JPH08269327A - Resin composition - Google Patents

Abstract

PURPOSE: To obtain a resin composition, containing a specific amount of a thermosetting resin in a thermoplastic resin, excellent in mechanical properties, fatigue characteristics and heat resistance and useful for structural members, mechanical parts, automotive members and substrates, etc., for space and aircraft. CONSTITUTION: This resin composition is obtained by blending 0.5-10 pts.wt., preferably 3-5 pts.wt. thermosetting resin with 100 pts. wt. thermoplastic resin of formula I [X is a direct bond, SO2 , CO, C(CH3 )2 , C(CF3 )2 or S; Y is a group of formula II, III, etc.], formula IV [R1 and R2 are each H, an alkyl, an alkoxy, a halogenated alkyl, a halogenated alkoxy or a halogen; (n) is 0-4], etc.

Description

Detailed Description of the Invention

[0001]

The present invention relates to mechanical properties, fatigue characteristics,
The present invention relates to a resin composition having excellent heat resistance and a molded product thereof.

[0002]

2. Description of the Related Art Polyimide, polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyether ketone ether ketone ketone,
High heat resistant resins such as polyphenylene sulfide, polyamide imide, and polyether imide are called super engineering plastics because they are significantly superior to general-purpose engineering plastics in terms of heat resistance, mechanical strength, chemical resistance, etc. It is used for electrical, electronic equipment, machinery, automobiles, etc. However, when a large load is repeatedly applied, such as structural members, machine parts, and automobile parts, and when it is continuously used at high temperatures, higher durability and mechanical properties are required. In some cases, conventional super engineering plastics may not have sufficient physical properties depending on the conditions of use. (Japanese Patent Laid-Open No. 62-253655)

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition having excellent durability and mechanical properties at room temperature and high temperature.

[0004]

Means for Solving the Problems The inventors of the present invention have made extensive studies to achieve the above-mentioned objects, and as a result, found a new resin composition having desired performance, and completed the present invention. That is, the present invention includes: 1) 100 parts by weight of a thermoplastic resin and 0.5 to 0.5 of a thermosetting resin.
A resin composition comprising 10 parts by weight as a main component, 2) a resin composition according to claim 1, which is a high heat resistant resin having a melting point of 250 ° C. or higher or a glass transition temperature of 100 ° C. or higher, 3) heat The plastic resin essentially has the formula (I)
A resin composition according to claim 1, which is a polyimide resin having a structure of formula (II)

[0005]

[Chemical 4] (Wherein in the formula (I), X is a direct bond, _-SO 2 -, -
_{CO -, - C (CH 3} ) 2 -, - C (CF 3) 2 -
Or it is -S-. Y is one or more groups selected from the group consisting of the following formulas.

[0006]

Embedded image

[0007]

[Chemical 6] (In the formula (II), R ₁ and R ₂ are each hydrogen, an alkyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group or a halogen group,
n is an integer of 0-4. Y is the same as the definition of Y in the formula (I). 4) A molded product using the high heat-resistant resin composition as described in 1, 2, or 3.

As the thermoplastic resin used in the present invention, for example, polyamino bismaleimide resin (for example, Kelimide resin (Rhone-Poulin) of the following structure [Chemical formula 7]),

[0009]

[Chemical 7] A bismaleimide triazine resin (for example, a BT resin (Mitsubishi Gas Chemical Co., Ltd.) having the following structure [Chemical formula 8]],

[0010]

Embedded image Polyamideimide resin (for example, Torlon (Amoco) having the following structure [Chemical formula 9],

[0011]

[Chemical 9] (R is an aromatic group.) A resin having a functional group (acetylene group, norbornene group, etc.) capable of thermally reacting and crosslinking at the molecular end or molecular chain (for example, the following structure:
0] resin) and the like.

[0012]

[Chemical 10] (However, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or the like.) That is, the resin composition of the present invention is a high heat-resistant resin 100.
A resin composition having excellent durability and mechanical properties at room temperature and high temperature, which is characterized by comprising 1 part by weight and 0.5 to 10 parts by weight of a thermosetting resin. However, the type of thermosetting resin used must be selected according to the extrusion and molding temperatures of the resin composition. That is, the curing temperature of the thermosetting resin needs to be about the same as the extrusion and molding temperatures of the resin composition. When the curing temperature is much lower than the extrusion and molding temperatures, the curing reaction is instantly completed, and the thermosetting resin is not sufficiently dispersed, so that the effect of the present invention cannot be obtained. On the other hand, if it is large and high, the thermosetting resin does not cure sufficiently, and there is no point in incorporating the thermosetting resin. Therefore, as long as it is a resin that can be cured by a crosslinking reaction (self-crosslinking and / or a crosslinking reaction with a thermoplastic resin) at the extrusion and molding temperatures of the resin composition, a resin other than the above-mentioned thermosetting resins can be used. It can be used in accordance with the object of the invention.

