JPH0431409A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. excellent in low-temp. curing properties, heat resistance, and mechanical strengths by compounding a maleimide compd. with an N-substd. linear aliph. amine having at least two N-vinylbenzyl groups. CONSTITUTION:A maleimide compd. (e.g. N,N'-diphenylmethanebismaleimide) is compounded with an N-substd. linear aliph. amine having at least two N- vinylbenzyl groups in the molecule [e.g. a compd. of the formula (wherein X is a residue of a linear aliph. amine from which y H atoms of amino groups are removed; and y is 2-6) obtd. from a linear aliph. amine, e.g. ethylenediamine] to give the title compsn., which is amorphous, lowly viscous, excellent in workability, low-temp. curing properties, heat resistance, and mechanical strengths, and hence widely used for an adhesive, for a casting, impregnating, or laminating material, and for a coating, insulating, or composite material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a curable polymaleimide resin composition. In particular, the present invention relates to a curable resin composition that is excellent in low-temperature curing, heat resistance, and mechanical properties.

[Conventional technology]

Curable compositions are widely used as adhesives, castings, coatings, impregnations, laminations, molding compounds, etc. in paints, insulating materials, composite structural materials, and the like.

Among them, polyimide resin is one of the most excellent materials, and various developments are underway. 62-53319
Known by the number.

[Problem to be solved by the invention]

However, the above-mentioned resin composition has a high curing temperature,
The curing time is long, and in terms of workability including this,
It is still not advantageous compared to existing general-purpose curable resins.
In addition, in recent years, curable resins have been used for a wide variety of purposes, so the curable resin compositions that have been used traditionally are
Conventionally known bismaleimides, aromatic amines, and epoxy resins are not satisfactory in all usage environments or conditions, especially in high-temperature usage, and their heat resistance and hot strength are insufficient. Even in the most typical compositions, such as a combination of
Sufficient materials were not yet available.

Therefore, the present invention solves the above-mentioned problems of conventional curable resin compositions, and has a low curing temperature, short curing time, excellent heat resistance and thermal stability, and excellent mechanical properties. The purpose is to provide a polyimide resin composition.

[Means to solve the problem]

The present inventors have discovered that a curable resin composition consisting of a maleimide compound and a vinylbenzyl ether compound bonded to an aromatic residue is effective, and has already been published in JP-A-64
-65110, but after further research,
We are looking for a curable resin composition with excellent heat resistance such as hot strength.

That is, the composition of the present invention is a curable resin composition comprising (A) a compound having a maleimide group in the molecule, and (B) an N-substituted chain aliphatic amine having two or more N-vinylbenzyl groups in the molecule. Compared to the invention of JP-A No. 64-65110, it can be cured at a similar low temperature, has a shorter curing time, and has even better thermal stability and mechanical properties, especially hot strength. The present invention provides a curable resin composition.

The present invention will be explained in more detail below.

Examples of the compound (A) having a maleimide group in the molecule, which is a component of the composition of the present invention, include N,N'-phenylene bismaleimide, N,N'-xylene bismaleimide, N,
N'-tolylene bismaleimide, N,N'-diphenylmethane bismaleimide, N,N'-diphenyl ether bismaleimide, N,N'-diphenylsulfone bismaleimide, N,N'-diphenylmethane and smethylmaleimide, N,N ~ Diphenyl ether and bismaleimides such as smethylmaleimide, or adducts of the above-mentioned bismaleimides with amino compounds or epoxy resin-modified amine compounds such as diaminodiphenylmethane, diaminodiphenyl sulfone, and diaminodiphenyl ether, which are still molecules. A typical example is a compound having two maleimide groups therein.

Furthermore, monofunctional maleimide compounds such as aromatic maleimides such as phenylmaleimide, alicyclic maleimides such as cyclohexylmaleimide, and alkylmaleimides such as laurylmaleimide can also be used, but they are preferably used in place of a part of the bismaleimide compound. be able to.

In addition, N-
An N-substituted chain aliphatic amine having two or more vinylbenzyl groups is -Funazura (1) % formula %) (wherein, X represents y hydrogen atoms in the amino group of the chain aliphatic amine. (where y has a value of 2 to 6).

