JPH0617424B2 - Curable composition - Google Patents

Description

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

[Prior Art] Curable compositions are widely used in paints, insulating materials, composite structural materials and the like as adhesion, casting, coating, impregnation, lamination, molding compounds and the like.

Among them, polyimide resin is one of the most excellent materials, and various developments have been promoted. For example, a composition of a polymaleimide compound and a reactive oligomer having an alkenyl ether at the end of the molecule is known from JP-A-62-53319.

[Problems to be Solved by the Invention] However, the curable composition described above has a high curing temperature and a long curing time, and in terms of workability including these, it is still more advantageous than existing general-purpose curable resins. Not really. In addition, since the curable resin has various uses in recent years, the curable resin compositions conventionally used are not all satisfactory in various use environments or use conditions. In particular, the heat resistance and hot strength at the time of using at high temperature are not sufficient, and even the most representative composition such as the conventionally known combination of bismaleimide, aromatic amine and epoxy resin is still insufficient. Materials were not provided.

Accordingly, the present invention solves the above problems of conventional curable compositions, has a low curing temperature, a short curing time, and is excellent in heat resistance and thermal stability, and further has excellent mechanical properties. An object is to provide a system curable composition.

[Means for Solving the Problems]

The present inventors have found that a curable composition comprising a maleimide compound and a vinylbenzyl ether compound bonded to an aromatic residue is effective, and already disclosed in JP-A 64-6511.
No. 0 was proposed, but further research was conducted to find a curable composition having excellent heat resistance such as hot strength.

That is, the composition of the present invention comprises (A) the general formula (I) (In the formula, R represents hydrogen or a methyl group, and Z represents a divalent aromatic group or a xylylene group.) A compound having a maleimide group in the molecule or an adduct thereof with a diamino compound A compound having two maleimide groups in the molecule, and (B) the general formula (II) (In the formula, X represents a hydrogen atom in the amino group of the aromatic amine.
N-substituted aromatic amine having an N-vinylbenzyl group and a vinylbenzyl ether group in the molecule represented by the following: m is a value of 1 to 16 and n has a valence of 1) And a curable composition containing, which can be cured at a similar low temperature as compared to the invention of JP-A-64-65110, has a short curing time, and further has excellent thermal stability and mechanical properties, It is intended to provide a curable composition having excellent hot strength.

The present invention will be described in more detail below.

The components of the composition of the present invention (A) (A) General formula (I) (In the formula, R represents hydrogen or a methyl group, and Z represents a divalent aromatic group or a xylylene group.) A compound having a maleimide group in the molecule or an adduct thereof with a diamino compound The compound having two maleimide groups in the molecule is, for example, N, N'-phenylene bismaleimide, N, N'-xylylene bismaleimide, N, N 'tolylene bismaleimide, N, N' diphenylmethane bismaleimide, N, N'-diphenylether bismaleimide, N, N'-diphenylsulfone bismaleimide, N, N'-diphenylmethanebismethylmaleimide,
Examples thereof include bismaleimides such as N, N ′ diphenyl ether bismethylmaleimide.

In addition, an adduct of the above-mentioned bismaleimide with an amino compound such as diaminodiphenylmethane, diaminodiphenyl sulfone, and diaminodiphenyl ether, or an adduct with an amino compound modified with an epoxy resin,
A compound which still has two maleimide groups in the molecule can also be used as the component (A) of the composition of the present invention.

It should be noted that aromatic maleimides such as phenylmaleimide and alicyclic maleimides such as cyclohexylmaleimide, alkylmaleimides such as monofunctional maleimide compounds such as laurylmaleimide can also be used, but are preferably used in place of part of the bismaleimide compound. it can.

In addition, N in the (B) molecule which is a component of the composition of the present invention.
-N-substituted aromatic amines having two or more vinylbenzyl groups and vinylbenzyl ether groups have the general formula (II) (In the formula, X represents a hydrogen atom in the amino group of the aromatic amine.
Represents a residue excluding the number, in the formula, m is a value of 1 to 6, n is 1 to
It has a value of 4).

