JPS6134464B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a heat-resistant resin composition, and particularly to a resin composition that has excellent heat resistance and adhesive properties. This resin composition is particularly useful as an electrically insulating material, and can be used in a wide range of applications such as solvent-free varnishes, casting resins, and laminating resins. Solvent-free varnishes are 100% free because they do not contain solvents.
Since there is no usable waste, it is preferable from the standpoint of safety and health, as well as the effective use of resources. Also,
Technically, it has the advantage of being able to obtain a void-free resin layer, and is becoming mainstream in place of conventional solvent-based varnishes. Polyester resins, epoxy resins, and the like are already known as solvent-free varnishes, but these all have the disadvantage of being severely degraded at high temperatures and cannot withstand long-term use at high temperatures. In general, when epoxy compounds are mixed with a curing agent and cured, they become resins with excellent electrical properties, dimensional stability, chemical resistance, etc., and are used in a wide range of fields. However, as mentioned above, it is not necessarily sufficient in terms of heat resistance. On the other hand, it is known that maleimide compounds undergo vinyl polymerization and are known to exhibit very high thermal stability. For example, a method for producing three-dimensional polyimide by heating and polymerizing N,N'-disubstituted maleimide alone is disclosed in French Patent No. 145514.
Known by the number. However, this three-dimensional polyimide has too high a crosslinking density and is brittle and easily cracks when heated and cooled, so it has drawbacks such as being impractical for purposes such as casting resins. Furthermore, there has been a proposal (such as Japanese Patent Publication No. 12600/1973) to blend this epoxy compound with a maleimide compound to provide a resin with high heat resistance, but although this blend of epoxy resin and maleimide compound has excellent heat resistance, However, it has the disadvantage that it has poor adhesion and tends to peel off when used for impregnation, casting, etc. The present inventors have conducted extensive research to improve these drawbacks, and as a result, have arrived at the present invention. That is, the present invention relates to a heat-resistant resin composition formed by blending a specific maleimide compound into a system of an epoxy compound and an acid anhydride, and is represented by the general formula (). (In the formula, R represents -H or an acetyl group) and a monomaleimide compound represented by the general formula () (In the formula, R' is a divalent organic group, m is 0.5 on average
A compound having at least two epoxy groups in one molecule and 100 parts by weight of an acid anhydride as a curing agent are blended with 5 to 200 parts by weight of a polymaleimide compound represented by This is a characteristic feature. In particular, it is characterized by providing heat resistance and adhesiveness by using a maleimide compound represented by the general formula (). In the present invention, the heat resistance is increased due to the maleimide crosslinked structure, and -
The presence of components with OH groups or _-OCOCH groups increases adhesiveness with other materials. In the present invention, the maleimide component has the general formula () (In the formula, R' represents a divalent organic group) A predetermined part by weight not exceeding 100 parts by weight is added to 100 parts by weight of the maleimide compound represented by the above general formulas () and (). Can be used within a range. General formula () that can be used in the present invention Examples of monomaleimide compounds represented by (wherein R is the same as above) include 3-hydroxyphenylmaleimide, 4-hydroxyphenylmaleimide, 3-acetoxyphenylmaleimide, 4
- Examples include acetoxyphenylmaleimide. Also, the general formula () The poly(phenylmethylene)polymaleimide compound represented by the formula (where m is from 0.5 to 4 on average) can be easily obtained by reaction of polyphenylmethylene polyamine and maleic anhydride. Furthermore, the general formula () that can be used in the present invention Examples of the compound represented by (in the formula, R' is a divalent organic group) include N,N'-(methylenedi-p-phenylene) dimaleimide,
p-phenylene) dimaleimide, N,N'-m-
Phenylene dimaleimide, N,N'-p-phenylene dimaleimide, N,N'-2,4-tolylene dimaleimide, N,N'-2,6-tolylene dimaleimide, N,N'-m- Xylylene dimaleimide, N,N'-p-xylylene dimaleimide,
N,N'-xysidipropylene dimaleimide, ethylenedioxybis-N-propylmaleimide,
Oxybis-N-ethylmaleimide, N,N'-
Ethylene dimaleimide, N,N'-trimethylene dimaleimide, N,N'-tetramethylene dimaleimide, N,N'-hexamethylene dimaleimide, N,N'-dodecamethylene dimaleimide,
etc. can be mentioned. Furthermore, the epoxy compounds that can be used in the present invention include bisphenol A diglycidyl ether type Epicote 828, 834, 1001,
Novolac type such as 1004 (Ciel Corporation)
DEN438 (Dow Corporation) and alicyclic type Chitsonox 221, 289 (Chitso Corporation) can be used, but are not limited to these. or,
Furthermore, the epoxy curing agent that can be used in the present invention has the general formula (However, R ₁ in the formula is