- Typical chain aliphatic amines used as raw materials in shipyard (1) are butylamine, isobutylamine, pentylamine, isoamylamine, hexylamine, methylene diamine, ethylene diamine, propylene diamine, trimethylene diamine, and tetramethylene diamine. , 1,3-diaminobutane, 2,3 diaminobutane, pentamethylene diamine, 2,4-diaminobentane, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, 1,2,3-1-lyaminopropane, Tris (2
-aminoethyl)amine, tetra(aminomethyl)methane, diethylenetriamine, triethylenetetramine,
Tetraethylenepentamine, heptamethylenediamine,
Nonaethylenedecamine, bis(3-aminoethyl)amine, diethylaminopropylamine, iminobispropylamine, bis(hexamethylene)triamine, trimethylhexamethylene diamine, diethylene glycol bispropylene diamine, polymethylene diamine, branched poly Methylene diamine, polyether diamine, 2゜5
-dimethylhexamethylenediamine, pentaethylenehexamine, aminoethylethanolamine, tri(methylamino)hexane, dimethylaminopropylamine,
Methyliminobispropylamine, amine-terminated polybutadiene acrylonitrile (Gutdrich, Hiker ■
＾TBN) etc.

N-substituted chain aliphatic amine (B
), for example, by adding commercially available chloromethylstyrene monomer to the chain aliphatic amine in a proportion of 2 to 6 vinylbenzyl groups, and dehydrochlorinating with an inorganic alkali using dimethyl sulfoxide as a solvent. Can be easily synthesized.

The composition ratio of the maleimide compound (A) and the N-vinylbenzyl chain aliphatic amine (B) in the present invention can be varied widely depending on the purpose of use.

When expressed as the equivalent ratio of each unsaturated group, A/B=100/
30 to 1/100, preferably 100150 to 1/3
0 is better. Within this range, the resin can be easily thermally cured without intentionally adding a radical initiator necessary for curing, and the reaction proceeds at a much lower temperature and in a shorter time than when each type of resin is thermally cured individually. In addition, the thermal decomposition initiation temperature in air is high and the decomposition loss is small.

The curable resin composition of the present invention comprises components (A> and (B))
In addition, known monomers such as styrene, vinyltoluene, allylphenol, allyloxybenzene, diallyl phthalate, acrylic ester, methicrylic ester,
Alternatively, vinyl ester resin, vinyl pyrrolidone, etc., typified by a reaction product of epoxy resin and (meth)acrylic acid, can be blended. In order to adjust the curing, hydroquinone, benzoquinone, copper salt, ammonium salt or aluminum salt of N-nitrosophenylhydroxylamine, etc. may be blended, and in order to accelerate the curing, known and publicly available radical initiators, such as Organic peroxides or an organic peroxide and its decomposition accelerator (REDOX) can also be blended.

Furthermore, the curable resin composition of the present invention can be cured with active energy rays, such as ultraviolet rays and laser beams, and can also be easily cured with electron beams by incorporating a publicly known photoinitiator.

The curable resin composition of the present invention can be used in kneaders, blenders,
Various other fillers and reinforcing fibers are prepared using rolls, etc., and dissolved in molding materials, composite materials, and solvents to produce surfaces, paints, adhesives, and reinforcing fibers such as glass fiber, carbon fiber, and aromatic polyamide. It can be impregnated into fibers, silicon carbide fibers, and alumina fibers to become useful molding and structural materials in handlay assemblies, prepregs, and filament windings.

〔Example〕

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

In addition, unless otherwise specified, parts in the examples are parts by weight.

To a solution of 15 parts (1.0 equivalents) of ethylenediamine (anhydrous) in 80 parts of dimethyl sulfoxide, 152.5 parts (1.0 equivalents) of commercially available chloromethylstyrene to which 500 ppm of hydroquinone was added was added at 60 to 70°C. 10
After dropping for 70 to 8 minutes, add 70 to 8 parts of potassium hydroxide aqueous solution [56.1 parts (1.0 equivalents) of potassium hydroxide, 35 parts of water].
The mixture was added dropwise at 0°C over 1 hour, and the reaction was further continued at 75°C for 4 hours.

