JPH07292075A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To prepare a thermosetting resin compsn. having excellent heat resis tance, mechanical strength, and moldability. CONSTITUTION:A thermosetting resin compsn. comprising: (i) an arom. polyamide oligomer, contg. a polymerizable unsatd. group, randomly having a repeating unit represented by the formula wherein R1 and R2 represent a divalent arom. group, R3 represents a divalent org. group having a polymerizable unsatd. group, and l and m are any integer, provided that l+m is 2 to 50; (ii) a maleimide compd.; (iii) an epoxy compd., and (iv) a glass fiber and/or a fused silica.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel thermosetting resin composition having excellent heat resistance, mechanical strength and processability.

[0002]

2. Description of the Related Art Conventionally, a thermosetting resin having an imide structure has been widely used industrially because it has excellent electrical insulating properties, heat resistance, and dimensional stability of molded products. However, the thermosetting resin using an aromatic bismaleimide is a material that is insoluble and infusible and has excellent heat resistance, but has a drawback that it is poor in workability, impact resistance and toughness. Therefore, as a method for improving the impact resistance and toughness of the aromatic bismaleimide, there is an attempt to use an aromatic diamine for the aromatic bismaleimide. For example, a polyamino bismaleimide resin (manufactured by Rhone Boulan, trade name: Kinel) consisting of N, N '-(4,4'-methylenediphenylene) bismaleimide and 4,4'-diaminodiphenylmethane is impact resistant and Since the toughness is superior to the aromatic bismaleimide alone,
As a molded product, it is widely used for structural members, sliding members, and the like. However, these thermosetting resins have not been satisfactory in terms of impact resistance and toughness.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermosetting resin composition which maintains conventional heat resistance and is excellent in workability, impact resistance and toughness.

[0004]

According to the present invention, there is provided a thermosetting resin composition which can achieve the above objects.

That is, the present invention provides (a) general formula (1)

[Chemical 3] (Wherein R ₁ and R ₂ are divalent aromatic groups, R ₃ is a divalent organic group having a polymerizable unsaturated group, l and m are arbitrary numbers, and 1 + m is 2 to 50), and a polymerizable unsaturated group-containing aromatic polyamide oligomer having a repeating unit represented by the formula (b) maleimide compound (c) epoxy compound and (d) glass fiber and /
Alternatively, it relates to a thermosetting resin composition containing fused silica.

The present invention also provides (a) general formula (1)

[Chemical 4] (Wherein R ₁ and R ₂ are divalent aromatic groups, R ₃ is a divalent organic group having a polymerizable unsaturated group, l and m are arbitrary numbers, and 1 + m is 2 to 50)) 5 to 60 parts by weight of a polymerizable unsaturated group-containing aromatic polyamide oligomer having a repeating unit represented by the formula (2) maleimide compound 5 to 70 parts by weight and (c) epoxy compound 2. 5 to 60 parts by weight, and (a)
Composition 100 in which the weight ratio of (b) to 6: 4 to 4: 6
The present invention relates to a thermosetting resin composition obtained by blending 10 to 300 parts by weight of (d) glass fiber and / or fused silica with respect to parts by weight.

The polymerizable unsaturated group-containing aromatic polyamide oligomer (hereinafter referred to as polyamide oligomer) having the repeating unit represented by the general formula (I), which is the component (A) used in the present invention, at random is produced. Considering easiness, heat resistance of the resin after curing, and adhesive strength, aromatic diisocyanate, aromatic dicarboxylic acid and unsaturated dicarboxylic acid having a polymerizable unsaturated bond (as an end capping agent if desired It is preferable to use the polyamide oligomer synthesized by heating and reacting (monocarboxylic acid) dissolved in a solvent.

Aromatic diisocyanates that can be used for producing the above-mentioned polyamide oligomer include 2,2-diphenylpropane-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate and biphenyl-4. , 4'-diisocyanate, diphenyl sulfide-4,4'-diisocyanate, diphenyl sulfone-
4,4'-diisocyanate, diphenyl ether-
4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate,
Tolylene-2,4-diisocyanate and tolylene-2,
Examples thereof include a mixture of 6-diisocyanate. Among these, diphenylmethane-4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,4-diisocyanate, which are relatively inexpensive, easily available, and industrially easy to handle. Nart and Tolylene-2,6
-A mixture of diisocyanate is preferably used. These aromatic diisocyanates may be used alone or in combination of two or more.