In the resin composition of the present invention, 0.5 to 10 parts by weight of the thermosetting resin is suitable for 100 parts by weight of the thermoplastic resin. It is preferably 1 to 7 parts by weight, more preferably 3 to 5 parts by weight. If it is less than 0.5 part by weight, the durability and mechanical properties which are the features of the present invention are not improved. On the other hand, if it is used in an amount of more than 10 parts by weight, the brittleness peculiar to the thermosetting resin is developed and mechanical properties are deteriorated. Further, the fluidity of the resin composition at the time of molding is deteriorated, the molding processability is deteriorated, and it becomes difficult to obtain a satisfactory molded product.

The high heat resistant resin used in the resin composition of the present invention has a melting point (hereinafter referred to as Tm) of 250 ° C.
Above or above, glass transition temperature (hereinafter referred to as Tg) is 1
A material having a temperature of 00 ° C or higher is preferable, and a material having a Tm of 300 ° C or higher and a Tg of 140 ° C or higher is preferable. For example, aromatic polyether sulfone, aromatic polyether imide, aromatic poly sulfone, aromatic polyamide imide, aromatic polyimide, aromatic polyphenylene sulfide, aromatic polyether ether ketone, aromatic polyether ketone,
Aromatic polyether ketone ether ketone ketone, aromatic polyether, aromatic polyester, and the like may be mentioned, and these may be used alone or in admixture of two or more. Specifically, the aromatic polyether sulfone has a structure of the formula (III) [Chemical Formula 11] (Tg; 225
℃, Tm; none),

[0015]

[Chemical 11] The aromatic polyether imide is represented by the formula (IV)
2] structure (Tg; 215 ° C., Tm; none),

[0016]

[Chemical 12] The aromatic polysulfone has a structure of the formula (V) [Chemical Formula 13] (Tg; 190 ° C., Tm; none),

[0017]

[Chemical 13] The aromatic polyimide has a structure of formula (I) and / or formula (II) (Tg; 170 to 260 ° C., Tm;
None to 390 ° C.), and the aromatic polyphenylene sulfide has a structure of the formula (VI) [Chemical Formula 14] (Tg; 88).
℃, Tm; 285 ℃),

[0018]

Embedded image The aromatic polyether ether ketone has the formula (VII)
Having a structure of [Chemical Formula 15] (Tg; 143 ° C., Tm; 33
4 ° C),

[0019]

[Chemical 15] The aromatic polyether ketone is represented by the formula (VIII)
6] structure (Tg; 154 ° C., Tm; 367)
℃),

[0020]

Embedded image The aromatic polyether ketone ether ketone ketone has a structure of formula (IX) [Chemical Formula 17] (Tg; 173
℃, Tm; 380 ℃),

[0021]

[Chemical 17] The aromatic polyether has a structure of the formula (X) [Chemical Formula 18] (Tg; 145 ° C., Tm; 340 ° C.),

[0022]

Embedded image And so on.

Further, within a range not impairing the object of the present invention,
Other thermoplastic resins may be blended in appropriate amounts depending on the purpose. Examples of the thermoplastic resin that can be blended include polyethylene, polypropylene, polystyrene, polyacetal, polyphenylene ether, polycarbonate, polyester and polyamide. It is also possible to mix the filler in an amount that does not impair the object of the invention. As the filler, graphite, carborundum, silica powder, molybdenum disulfide, wear resistance improving material such as fluororesin, carbon fiber, glass fiber, aromatic polyamide fiber, alumina fiber, boron fiber, silicon carbide fiber, titanic acid Reinforcing materials such as potassium whiskers, aluminum borate whiskers, carbon whiskers, asbestos, metal fibers, ceramic fibers, antimony trioxide,
Flame-retardant improving materials such as magnesium carbonate and calcium carbonate,
Clay, mica and other electrical property improving materials, asbestos,
Tracking resistance improver such as silica, graphite, acid resistance improver such as barium sulfate, silica, calcium metasilicate, thermal conductivity improver such as iron powder, zinc powder, aluminum powder, copper powder, other glass beads, talc, Diatomaceous earth,
Alumina, Silasbaln, hydrated alumina, metal oxides,
Colorants, release agents, various stabilizers, plasticizers and the like.

