JPH0212966B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyfunctional maleimide composition with accelerated gelation and curing speed,
Specifically, it is a curable resin composition with increased gelation and curing speed, which is made by adding and mixing 0.0001 to 10 wt% of a metal chelate to a polyfunctional maleimide.

Conventionally, polyfunctional maleimides have been used as insulating materials, structural materials, etc. because their cured products have high heat resistance.
Various research and developments are being carried out in the fields of molding materials, adhesives, etc. Polyfunctional maleimides can be gelled and hardened simply by heating, but heating at high temperatures and for long periods of time is usually required. That is, it requires a large amount of energy and has poor productivity.

The present invention was completed based on the results of research into solving the above-mentioned drawbacks and the discovery that metal chelates have the effect of accelerating the gelation and curing speed of polyfunctional maleimides.

The present invention will be explained below.

The polyfunctional maleimides of the present invention are N in the molecule.
- A polyfunctional maleimide containing two or more maleimide groups, a prepolymer of the maleimide, or a prepolymer of the maleimide and an amine. What is polyfunctional maleimide?The following general formula (1) (In the formula, R is a divalent, usually less than pentavalent aromatic or alicyclic organic salt, and X ¹ and X ² are hydrogen, halogen,
or an alkyl group, where m is 2 or more and usually 5 or less. ) is a compound represented by The maleimide represented by the above formula has maleic anhydride and an amino group of 2 to 2.
It can be produced by a method known per se, in which maleamic acid is prepared by reacting with a polyamine having five polyamines, and then the maleamic acid is cyclized by dehydration. It is preferable that the polyamines used are aromatic amines in terms of the heat resistance of the final resin, but if flexibility and flexibility of the resin are desired, alicyclic amines may be used alone or in combination. good. Furthermore, it is particularly desirable that the polyvalent amines be primary amines in terms of reactivity, but secondary amines can also be used. Suitable amines include meta or paraphenylene diamine, meta or para xylylene diamine, 1,4- or 1,3-cyclohexane diamine, hexahydroxylylene diamine,
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-aminophenyl)cyclohexane, 2,2- Bis(4-aminophenyl)propane, 2,2-bis(4-amino-3-
methylphenyl)propane, bis(4-amino-
3-chlorophenyl)methane, 2,2-bis(3,5-dibromo-4-aminophenyl)propane, bis(4-aminophenyl)phenylmethane, 3,4-diaminophenyl-4'-aminophenylmethane, 1, These include 1-bis(4-aminophenyl)-1-phenylethane, melamines having an s-triazine ring, and polyamines made by reacting aniline with formalin and linking benzene rings with methylene bonds.

In the present invention, the above-mentioned polyfunctional maleimide can also be used in the form of a prepolymer instead of in the form of a so-called monomer.

The metal chelate of the present invention is used as a catalyst or promoter in the polymerization of polyfunctional maleimides. A large number of metal chelates are known,
Much data is collected and known in the art regarding their manufacture, properties and uses. A metal chelate is a substance consisting of a metal and a compound with two or more donor atoms that can be used as ligands to form the metal chelate. As the metal, chelates using transition metals, particularly iron, cobalt, zinc, copper, manganese, zirconium, titanium, vanadium, aluminum, and magnesium are easily available and preferred. On the other hand, as a compound having two or more donor atoms that can be used as a ligand for the production of a metal chelate, bidentate or tridentate ligands are easily available and are preferred.

The metal chelates of the present invention include acetylacetone, benzoylacetone, hexafluoroacetylacetone, 2-acetylphenol, ethyl acetate, oxalic acid, malonic acid, phthalic acid, catechol, salicylic acid, utanolamine, hydroxyquinoline, 2-hydroxypyridine, -Aminophenol, 2-acetylpyridine, 2-pyridine aldehyde, 2-amino complex acid, N-(n-butyl)salicylamidoimine, phenyl-β-ketoimine, ethylenediamine, 1,2-diaminobenzene, 0-phenanth Lolin, dimethylglyoxime, 2-mercaptoethylamine, 2-aminothiophenol, methylthiosemicarbazide, 0-mercaptobenzoic acid, thioglycolic acid, 0-methylthiobenzoic acid, s-methylthioglycolic acid, dimethylthioethane, 1,2- Benzenedithiol, ethanedithiol, 0-methylthiobenzenethiol, 8-(α-pyridylmethyleneamino)quinoline, diethylenetriamine,
Phenylbis(2-diethylphosphinophenyl)phosphine, salicylidene-2-aminomethylpyridine, bis(acetylacetone)ethylenediimine, 1,2-bis(α-pyridylmethyleneamino)ethane, triethylenetetramine, 1,
9-bis(2-pyridyl)-2,5,8-triazanonane, 1,8-bis(salicylideneamino)
-3,6-dithioctane, ethylenediaminetetraacetic acid, 1,5,5,5-hexafluoro-2,
4-pentanedione, 2,4-pentanedione,
Examples include 2-hydroxybenzaldehyde, 8-hydroxyquinoline, and the like.