Examples of the aromatic dicarboxylic acid that can be used in the present invention include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid and mixtures thereof.

The unsaturated dicarboxylic acid having a polymerizable unsaturated bond which can be used in the present invention includes endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, maleic acid and phthalic acid. , Itaconic acid and the like and mixtures thereof.

In the present invention, examples of the end-capping monocarboxylic acid that can be used if necessary include aromatic monocarboxylic acids and aliphatic monocarboxylic acids, and the aromatic monocarboxylic acids include benzoic acid and toluyl. Acid, dimethyl benzoic acid, trimethyl benzoic acid, ethyl benzoic acid,
Examples of the aliphatic monocarboxylic acid such as tetramethylbenzoic acid and pentamethylbenzoic acid include acetic acid and propionic acid.

The reaction for producing a polyamide oligomer using these raw materials is carried out in a solvent in which an aromatic diisocyanate, an aromatic dicarboxylic acid, an unsaturated dicarboxylic acid, a monocarboxylic acid for endcapping and a polyamide oligomer produced are dissolved. Alternatively, it is carried out in a solvent mixture.

The solvent used is a polar solvent, particularly preferred are N, N-dimethylacetamide, N, N-
Dimethylformamide, N-methyl-2-pyrrolidone,
Dimethyl sulfoxide, 1,1,3,3-tetramethylurea and mixtures thereof. Also, they must be almost completely anhydrous.

The condensation reaction can be carried out at a temperature of 50 to 200 ° C., preferably 80 to 190 ° C. in the presence of a polymerization inhibitor and a catalyst in order to prevent the polymerization of the unsaturated dicarboxylic acid.

In the present invention, the maleimide compound as the component (b) used as a mixture with the polyamide oligomer as the component (a) includes (i) phenylmaleimides (ii) aromatic diamine and maleic anhydride. And (3) polymaleimides synthesized from polyamines such as aniline-formaldehyde condensates and maleic anhydride, and mixtures thereof. Although phenylmaleimides have a low melting point and have a wide compatibility with polyamide oligomers, they also have a slight lack of heat resistance, and dimaleimides made from aromatic diamines are generally used.

Examples of these are N-phenylmaleimide, N- (O-chlorophenyl) maleimide, N, N '.
-Diphenylmethane bismaleimide, N, N'-diphenyl ether bismaleimide, N, N'-paraphenylene bismaleimide, N, N '-(2-methylmetaphenylene) bismaleimide, N, N'-metaphenylene bismaleimide, N , N '-(3,3'-dimethyldiphenylmethane) bismaleimide, N, N'-(3,3'-diphenylsulfone) bismaleimide or aniline-
Examples thereof include maleimide compounds of formaldehyde condensates.

The polyamide oligomer represented by the general formula (I) used in the present invention generally has a slow curing rate, and it is necessary to heat it to a high temperature for a long time even if a radical generator is used as a catalyst. However, the curing rate can be improved by adding a maleimide compound.

Further, it has the effect of improving the moldability (decreasing the melting point) of the composition containing the maleimide compound before curing and the effect of enabling processing at low pressure.

As the epoxy compound of the component (c) used in the present invention, a bisphenol A type resin (Epicoat 825, 827, 828, 828XA, 834, 834) is used.
815, 1001, 1002, etc., manufactured by Yuka Shell Epoxy Co., Ltd., brominated bisphenol A type resin (Epicoat 5050, 5050-T-60, 5051F, 5).
051H, etc., manufactured by Yuka Shell Epoxy Co., Ltd., bisphenol F type resin (Epicoat 807, etc., manufactured by Yuka Shell Epoxy Co., Ltd.), O-cresol novolac type resin (EOCN-102S, -103S, -104S). Etc., manufactured by Nippon Kayaku Co., Ltd., phenol novolac type resin (EP
PN-201, etc., manufactured by Nippon Kayaku Co., Ltd., and Epicoat 152, 154, etc., manufactured by Yuka Shell Epoxy Co., Ltd.), cycloaliphatic epoxy resin (CY179, 177).
Etc., manufactured by Ciba Geigy, and ERL4221, 429
9, etc., manufactured by UCC), glycidyl ester-based resin (Araldite CY182, 192, etc., manufactured by Ciba Geigy, Showaine 508, etc., Showa Denko KK, Epicron 200, 400, Dainippon Ink & Co., Ltd. ), Glycidyl amine compounds (tetraglycidyl diaminodiphenylmethane, N, N, N ', N'-tetraglycidyl m-
Xylylenediamine, triglycidyl paraaminophenol, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, etc.) or heterocyclic epoxy compounds (triglycidyl isocyanate, 1,3-diglycidyl hydantoin, etc.) These can be used, and these can also be used alone or as a mixture of two or more kinds.