【formula】

【formula】

【formula】 【formula】

【formula】

[Formula] -CH=CH-, -CH ₂ -CH ₂ -,

As shown in [Formula] etc. ), or

[Formula] Acid anhydride (R ₄ is

【formula】

【formula】

【formula】

【formula】

[Formula] etc.). The composition of the present invention is characterized in that 5 to 200 parts by weight of the above maleimide compound is blended with 100 parts by weight of the mixture of the epoxy compound and acid anhydride shown above. Furthermore, the amount of hydroxyphenylmaleimide and acetoxyphenylmaleimide in the maleimide compound is 10% of the total maleimide weight.
~50%. In the present invention, when the amount of the maleimide compound is less than 5 parts by weight with respect to 100 parts by weight of the mixture of epoxy compound and acid anhydride,
If the amount exceeds 200 parts by weight, sufficient heat resistance will not be obtained, and although heat resistance will improve, the crosslinking density of maleimide will increase and mechanical strength will decrease. Furthermore, if the proportion of the monomaleimide compound represented by the above general formula () in all maleimide compounds exceeds 50%, the heat resistance will not be sufficient;
% or less, the effect of improving adhesive strength cannot be obtained. The resin composition of the present invention obtained as described above has excellent heat resistance and adhesion, as well as excellent impregnability and castability, so it is particularly useful as an electrical insulating material. It can be effectively applied to various things by using a combination of agents and the like. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 21 parts by weight of Epicote 828, 11 parts by weight of Epicote 834
Parts by weight, 15 parts by weight of Chitsonox 221, 10 parts by weight of 4-acetoxyphenylmaleimide, N,N′-
(methylene-di-p-phenylene) dimaleimide
10 parts by weight of poly(phenylmethylene) polymaleimide were added and dissolved, and 22 parts by weight of methylnadic anhydride and 1 part by weight of DMP-30 were added to prepare a resin composition. 150℃ for 10 hours, then 200℃
It was cured for 8 hours to obtain a cured product. The heat distortion temperature (TMA method) of this cured product was 160°C. 240 more
The weight loss in air after 500 hours at °C was 9.4%. Straka method (using 1.0mmφ copper wire, 25℃,
The adhesive strength at a tensile speed of 200 mm/min) was 20.5 kg. The value after heat deterioration at 240°C for 500 hours was 15.5 kg. Furthermore, the peeling strength (T-shaped peeler with a peeling speed of 10 ipm, bonding 4 inches of aluminum plate 1 inch wide, 0.025 inch thick, and 5 inches long) at 25°C.
It was 12.1psi. In addition, the adhesive strength using the helical coil method (using 1.0 mmφ copper wire and winding around a 6.0 mmφ mandrel) was 31.0 kg at 25°C. Examples 2 to 3 Comparative Examples 1 to 3 Resin compositions and corresponding cured products were obtained in the same manner as in Example 1 with the formulations shown in Table 1, respectively. The results measured for these samples are
Also listed in the table. Incidentally, the bismaleimide compound represented by the above-mentioned general formula () tends to crystallize due to its structure and has low solubility in epoxy compounds and the like, which poses a practical problem. In other words, it does not dissolve in the epoxy compound beyond a certain concentration,
Not used as a varnish. On the other hand, the polymaleimide compound represented by the general formula () has a lower melting point and improved solubility due to the intramolecular fusion effect.

[Table] Comparative Example 4 A composition consisting of 5 g of 4-hydroxyphenylmaleimide, 15 g of bismaleimide (), 828.45 g of Epicote as an epoxy compound, and 35 g of methyltetrahydrophthalic anhydride is a stable varnish that crystallizes at temperatures below 40°C. It cannot be a physical object. Example 4 A composition with the same composition as above, in which the maleimide is of the general formula () (m is 1.0 on average), is stable even when cooled to room temperature and becomes a varnish-like product, and the cured product is hydroxyphenylmaleimide. The hydroxyl group increases adhesion.

[Table] As explained above, the resin composition according to the present invention has particularly excellent heat resistance and adhesive properties, and has extremely great industrial value.

Claims (1)

[Claims] 1 General formula () (In the formula, R represents -H or an acetyl group) and a monomaleimide compound represented by the general formula () (In the formula, m indicates a number from 0.5 to 4 on average) For 5 to 200 parts by weight of a polymaleimide compound represented by the formula, a compound having at least two epoxy groups in one molecule and an acid anhydride as a curing agent. 100
A heat-resistant resin composition characterized in that it contains parts by weight. 2 The monomaleimide compound is 10 to 10% of the total amount of the monomaleimide compound and the polymaleimide compound.
50% by weight of the heat-resistant resin composition according to claim 1. 3 General formula () (In the formula, R represents -H or an acetyl group) and a monomaleimide compound represented by the general formula () Polymaleimide compound represented by (in the formula, m represents a number from 0.5 to 4 on average) 5 to 200
A compound having at least two epoxy groups in one molecule and an acid anhydride as a curing agent, based on parts by weight.
100 parts by weight of the bismaleimide compound represented by the general formula () and 100 parts by weight of the maleimide mixture of the general formula () and the general formula (). [Here, R' is a group [formula] (Z represents -O-, -CH ₂ -, -S-)] in a predetermined weight part not exceeding 100 parts by weight. resin composition.