JPH11292981A - Kneaded material of thermoplastic resin and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject foam-free kneaded material having excellent color tone, appearance, heat resistance and mechanical properties, useful in the field of electric/electronic field, or the like, by kneading a mixture of a thermoplastic resin and a specific amount of carbon dioxide gas and diffusing the carbon dioxide gas. SOLUTION: A mixture of (A) 100 pts.wt. of a thermoplastic resin e.g. a (rubber-reinforced) polystyrene, acrylic resin, modified polyphenylene ether resin [to be concrete, a resin obtained by adding <=500 pts.wt. of a (high-impact) polystyrene to 100 pts. wt. of a polyphenylene ether of a repeating unit of the formula (R1 to R4 are each H, a halogen, a primary or secondary 1-7C alkyl, phenyl or the like)]} and (B) 0.3-20 pts.wt. of carbon dioxide gas is melted and kneaded at a temperature of the glass transition temperature of the component A+<=150 deg.C to diffuse the component B during the kneading. Preferably, the component A having 110-250 deg.C glass transition temperature is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a kneaded thermoplastic resin which can be used as a plastic material in the fields of electric / electronics, automobiles, various other industrial materials, and food / packaging, and molded using the kneaded material. The present invention relates to a thermoplastic resin molded article.

[0002]

2. Description of the Related Art Thermoplastic resins have excellent workability and productivity.
Products and parts with the desired shape can be efficiently produced by molding methods such as melt injection molding and melt extrusion molding, so products in the electrical and electronic fields, automotive fields, various other industrial materials fields, and food and packaging fields It is widely used as a material for parts. In recent years, especially in the electric and electronic fields, the automobile field, and other various industrial fields, the demand for heat resistance of products and parts has become strict, so many high heat resistant thermoplastic resins have been developed. With the improvement of the temperature, the processing temperature of the melt-kneading for processing the thermoplastic resin into a pellet-shaped thermoplastic resin kneaded material also rises and approaches the decomposition temperature, which causes various problems.

[0003] That is, when the processing temperature of melt kneading for processing into a thermoplastic resin kneaded product approaches the decomposition temperature, discoloration and carbonization occur due to thermal degradation. A problem occurs in color tone and appearance.
In order to solve this problem, in the prior art, a method has been proposed in which additives such as a heat stabilizer and an antioxidant are added to a thermoplastic resin and melt-kneaded, but in the case of a high heat-resistant thermoplastic resin kneaded product. Due to the high processing temperature of the melt-kneading, the color tone and appearance of the molded product are not sufficiently improved even if additives are added.

[0004] Further, when molding is performed using a thermoplastic resin kneaded material in which an additive is added in an increased amount, there arises a problem that heat resistance and mechanical properties are deteriorated. Furthermore, as a technique for improving the color tone and appearance, a method of adding a plasticizer such as mineral oil to a thermoplastic resin to lower the processing temperature for melt-kneading has been used for a long time. The molded product obtained using is good in color tone and appearance,
Heat resistance and mechanical properties decrease. Therefore, the thermoplastic resin kneaded product of the prior art and the molded product obtained by processing the same do not sufficiently meet the demands of the industry because the color tone / appearance and heat resistance / mechanical properties are insufficiently balanced.

Japanese Patent Application Laid-Open No. H10-34726 discloses a method of extruding a difficult-to-mold resin material by adsorbing an inorganic gas such as carbon dioxide to the resin in advance, plasticizing and extruding the resin. In this method, since the resin is shaped while containing the inorganic gas, the extruded product is easily foamed. To prevent foaming on the surface of the extruded product, it is necessary to sufficiently cool the surface in a die, and the thermoplastic resin is used. Manufacturing of,
In particular, there is a problem in terms of productivity even if it is applied to the production of a kneaded thermoplastic resin. Also, Japanese Patent Application Laid-Open No. 9-1047
80 and JP-A-10-53662 disclose a method of injecting a foaming agent such as pressurized carbon dioxide into an extruder as a method for producing an extruded foam. And has nothing to do with the method for producing a resin kneaded product having good resin physical properties.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a molded article obtained by using, for example, a pellet-shaped thermoplastic resin kneaded material, in which the color tone / appearance and the heat resistance / mechanical properties are sufficiently balanced, and It is an object of the present invention to provide a molded article which sufficiently responds to That is, the present invention provides a thermoplastic resin kneaded product which improves color tone and appearance by suppressing discoloration and carbonization due to thermal deterioration of a thermoplastic resin in a melt-kneading process, and which maintains heat resistance and mechanical properties. With the goal.