Of these epoxy compounds, bisphenol A type resins and glycidyl amine compounds are preferable, and glycidyl amine compounds are more preferable. Among the glycidylamine compounds, especially tetraglycidyldiaminodiphenylmethane, N, N, N ′,
The use of N′-tetraglycidyl m-xylylenediamine and 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane is preferred.

The epoxy compound as the component (c) used in the present invention improves the adhesiveness between the glass fiber and / or the fused silica as the component (d) and the resin [the component (a) and the component (b)]. In addition, it improves the mechanical properties of the molded product and at the same time lowers the softening point of the composition, which is effective in improving the processability.

The glass fiber used in the present invention is
Molten glass is rapidly cooled while being drawn by various methods, and is made into a fine fiber having a predetermined diameter, a single fiber bundle is bundled with a sizing agent, a roving in which the strands are uniformly aligned and bundled, And crushed glass fiber and the like, and any of them can be used in the present invention. The glass fiber has a silane coupling agent such as aminosilane or epoxysilane, a chromic chloride, or the like in order to have an affinity with the base resin comprising the component (a), the component (b) and the component (c) of the present invention. A surface treatment agent can be used depending on the purpose. The length of the glass fiber in the present invention greatly affects the physical properties of the obtained molded product and the workability at the time of manufacturing the molded product. Generally, as the glass fiber length increases, the physical properties of the molded product improve, but conversely, the workability during the manufacturing of the molded product deteriorates. For this reason, in the present invention, glass fibers having a length of 0.1 to 6 mm, preferably 0.1 to 4 mm are suitable in terms of balance of physical properties and workability of the molded product.

As the fused silica (fused quartz filler) used in the present invention, those having a particle size of 2 to 50 .mu. The fused silica may use a silane coupling agent such as aminosilane or epoxysilane, a chromic chloride, or a surface treatment agent depending on the purpose in order to have an affinity with the base resin of the present invention.

The glass fibers and / or fused silica are
10 to 300 parts by weight, preferably 20 to 250 parts by weight, can be used per 100 parts by weight of the base resin [composition comprising the component (a), the component (b) and the component (c)]. 1
If it is less than 0 parts by weight, the reinforcing effect peculiar to the glass fiber and / or the fused silica, which is a feature of the present invention, cannot be obtained. On the other hand, if it is used in an amount of more than 300 parts by weight, the fluidity of the composition at the time of molding becomes poor and it becomes difficult to obtain a satisfactory molded product.

The base resin of the present invention, that is, the mixing ratio of the polyamide oligomer as the component (a), the maleimide compound as the component (b), and the epoxy compound as the component (c) is
When the total amount of base resin is 100 parts by weight, (a) component 5
-60 parts by weight, preferably 20-50 parts by weight, (b) component 5-70 parts by weight, preferably 20-50 parts by weight, (c)
The amount of the component is 2.5 to 60 parts by weight, preferably 5 to 50 parts by weight. Further, the mixing ratio of the component (a) and the component (b) is preferably 6: 4 to 4: 6 by weight.

The mixing ratio of the component (a) is less than 5 parts by weight,
When the mixing ratio of the component (B) is less than 5 parts by weight, the adhesiveness is good, but the heat resistance is problematic. On the other hand, (a)
When the mixing ratio of the components exceeds 60 parts by weight and when the mixing ratio of the component (b) exceeds 70 parts by weight, the heat resistance is good but the adhesiveness does not reach a satisfactory level. (C)
If the mixing ratio of the components is less than 2.5 parts by weight, the adhesiveness with the glass fiber and / or the fused silica is poor, while (c)
If the mixing ratio of the components exceeds 60 parts by weight, there is a drawback that the heat resistance is poor.

The mixing ratio of the component (a) and the component (b) is preferably 6: 4 to 4: 6 by weight.
If the mixing ratio of the component (a) exceeds 6 by weight, the crosslink density decreases and the physical heat resistance decreases. On the other hand, (b)
If the mixing ratio of the components exceeds 6 by weight, the crosslinking density increases and the physical heat resistance improves, but the cured product becomes brittle.

The thermosetting resin composition of the present invention can be produced by a generally known method, but it is particularly preferable to produce it by the following methods (1) and (2).