Next, a large excess of water was added to the system, and after stirring, water-dimethyl sulfoxide was removed, and an oily substance was extracted with benzene. The benzene layer was washed repeatedly with water until the pH of the aqueous layer reached 7.
Benzene is removed under reduced pressure to produce N, N, N', N as an oil.
'-Tetravinylbenzylethylenediamine, N
-TVBED8> was obtained in a yield of 95%. Furthermore, the same synthesis is possible by using dioxane or N,N-dimethylformamide instead of the dimethyl sulfoxide used here.

In the same manner, hexamethylene diamine was used instead of ethylene diamine (hereinafter referred to as N-TVBI (MD^)), and diethylene triamine was used (N-PVBD).
ET^), using triethylenetetramine (
N-vinylbenzylamines were synthesized using N-HVBTET^).

Table 1 shows the properties of each N-vinylbenzylamine. Each N-vinylbenzylamine was soluble in various organic solvents such as benzene, toluene, acetone, and MEK.

Similar tests were conducted on hair, nonylbenzylamine, and BMI. The results are shown in Table-2.

358 parts of N,N'-diphenylmethane bismaleimide (
1.0 mol) and 99 parts of diaminodiphenylmethane (
0.5 mol) was thoroughly ground and mixed in a ball mill, melted and stirred in a container at 170° C. for 10 minutes, and the container was immediately cooled with water to obtain a solid.

This reactant was soluble in solvents such as N-methylpyrrolidone and dimethylformamide, and was also soluble in low-boiling point solvents such as acetone and methyl ethyl ketone (hereinafter referred to as D
DM modified BMI).

K1 fake" Synthesized in Reference Example 1 N-TVBEDA, N-TVBHI
4DA, N-PVBDETA, N-)IVBTET^,
Samples were prepared by mixing 1 equivalent of each of them with 1 equivalent of diphenylmethane bismaleimide (hereinafter referred to as BMI) manufactured by Mitsui Toatsu, and the samples were placed on a hot plate at 120° C. to examine gelation. For comparison, each N-BiN
-TVBEDA, N-TVBHNDA, N-PVBDE
A sample in which 1.0 equivalent of BMI was mixed with 1.0 equivalent of each of TA and N-HVBTET^ and 1.0 equivalent of DDM-modified EIMI synthesized in Reference Example 2 were mixed in the theoretical equivalent, and the mixture was heated at 120°C. It was molded for 30 minutes. Continued to 250 after demolding
After post-curing at ℃ for 5 hours, thermal decomposition start temperature in air, bending strength at room temperature and hot according to JIS K 6911, and bending elastic modulus were measured. The results are shown in Tables 3 and 4.

The flexural strength and flexural modulus of the material were measured. The results are also shown in Table 4.

Temperature ratio at 5% weight loss at a vehicle heating rate of 0°C/min As a comparison, the present inventors used a vinyl benzyl ether compound consisting of a maleimide compound and an aromatic residue bonded together. Curable composition (JP-A-64-6511)
As an example of No. 0), for 1 equivalent of bisphenol A divinylbenzyl ether (BADVBE), Example 1
The BMI used in Example 2 or the DDM-modified BMI synthesized in Reference Example 2 were each mixed in an amount of 1.0 equivalent theoretically.
Molding was carried out at 80°C for 30 minutes. Subsequently, the curable resin composition according to the present invention is amorphous and has a low viscosity due to the above-mentioned structure. Because of its excellent workability and excellent low-temperature curing, heat resistance, and mechanical strength, it can be used as an adhesive, casting, coating, impregnation, or laminated molding compound, or as a paint, insulating material, or composite structural material. , can be widely used in industry.

Claims (1)

[Claims] (A) A compound having a maleimide group in the molecule, and (B
) A curable resin composition comprising an N-substituted chain aliphatic amine having two or more N-vinylbenzyl groups in the molecule.