JPS62127316A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition excellent in processability, heat resistance and adhesion, by mixing a specified phenol, novolak resin with a polymaleimide compound and, optionally, a curing catalyst. CONSTITUTION:A novolak resin with an average number of nucleic of 2-15, obtained from a phenol (substituted with an alkyl, aryl or the like group) and an aldehyde, is reacted with an aryl halide in the presence of an alkali to obtain an aryl-etherified phenol novolak resin. This resin is partially epoxidized to obtain a phenol novolak resin (A) in which the phenolic hydroxyl groups are epoxidized or aryl-etherified and the ratio of the hydroxyl groups aryl-etherified to those epoxidized is 0.5-9.0. Component A is mixed with a polymaleimide compound (B) having at least two maleimide groups in the molecule in such an amount to provide a ratio of the number of the double bonds in component B to that of the double bonds in component A of 0.5-3 and, optionally, a curing agent (C).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition, and more particularly to a thermosetting resin composition having excellent processability, heat resistance, and adhesive properties. 0 is used in various electrical insulation materials, structural materials, etc. as impregnation, lamination, and molding materials.
In recent years, the conditions for using materials in each of these applications have tended to become stricter, and the heat resistance of materials has become an especially important property.In addition, in laminates, etc., it is important to have not only heat resistance but also adhesion to the base material. Traditionally, thermosetting polyimide resins have been used for this purpose, but they require heating at high temperatures and for long periods of time to harden, and they also have problems with the base material. Adhesion was insufficient.

In addition, 1# epoxy resin with improved thermal properties has excellent processability.
Although the adhesion was impaired, the mechanical properties at high temperatures, electrical properties, and high-level energization performance such as poor heat resistance during the mounting stage were insufficient.

As an alternative material to these materials, for example, a thermosetting mixture consisting of polyimide, an allyl group-containing epoxy compound having a specific structure, and a five-year-old agent (Japanese Unexamined Patent Publication No. 52-1548
97) has been proposed, but the allyl ρ group-containing epoxy compound used here is an epoxidized Claisen rearrangement of an allyl ether compound, in which the nuclear substituted allyl group and the epoxy group are anti-aromatic. Perhaps because it is located at the ortho position of the ring, it is difficult to obtain a uniform ε-formed compound, and especially in the case of novolak type, one of the groups tends to remain unresolved. 1 Thermal characteristics'
There was a problem with 9.

Against this background, the present inventors have developed a resin composite material with excellent heat resistance properties. As a result, certain resins,
The present inventors have discovered that a composition containing a maleimide compound and, if necessary, a curing agent is suitable for the above-mentioned purpose and has completed the present invention.

That is, the present invention provides (5) a hook tree of phenols having epoxidized and allyl etherified phenolic hydroxyl groups, (B) a polymaleimide compound having two or more maleimide groups in the molecule, and As necessary (C1
A thermosetting tree containing a hardening agent! A beak composition is provided.

Component (3) used in the present invention is an a/L'″f group,
ary/V group, afurkyl group, akenyl group, or unsubstituted or unsubstituted phenols, specifically phenol, cresol, ethylphenol, isopropylphenol, butylphenol, octylphenol, Nonylphenol, vinylphenol, impropenylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, xylenol, methylbutylphenol, methoxyphenol, ethoxyphenol, α-methylbenzylphenol, β-phenylethylphenol, dihydroxybenzene (isomers of each ), bispheno-/vA, etc., and an aldehyde such as formaldehyde, furfural, acrolein, glyoxal, etc. by a known method. By partially epoxidizing the allyl etherified phenol Novohook resin obtained by reacting the Novohook resin having the following with an allyl halide such as allyl chloride, allyl bromide, allyl iodide, etc. in the presence of an alkali. The method for partially epoxidizing the phenolic Novowoc resin is to partially epoxidize the phenolic Novowoc resin to the desired allyl etherification compound, and then convert the remaining hydroxyl groups to epichlorohydrin, shrimp bromohydrin, etc. A method of reacting methylepichlorohydrin with shrimp halohydrin in the presence of an alkali,
Alternatively, after almost completely allyl etherification, there is a method of partially epoxidizing with a peroxide such as hydrogen peroxide or peracid to achieve a desired epoxidation rate.

Here, the ratio of allyl etherified hydroxyl groups to epoxidized hydroxyl groups should preferably be between 0.5 and 90, more preferably between 07 and 4.0.

If the ratio of allyl ether groups is large, the adhesion properties will be reduced, while if the ratio is small, the IIthIP properties will be reduced. It is a compound containing two or more.