(1) A polyamide oligomer as a component (a), a maleimide compound as a component (b), an epoxy compound as a component (c) and glass fiber and / or fused silica as a component (d) are mortar, Henschel mixer, drum blender. , Using a tumbler blender, a ball mill, etc., and if necessary, kneading with a melt mixer, a heat roll, etc., and then pelletizing or powdering.

(2) The polyamide oligomer as the component (a), the maleimide compound as the component (b) and the epoxy compound as the component (c) are dissolved or suspended in an organic solvent in advance, and the glass fiber is added to the solution or suspension. And / or soaking the fused silica, then removing the solvent with a hot air drier and pelletizing or powdering.

The thermosetting resin composition of the present invention can be cured by the combined use of a radical generating catalyst, and the heat resistance can be markedly improved. There is no particular limitation on the radical generating catalyst, but the molding temperature is 100%.
When the temperature is higher than 0 ° C, a so-called high temperature decomposition type, for example, dicumyl peroxide type is used. The amount used is suitably 0.5 to 3 phr. Further, in the thermosetting resin composition of the present invention, in order to further cure or adjust the resin stability, if necessary, hydroquinone, benzoquinone, copper salts, tetramethylthiuram compounds, nitrophenylhydroxy compounds, etc. The thing etc. can be mix | blended.

To the composition of the present invention, within the range that does not impair the object of the present invention, 1 or more usual additives such as an antioxidant and a heat stabilizer, an ultraviolet absorber, an antistatic agent, a lubricant and a coloring agent are added. More than one species can be added. In addition, carbon fibers, aromatic polyamide fibers, alumina fibers, potassium titanate fibers and other reinforcing materials and clay, mica, graphite, glass beads, alumina fused silica and other fillers should be added in appropriate amounts according to the purpose. Is also possible.

The thermosetting resin composition of the present invention is molded by a known molding method such as a compression molding method, a transfer molding method, an extrusion molding method or an injection molding method, and is put into practical use.

[0034]

The present invention will be described in more detail with reference to the following examples.

Synthesis Example 1 50 equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube
Isophthalic acid 23.24 in a 0 ml separable flask
g (0.14 mol), endomethylene tetrahydrophthalic acid 10.92 g (0.06 mol), benzoic acid 4.88
g (0.04 mol), DMF 100 g, mixed tolylene diisocyanate (2,4-tolylene diisocyanate /
2,6-Tolylene diisocyanate (8/2) 38.2
8 g (0.22 mol), dibutyltin dilaurate 0.0
4 g and 2,5-toluquinone (0.05 g) were charged, and nitrogen gas was passed while stirring to gradually raise the temperature to 110 ° C., and the reaction was continued at this temperature for 1 hour.

Next, the temperature was raised to 140 to 145 ° C., the reaction was continued for 5 hours, and then cooled to room temperature. The infrared absorption spectrum of the obtained polymer solution was measured, but no absorption by the NCO functional group was observed.

This polymer solution was gradually added to a large amount of water under vigorous stirring to precipitate crystals. The precipitated crystals are then suction filtered, washed with water and dried, melting point 190-2.
Crystals of polyamide oligomer [I] at 30 ° C. were obtained.

Synthesis Example 2 The same operation as in Example 1 was carried out except that 16.6 g (0.10 mol) of isophthalic acid and 18.2 g (0.1 mol) of endomethylenetetrahydrophthalic acid were used, and the melting point was 180 to
Crystals of the polyamide oligomer [II] at 220 ° C. were obtained.

Synthesis Example 3 29.05 g (0.175 mol) of isophthalic acid and 13.65 g (0.07) of endomethylenetetrahydrophthalic acid.
5 mol), benzoic acid 1.22 g (0.01 mol), and mixed tolylene diisocyanate 44.37 g (0.255 mol) were used, the same operation as in Example 1 was performed, and the melting point was 2.
Crystals of polyamide oligomer [III] at a temperature of 00 to 240 ° C. were obtained.

Synthesis Example 4 50 equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube
Isophthalic acid 23.24 in a 0 ml separable flask
g (0.14 mol), fumaric acid 6.96 g (0.06 mol), benzoic acid 4.88 g (0.04 mol), DMF1
00g, mixed tolylene diisocyanate 38.28g
(0.22 mol), dibutyltin dilaurate 0.04
g, 2,5-toluquinone (0.05 g) were charged, and nitrogen gas was passed while stirring to gradually raise the temperature to 110 ° C., and the reaction was continued at this temperature for 1 hour.