Typical aminophenols as the raw material of the general formula (II) are o-aminophenol, m-aminophenol, p
-Aminophenol, N-methyl-p-aminophenol, 4-oxydiphenylamine, 3-amino-2-oxytoluene, 4-amino-2-oxytoluene, 5-
Amino-2-oxytoluene, 6-amino-2-oxytoluene, 2-amino-3-oxytoluene, 4-amino-3-oxytoluene, 6-amino-3-oxytoluene, 2-amino-4-oxy Toluene, 3-amino-
4-oxytoluene, 5-amino-3-oxy-o-xylene, 6-amino-3-oxy-o-xylene, 3-
Amino-4-oxy-o-xylene, 5-amino-4-
Oxy-o-xylene, 5-amino-2-oxy-m-
Xylene, 5-amino-4-oxy-m-xylene, 2
-Amino-5-oxy-m-xylene, 4-amino-5
-Oxy-m-xylene, 3-amino-2-oxy-p
-Xylene, 5-amino-2-oxy-p-xylene,
6-amino-2-oxy-p-xylene, 3-aminocatechol, 4-aminocatechol, 3-aminoguaiacol, 6-aminoguaiacol, 4-aminoguaiacol, 5-aminoguaiacol, 2-aminoresorcin,
4-aminoresorcin, 5-aminoresorcin, 2-aminohydroquinone, 2,4-diaminophenol,
2,6-diaminophenol, 2,6-diaminophenol, 2-5-diaminophenol, 4,5-diaminophenol, 3,4-diaminophenol, 3,5-diaminophenol, 4,6-diaminoresorcinol, 2 ，
4,6-triaminophenol and the like can be mentioned.

N-substituted aromatic amine (B) having N-vinylbenzyl group and vinylbenzyl ether group represented by general formula (II)
Is easily synthesized, for example, by adding a commercially available chloromethylstyrene monomer to the above aminophenols at a ratio of 2 to 6 vinylbenzyl groups, and dehydrochlorinating with an inorganic alkali using, for example, dimethyl sulfoxide as a solvent. can do.

The composition ratio of the maleimide compound (A) and the N-substituted aromatic amine (B) having an N-vinylbenzyl group and a vinyl benzyl ether group in the present invention can be widely varied depending on the purpose of use. In terms of the unsaturated group equivalent ratio, A / B = 100/30 to 1/100, preferably 100/50 to 1/30. Within this range,
Without intentionally adding the radical initiator needed for curing,
They are easily heat-cured, the reaction proceeds at a much lower temperature and in a shorter time than the heat-curing alone, and the thermal decomposition start temperature in air is high and the decomposition weight 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, diallylphthalate, acrylic acid ester, methacrylic acid ester,
Alternatively, a vinyl ester resin typified by a reaction product of an epoxy resin and (meth) acrylic acid, vinylpyrrolidone, or the like can be blended. Hydroquinone, benzoquinone, a copper salt, an ammonium salt of N-nitrosophenylhydroxylamine, an aluminum salt or the like may be added to the composition for curing, and further known publicly known radical initiators such as organic compounds may be added to accelerate the curing. Peroxides or organic peroxides and their decomposition accelerators (REDOX) can also be blended.

In addition, the curable resin composition of the present invention can be cured with active energy rays such as ultraviolet rays and laser beams by blending with a publicly known and used photoinitiator, and can be easily cured with an electron beam.

The curable resin composition of the present invention comprises a kneader, a blender,
By rolls and the like, various other fillers and reinforcing fibers are blended to form molding materials and composite materials, and dissolved in a solvent to produce varnish, paint, adhesive, and glass fibers that are reinforcing fibers,
Carbon fiber, aromatic polyamide fiber, silicon carbide fiber,
Alumina fibers can be impregnated into useful molding and structural materials for hand lay-up molding, prepreg and filament windowing.

[Examples] Hereinafter, the present invention will be further described with reference to Examples. Unless otherwise specified, the parts in the examples are parts by weight.