(In the formula, R represents a hydrogen atom or a lower alkyl group.

) Specific examples of the N,N-bismaleimide compounds include N,N'-diphenylmethane bismaleimide, N,N'-phenylenebismaleimide F, N,N'-
diphenyl ether bismaleimide, N,N'-)phenylsulfoniimide, N,N'-dicyclohexylmethane bismaleimide F, N,N-xylene bismaleimide,
N,N'-tolylene bismaleimide, N,N-quinrylene bismaleimide, N,N'-nophenyμsmaleimide, N,N'-diphenylmethane bismethylmaleimide, N,N'-diphenyl ether bismethylmaleimide, N, N'-Diphenylnurphonebismethylmaleimide (including major isomers), N. *-Ethylene bismaleimide, N.

N'-hexamethylene bismethylmaleimide, N'-hexamethylene bismethylmaleimide, and N, N
Examples include a prepolymer having an N, N'-bismaleimide core at the end obtained by cauterizing a '-bismaleimide compound and a diamine, and a maleimide or methylmaleimide of an aniline/formalin@condensate.

Particularly preferred are N,N'-diphenylmethane bismaleimide and N,N-diphenyl ether bismaleimide.

Examples of component (C) used in the present invention as needed include bisphenol A and tetrabromobisphenol A. Bispheno-A/P, BinuphenolvS, Bis(
4-hydroxyphenyl)cyclohexane, bis(4-
Hydroxyphenylethane, 1,3.3-)rimethyl-
1-m-hydroxyphenylindan-5- or 7-
All, 1.8.8-) Limef IV -1-p-Hydroquine phenyl indan-6-ol, resorcinol, hydroquinone, catechol A/, polyphenol compounds such as phenols Novowoc, which are raw materials for the recovered portions listed in n. , maleic acid, lid/l/9, nadic acid, methyl-tetophhydrophtha/L'^y1 polycarphonic acids such as methylnadic acid and their hydrates, diaminodiphenylmethane,
Diaminodiphenylsulfone, soaminodiphenyl ether, phenylenediamine, diaminocyclohexylmethane, gysylylenediamine, toluenediamine, xylenediamine, diaminodiphecinyl diclohexane, dichloro-diaminodiphenylmethane (each containing isomers), ethylenediamine, hexamethylene Polyamine compounds such as diamines, boron trifluoride complexes, heptamine trifluoride amine complexes such as boron trifluoride piperidine complexes, imidazole derivatives, tertiary amines, quaternary ammonium salts In addition, active hydrogen-containing compounds that can react with epoxy groups such as dicyandiamide and tetramethylguanidine can be exemplified. This can be selected as appropriate depending on the situation, but in general, the ratio of the double bonds in the FB component to the double bonds in the recovered component is 0.5 to 3, and when using the component (C), the ratio of ( It is preferable to select component C) so that the active hydrogen ratio is 8 or less.

In the present invention, each component can be reacted in advance to the extent that gelation does not occur, but when using 8 min, the recovered component is first reacted with the FC) component, and then the FB) component is reacted. is preferable in terms of cured physical properties.

The resin composition of the present invention can be easily cured by heat. In this case, curing is accelerated by adding radical polymerization initiators such as azo compounds and organic peroxides, ionic catalysts such as tertiary amines, quaternary ammonium salts, imidazoles, and boron trifluoride/amine salts. You can also do that.

The resin composition of the present invention can be processed in a mixer or kneader at a relatively low temperature.
It is possible to prepare a casting or molding material by blending various fillers and reinforcing materials using a roll, etc. Furthermore, it can be dissolved in molten 4J and applied to various reinforcing fibers such as glass fibers and carbon VR pheasants. It can also be used as a complimentary material. Also,
Depending on the purpose, other known thermosetting resins such as other allyl resins, epoxy resin, unsaturated polyester/L' resin, pheno-A/jugetsuji, silicone jyojinji, triazine resin, etc. may be used. May be added.