Particularly useful are acetylacetone, hexafluoroacetylacetone, salicylaldehyde, benzoylacetone, 1-(2-pyridyl)-3-(2-benzothiazolyl)-2,3-diazo-1-propane, oxalic acid, and ethylenediamine.

The above amount of metal chelate of the present invention used is 0.0001
-10wt%, preferably 0.001-5wt%. It varies depending on the type of metal chelate and the type of polyfunctional maleimide used, but if it is less than 0.0001wt%, its catalytic or accelerating effect on gelation and curing reactions will be small, and if it is more than 10wt%, the properties of the cured product will be affected. It is undesirable because it has a negative effect on

The metallate of the present invention may be added to the polyfunctional maleimides by mixing in solid form such as powder, by dissolving it in a solvent, or by adding it to the polyfunctional maleimide using another reactive diluent. It may be dissolved and added. They may be heated and mixed in a molten state.

The composition of the present invention may contain various additives as desired, as long as the original properties of the composition are not impaired. These additives include:
Natural or synthetic resins for imparting new properties to the composition of the invention; fibrous reinforcement; fillers;
Various known additives such as dyes and pigments; thickeners; lubricants; and flame retardants are included, and may be used in appropriate combinations as desired.

The curable resin composition of the present invention as described above is excellent in terms of its rapid gelation and curing speed, and has extremely great practical significance.

The present invention will be explained below with reference to Examples.

Example 1 Bis(4-maleimidophenyl)methane 100
g was dissolved in 400 g of N,N dimethylformamide, and 1 g of iron acetylacetonate was dissolved in 10 g of N,N dimethylformamide and mixed.

The time required for gelation of the obtained solution on a heating plate at 170°C (abbreviated as gel time) was measured. Gel time was 1 minute 16 seconds.

Comparative Example 1 The same procedure as Example 1 was carried out except that iron acetylacetonate was not added.

Gel time was over 20 minutes. (It did not gel even after 20 minutes.) Example 2 Bis(4-maleimidophenyl)methane 100
g and 0.1 g of zinc acetylacetone were mixed in powder form.

The gel time of the obtained powder mixture at 170°C was 5 minutes and 20 seconds.

Comparative Example 2 The same procedure as Example 2 was carried out except that zinc acetylacetone was not added.

Gel time was over 20 minutes. (It did not gel even after 20 minutes.) Example 3 Prepolymer of bis(4-cyanatophenyl)methane and amine (Kelimide 601: manufactured by Rhone Poulenc) 100g and copper acetylacetone 0.05g
g was dissolved in 400 g of N,N dimethylformamide, and the gel time was measured.

The gel time was 4 minutes and 41 seconds at 170°C.

Comparative Example 3 The same procedure as Example 3 was carried out except that copper acetylacetone was not added.

The gel time was 6 minutes and 1 second at 170°C.

Example 4 A glass cloth was impregnated with the varnish obtained in Example 1 and dried at 140°C for 6 minutes to obtain a prepreg. 8 sheets of the obtained prepreg were stacked and heated at 200℃ for 3
Time press cured.

The glass transition temperature of the obtained laminate was 292°C.

Comparative Example 4 Example 4 except that the varnish obtained in Comparative Example 1 was used.
I did the same thing.

The glass transition temperature of the obtained laminate was 220°C.

Claims (1)

[Claims] 1 Adding metal chelates to polyfunctional maleimides
A curable resin composition with accelerated gelation and curing speed, which is obtained by adding and mixing 0.0001 to 10 wt%.