Reference Example 1 Product of Reaction of p-Aminophenol with Chloromethylstyrene 36.3 parts (1.0 equivalent) of p-aminophenol dissolved in 150 parts of dimethyl sulfoxide was added to an aqueous solution of potassium hydroxide [potassium hydroxide 56 1 part (1.0 equivalent), 35 parts of water] 152.5 parts (1.0 equivalent) of commercially available chloromethylstyrene added with 500 ppm of hydroquinone was added dropwise at 70 to 80 ° C. over 1 hour, and further 80
The reaction was continued at 4 ° 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 repeatedly washed with water until the pH of the aqueous layer reached 7, and benzene was removed under reduced pressure to obtain a product containing N, N-divinylbenzyl-p-aminophenoldivinylbenzyl ether (hereinafter, N-DVB-p-APDVBE). To be obtained) with a yield of 95%. Further, dioxane or N, N'-dimethylformamide can be used in place of the dimethyl sulfoxide used here to perform the same synthesis.

Table 1 shows the properties of each N-DVB-p-APDVBE. N-D
VB-p-APDVBE is benzene, toluene, acetone, ME
It was soluble in various organic solvents such as K.

Reference Example 2 Synthesis of diaminodiphenylmethane-modified bismaleimide by reaction of bismaleimide and diaminodiphenylmethane N, N′-diphenylmethane bismaleimide 358 parts (1.0 mol) and diaminodiphenylmethane 99 parts (0.5 mol) were sufficiently added in a ball mill. The mixture obtained by pulverizing and mixing was melt-stirred in a container at 170 ° C. for 10 minutes and immediately cooled with water to obtain a solid. This reaction product was soluble in a solvent such as N-methylpyrrolidone and dimethylformamide, and also soluble in a low boiling point solvent such as acetone and methyl ethyl ketone. (Hereinafter, referred to as DDM-modified BMI).

Example 1 A sample was prepared by mixing 1 equivalent of N-DVB-p-APDVBE synthesized in Reference Example 1 with 1 equivalent of diphenylmethane bismaleimide (hereinafter referred to as BMI) manufactured by Mitsui Toatsu Co., Ltd. It was placed on a hot plate at ℃ and examined for gelation. For comparison, N-vinylbenzylamine and BM, respectively
The same test was performed for I. The results are shown in Table-2.

Example 2 A sample in which 1.0 equivalent of BMI was mixed with 1.0 equivalent of N-DVB-p-APDVBE and 1.0 equivalent of theoretical equivalent of DDM-modified BMI synthesized in Reference Example 2 were mixed at 120 ° C. Molded for 30 minutes. The temperature after initiation of thermal decomposition at 250 ° C. for 5 hours after demolding, and the flexural strength and flexural modulus at room temperature and hot according to JIS K 6911 were measured. The results are shown in Table-3 and Table-4.

Comparative Example 1 For comparison, a curable composition comprising a vinylbenzyl ether compound in which a maleimide compound proposed by the present inventors and an aromatic residue were previously bound (Japanese Patent Laid-Open No. 64-65110).
As an example, the BMI used in Example 1 for 1 equivalent of bisphenol A divinylbenzyl ether (BADVBE).
Alternatively, the DDM-modified BMI synthesized in Reference Example 2 was mixed in a theoretical equivalent amount of 1.0 equivalent and molded at 180 ° C. for 30 minutes. The flexural strength and flexural modulus at room temperature and hot according to JIS K 6911 were measured for those subsequently cured at 250 ° C. for 5 hours. The results are also shown in Table-4.

EFFECTS OF THE INVENTION The curable resin composition according to the present invention is amorphous and has a low viscosity because of the constitution as described above, and therefore has excellent workability and excellent low-temperature curability, heat resistance and mechanical properties. Due to its strength, it can be widely used in industry as adhesive, casting, coating, impregnation, laminating compound or as paint, insulating material or composite structural material.

Claims (1)

[Claims] 1. A general formula (I) (In the formula, R represents hydrogen or a methyl group, and Z represents a divalent aromatic group or a xylylene group.) A compound having a maleimide group in the molecule or an adduct thereof with a diamino compound A compound having two maleimide groups in the molecule, and (B) the general formula (II) (In the formula, X represents a hydrogen atom in the amino group of the aromatic amine.
N-substituted aromatic having N-vinylbenzyl group and vinylbenzyl ether group in the molecule represented by the following: m is a value of 1 to 6, and n is a value of 1 to 4) A curable composition comprising: an amine.