Thus, the 1N finger composition of the present invention has excellent processability, thermal properties, and adhesive properties, and is useful as a material for casting, impregnation, lamination, and molding. In order to explain the present invention in detail, elements and examples are shown, but the present invention is not limited thereto. F indicates units.

eExample 1 (Partial allyl etherification) O-Taresol pot hook resin 2 with a softening point of 90°C was placed in a reactor equipped with a thermometer, a stirrer, a dropping port and a continuous flow condenser.
Add 36 parts (2 parts) and 840 parts of dimethylformamide, and after completely dissolving the resin, add 62 parts (1.5 parts) of 9796 soda. Stir well. While maintaining the temperature of the reaction thread at 40°C, 120 parts of allyl chloride (1,58 parts per needle) was added dropwise over 1 hour.
Raise the temperature in a ℃ oven and hold at the same temperature for 6 hours. Next, after distilling off dimethylformamide, 300 parts of toluene was added to dissolve the resin, and the inorganic salts were removed by washing with water and filtration.
By concentrating the p solution, allyl etherification rate 75 g6, OH equivalent 5921
0 (Epoxidation) Obtained 282 parts of red-orange viscous liquid resin of /・q Temperature needle, stirrer, lower pot and water recovery i1+If
The above partial allyl etherification rate 28 was added to the reactor marked with f.
Charge 6.8 parts (0.4 parts) and 870 parts (4.0 parts) of epichlorohydrin, and increase the pressure of the reaction system to 150 HP.
Then, gradually heat the thread and bring it to a boil, then add 85 parts of 48 eucaustic soda aqueous solution (0.42% light) to a reaction temperature of 62°C.
Gradually add over 2 hours to 1 hour while holding at a temperature of 2 hours. During the reaction, water is removed from the reaction system in the form of an azeotrope with epichlorohydrin, and after the completion of dropping caustic soda to imitate epichlorohydrin, the same conditions are maintained for an additional 30 minutes.

Next, the salt was separated from the reaction mixture and the mother liquor was concentrated to obtain 240 parts of a yellow-orange viscous liquid with an epoxy equivalent of 658 P/eq. (referred to as AEN-1)) Reference Example 2 (Partial allyl etherification) In Reference Example 1, 600 parts of dimethyl sulfoxide and 41 parts of 97% caustic soda (1,
0 equivalent yellow), ant chloride/L/82 parts (1,08 equivalent A1°)
262 parts of a reddish-brown semi-solid resin having an allyl etherification rate of 50 or more and an OR equivalent of 276 F/·q, which does not have a nuclear substituted aryl group, was obtained in the same manner except that .

(Epoxidation) In Reference Example 1, the above partially allyl etherified product 220
．． 8 parts (0.8 equivalents), 444 parts of epichlorohydrin (
4,8 equivalents), 48g6 Caustic soda aqueous solution M70 parts (0,
84 equivalents) was used in the same manner, except that 84 equivalents of epoxy were used.
48 P/eq O 248 parts of yellow-orange semi-iH type resin were obtained (referred to as AEN-2) Example 1 1,200 parts of AEN-obtained in β element side-1 N, N'
-! /phenylmethane bismaleimide 269ffit7
00 parts of N,N-dimethylformamide (DMF')
Dissolve this solution in Gafnu Cloth (Yaribo P11KS-
1600, A-1100) Impregnated with K.

Next, the prepreg was heated in an oven at 180° C. for 10 minutes, and the prepreg was injected. Six sheets of this prepreg were stacked and molded at 180°C under a pressure of 50 νH for 60 minutes, and then cured in a 180°C oven for 2 days to obtain a laminate in the same manner as in 90.
Table 1 shows the physical properties of the six prepregs.

Example-2 386 parts of A EN-2 obtained in Reference Example-2 and N, N
'-269 parts of dipheniμ methane bisleimide 900 parts
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.

Example-8 2,886 parts of AEN-2 obtained in Reference Example-2, 55 parts of bispheno-A/A, and 10.2 parts of 2,4.6-)lis(dimethylaminomethy/L/)pheno-/I were combined at 180 parts. The mixture was reacted for 80 minutes at °C, and then 269 parts of N,N'-diphenylmethane bismaleimide was added to dissolve 990 parts of DMFK. 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 N, 4 to 179 parts of N-diphenylmethane bismaleimide
．． Add 37 parts of 4'-diphenymethane and stir at 180°C for 5 minutes. Next, 20 parts of DMFJ was added and dissolved uniformly. 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 of the present invention has excellent heat resistance, water resistance, electrical insulation and adhesive properties. Furthermore, it can be seen that the composition according to the present invention has excellent solubility in solvents and excellent processability such as curing at a temperature of 180°C.

Claims (2)

[Claims] (1) (A) A phenolic novolak resin in which the 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 comprising: (2) The thermosetting resin composition according to claim 1, wherein the ratio of allyl etherified hydroxyl groups to epoxidized hydroxyl groups is from 0.5 to 9.0.