water is removed from the reaction system in the form of an azeotrope with epichlorohydrin and epichlorohydrin is circulated. After the completion of the caustic soda dropping, the same conditions are maintained for another 30 minutes.

Then, salt was separated from the reaction mixture, and the mother liquor was concentrated to obtain 240 parts of a yellow-orange viscous liquid having an epoxy equivalent of 658 g / eq. (AEN-1) Reference Example 2 (Partial Allyl Etherification) In Reference Example 1, instead of dimethylformamide, dimethyl sulfoxide 600 parts 97% caustic soda 41 parts (1.
0 equivalents) and allyl chloride 82 parts (1.08 equivalents) were used in the same manner except that 262 parts of a red-brown semi-solid resin having an allyl etherification rate of 50% and an OH equivalent of 276 g / eq without having a nuclear-substituted allyl group were used. Got

(Epoxidation) In Reference Example 1, the partial allyl ether compound 22
0.8 parts (0.8 equivalents), epichlorohydrin 444 parts (4.8 equivalents), 48% caustic soda aqueous solution 70 parts (0.
Epoxy equivalent 34
248 parts of 8 g / eq of yellow-orange semi-solid resin was obtained. (AEN-
Set to 2. ) Example 1 AEN-1 obtained in Reference Example-1, 200 parts and N, N '
-269 parts of diphenylmethane bismaleimide was dissolved in 700 parts of N, N'-dimethylformamide (DMF), and this solution was mixed with glass cloth (KS-1600, manufactured by Kanebo Ltd.).
A-1100). Then, it was treated in an oven at 180 ° C. for 10 minutes to obtain a prepreg. Sixty prepregs were stacked on each other at a pressure of 50 kg / cm ² with a 180 ° C press to 60
It was molded for minutes and then post-cured in an oven at 180 ° C. for 2 days to obtain a laminate. In the same manner, a 1 mm thick copper clad laminate was obtained using 6 prepregs and steel foil (TAI treatment 35μ manufactured by Furukawa Circuit Kit Co., Ltd.). Physical properties are shown in Table-1.

Example-2 AEN-2 obtained in Reference Example-2, 336 parts and N, N '
-Diphenylmethane bismaleimide (269 parts) was dissolved in 900 parts of DMF to obtain a laminate and a copper-clad laminate in the same manner as in Example-1. The physical properties are shown in Table 1.

Example-3 336 parts of AEN-2 obtained in Reference Example-2, 55 parts of bisphenol A and 0.2 parts of 2,4,6-tris (dimethylaminomethyl) phenol were reacted at 180 ° C. for 30 minutes, and then N was added. 269 parts of N'-diphenylmethane bismaleimide are added and dissolved in 990 parts of DMF. Using this solution, a laminate and a copper-clad laminate were obtained in the same manner as in Example-1. The physical properties are shown in Table 1.

Comparative Example To 179 parts of N, N'-diphenylmethane bismaleimide was added 37 parts of 4,4'-diphenylmethane, and the mixture was mixed at 180 ° C for 5 hours.
Stir for a minute. Next, 320 parts of DMF is added and uniformly dissolved. Using this solution, a laminate and a copper-clad laminate were obtained in the same manner as in Example-1. The physical properties are shown in Table 1.

As is clear from Table 1, the cured product obtained from the composition according to the present invention has excellent heat resistance, water resistance, electrical insulation and adhesiveness. Further, it can be seen that the composition according to the present invention has excellent solubility in a solvent and excellent processability such as curing at a temperature of about 180 ° C.

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Claims (2)

[Claims] 1. A phenol novolac resin in which (A) a phenolic hydroxyl group is epoxidized and allyl etherified (B) a polymaleimide compound having two or more maleimide groups in the molecule, and (C) a curing agent if necessary. A thermosetting resin composition containing an agent. 2. The thermosetting resin composition according to claim 1, wherein the ratio of allyl etherified hydroxyl groups to epoxidized hydroxyl groups is 0.5 to 9.0.