Next, the temperature was raised to 140 to 145 ° C., the reaction was continued for 5 hours, and then cooled to room temperature. The infrared absorption spectrum of the obtained polymer solution was measured, but no absorption by the NCO functional group was observed. This polymer solution was gradually added to a large amount of water under vigorous stirring to precipitate crystals. Next, the precipitated crystals are suction filtered, washed with water and dried to give a polyamide oligomer [I
V] crystals were obtained.

Example 1 Polyamide oligomer [I] 40 synthesized in Synthesis Example 1
g, N, N'-diphenylmethane bismaleimide 40
g, N, N, N ', N'-tetraglycidyl m-xylylenediamine 20 g, zinc stearate 3 g, milled fiber (glass powder, EPG140M-80
A: 200 g of Nippon Electric Glass Co., Ltd. product, 2 g of dicumyl peroxide, 0.05 g of hydroquinone were weighed,
Stir-mix until uniform. The above mixture was kneaded with a hot roll heated to 120 ° C. for 12 minutes to obtain a sheet-like uniform composition. This sheet-shaped composition is cooled and then crushed,
Bending strength was measured by compression molding under the molding conditions shown below.

Molding conditions: preheating 80 ° C., 30 minutes; molding temperature 160 ° C. molding time 20 minutes; molding pressure 50 kg / cm ² post-curing 180 ° C., 5 hours

Bending strength 15.4 kgf / mm ² Bending elastic modulus 1560 kgf / mm ² Thermal deformation temperature 250 ° C. <Charpy impact value (No. 1 E-D) 10.3 Thermal expansion coefficient 7.5 × 10 ⁻⁵ / ° C. Disc Shrinkage 0.290% Barcol hardness (934-1) 74

Examples 2 to 7 The same operations as in Example 1 were carried out except that the formulation (unit: parts by weight) shown in Table 1 was used. The results are shown in Table 2.

[0046]

[Table 1]

[0047]

[Table 2]

Comparative Example 1 A mixture obtained by removing N, N, N ', N'-tetraglycidyl m-xylylenediamine from the formulation of Example 1 at 120 ° C.
It was kneaded for 12 minutes with a hot roll heated to 1, but it was not wound around the roll. Next, the temperature of the hot roll was raised to 130 ° C. and kneading was performed for 12 minutes to obtain a sheet-like uniform composition. This sheet-shaped composition was cooled and then pulverized, and compression-molded under the following molding conditions, but gelation proceeded too much and molding was impossible. Molding conditions: preheating 80 ° C, 30 minutes; molding temperature 160 ° C molding time 20 minutes; molding pressure 50 kg / cm ²

[0049]

The polyamide oligomer, the maleimide compound, the epoxy compound and the glass fiber of the present invention and / or
Alternatively, the thermosetting resin composition containing fused silica has excellent heat resistance, mechanical strength and processability, and
It is expected to have a wide range of uses such as electronic parts, various structural members, sliding parts, etc., and has a great industrial use effect.

Claims (3)

[Claims] 1. (a) General formula (1): (Wherein R ₁ and R ₂ are divalent aromatic groups, R ₃ is a divalent organic group having a polymerizable unsaturated group, l and m are arbitrary numbers, and 1 + m is And a polymerizable unsaturated group-containing aromatic polyamide oligomer having a repeating unit represented by the formula (2) to 50) at random (b) maleimide compound (b) epoxy compound and (d) glass fiber and / or fused silica. Thermosetting resin composition. 2. (a) General formula (1): (Wherein R ₁ and R ₂ are divalent aromatic groups, R ₃ is a divalent organic group having a polymerizable unsaturated group, l and m are arbitrary numbers, and 1 + m is 2 to 50.) 5 to 60 parts by weight of a polymerizable unsaturated group-containing aromatic polyamide oligomer having a repeating unit represented by the formula (2) maleic compound 5 to 70 parts by weight and (c) epoxy compound 2. 10 parts by weight of (d) glass fiber and / or fused silica per 100 parts by weight of the composition consisting of 5 to 60 parts by weight, and the weight ratio of (a) to (b) is 6: 4 to 4: 6. Three
A thermosetting resin composition containing 100 parts by weight. 3. The epoxy compound is N, N, N ', N'-
Tetraglycidyl m-xylylenediamine and / or 1,3-bis (N, N-diglycidylaminomethyl)
The thermosetting resin composition according to claim 1, which is cyclohexane.