The resin composition of the present invention can be produced by a generally known method, but the following method is particularly preferable. (1) High heat resistant resin powder, carbon fiber mortar, Henshall mixer, drum blender, tumbler blender,
Preliminary mixing is performed using a ball mill, ribbon blender, etc., and then kneading is performed using a commonly known melt extruder, melt mixer, hot roll, etc., and then pelletized or powdered. (2) Highly heat-resistant resin powder is previously dissolved or suspended in an organic solvent, and carbon fibers are immersed in this solution or suspension,
After that, the solvent is removed in a hot air oven and then pelletized or powdered. In this case, examples of the solvent used include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide,
N, N-dimethylmethoxyacetamide, N-methyl-
2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2
-Bis (2-methoxyethoxy) ethane, bis [2-
(2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea, hexamethylphosphoramide and the like. These organic solvents may be used alone or in combination of two or more. The high heat resistant resin composition of the present invention includes an injection molding method, an extrusion molding method,
It is molded by a known molding method such as a compression molding method or a transfer molding method and put into practical use. The resin composition of the present invention molded in this manner is excellent in durability and mechanical properties, especially at high temperatures, and can be used for structural members, machine parts, automobile parts and the like, and is very useful. Further, these molded products can be improved in mechanical properties and thermophysical properties by heat treatment at an appropriate temperature for the purpose of removing residual stress and / or crystallization.

[0025]

EXAMPLES The production examples of the resin composition of the present invention and the physical properties of the obtained resin compositions will be described in detail below with reference to Examples and Comparative Examples. Examples 1 to 4 Polyimide resin Aurum PL4 as highly heat resistant resin
50 (Mitsui Toatsu Kagaku) and Torlon (Amoco) as thermosetting resins were mixed and mixed in the proportions shown in Table 1, and then melt-kneaded at 410 ° C. with an extruder having a diameter of 40 mm to obtain pellets. . The pellets thus obtained were molded using a normal injection molding machine under the conditions of a cylinder temperature of 420 ° C. and a mold temperature of 180 ° C. to obtain a test piece. Table 1 shows the measurement results of various physical properties. The test methods for each physical property are as follows. -Tensile strength According to ASTM D-638.・ Fatigue test Tensile fatigue test, unilateral swing, stress 11 kg
/ mm ² , stress ratio 0, frequency 30Hz, room temperature,
The number of repetitions until breaking was measured. The test piece used is A
STM No. 1 dumbbell tensile test piece. The conditions for measuring physical properties in the following examples and comparative examples are the same as the conditions in this example.

Comparative Examples 1 and 2 Table 1 shows the results of Examples 1 to 4 when the thermosetting resin was used in an amount outside the range of the present invention.

[0027]

[Table 1] *) Composition ratio of resin component. Carbon fiber is 30 parts by weight with respect to 70 parts by weight of resin content.

[0028]

The resin composition of the present invention is a resin composition having excellent durability and mechanical properties at room temperature and high temperature.
Therefore, it is a very useful material used for structural members, mechanical parts, automobile parts, and base materials for space / aircraft, etc., which require these physical properties, and has a very great industrial application effect.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Jun Morita 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Hiroyuki Furukawa 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemical Within the corporation

Claims (4)

[Claims] 1. A resin composition comprising 100 parts by weight of a thermoplastic resin and 0.5 to 10 parts by weight of a thermosetting resin as main components. 2. The resin composition according to claim 1, wherein the thermoplastic resin is a high heat resistant resin having a melting point of 250 ° C. or higher or a glass transition temperature of 100 ° C. or higher. 3. The resin composition according to claim 1, wherein the thermoplastic resin is essentially a polyimide resin having a structure of formula (I) [Chemical formula 1] and / or formula (II) [Chemical formula 3]. Embedded image (However, in the formula (I), X is a direct bond, -SO _2- , -C
_{O -, - C (CH 3} ) 2 -, - C (CF 3) 2 - or -S
− Y is one or more groups selected from the group consisting of the following chemical formulas. Embedded image Embedded image (In the formula (II), R ₁ and R ₂ are each hydrogen, an alkyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group or a halogen group, and n is 0 to 4).
Is an integer. Y is the same as the definition of Y in the formula (I). ) 4. A molded product using the high heat resistant resin composition according to claim 1.