[0007]

The inventors of the present invention have studied a method for producing a thermoplastic resin kneaded material having excellent moldability, color tone and appearance, and excellent heat resistance and mechanical properties. In processing, the thermoplastic resin (A) 1
A mixture containing 0.3 to 20.0 parts by weight of carbon dioxide gas (B) is melt-kneaded with respect to 00 parts by weight, and the production method of dispersing carbon dioxide gas (B) during melt-kneading produces no foaming. It has been found that a thermoplastic resin kneaded product having good color tone, appearance, heat resistance and mechanical properties can be produced with high productivity. Furthermore, the molded article obtained by reworking the obtained thermoplastic resin kneaded material by various molding methods has found that all of the color tone / appearance and heat resistance / mechanical properties are good, and have completed the present invention. .

That is, in the thermoplastic resin kneaded product of the present invention, the resin viscosity at the time of melt kneading is reduced due to the plasticizing effect of carbon dioxide gas, and shear heat generation can be effectively suppressed, so that thermal deterioration, discoloration and carbonization do not occur. It has excellent color tone and appearance. Furthermore, in the present invention, carbon dioxide gas is released during melt-kneading, so that carbon dioxide gas does not remain in the processed thermoplastic resin kneaded material, so that the thermoplastic resin maintains its original heat resistance and mechanical properties. Therefore, this thermoplastic resin kneaded product has no foaming, has good color tone / appearance, heat resistance / mechanical properties, and can provide products / parts in various industrial fields that sufficiently meet the demands of the industrial world. Become. In addition, molded products obtained by further reworking this thermoplastic resin kneaded product also have good color tone, appearance, heat resistance and mechanical properties, and provide products and parts in various industrial fields that fully meet the demands of the industry. It becomes possible to do.

The thermoplastic resin (A) of the present invention can produce products and parts having a desired shape by a molding method such as a melt extrusion molding method or a melt injection molding method, and can be used in the electric and electronic fields, the automobile field, and various other industries. It is a plastic material widely used as a material for products and parts in the materials field. As long as the thermoplastic resin (A) of the present invention is a moldable plastic material, its primary structure, tacticity, high-order structure and other polymer structures, shapes and manufacturing methods can be adopted. The thermoplastic resin (A) of the present invention is classified into an amorphous thermoplastic resin and a crystalline thermoplastic resin.

Specific examples of the amorphous thermoplastic resin of the present invention include polystyrene, polyvinyl chloride, acrylic resin, styrenic resin, polyarylate, modified polyphenylene ether resin, polycarbonate, polyetherimide, and polyether sal. It is a thermoplastic plastic material such as fon or polysulfone, and a blend of one or more of these plastic materials.

The styrenic resin of the present invention is a homopolymer or a copolymer containing styrene as an essential raw material, and a polymer blend obtained by obtaining these polymers from other resins. The styrene resin of the present invention is polystyrene or ABS.
It is preferably a resin. The polystyrene of the present invention is a styrene homopolymer or a rubber-reinforced polystyrene in which rubber is distributed in a resin phase.

The modified polyphenylene ether resin of the present invention is a resin obtained by melting and kneading polyphenylene ether, and a polymer alloy or a polymer composite obtained by mixing and melting and kneading polyphenylene ether with another composition. The preferred modified polyphenylene ether resin of the present invention is polyphenylene ether 10
0 parts by weight of polystyrene, high impact polystyrene, syndiotactic polystyrene, or rubber-reinforced syndiotactic polystyrene in a range of 500 parts by weight or less, preferably 200 parts by weight or less. The polyphenylene ether of the present invention (hereinafter simply referred to as PP
The abbreviation E is one in which the bonding unit is represented by Chemical Formula 1.

[0013]

Embedded image

Wherein R1, R2, R3 and R4
Is hydrogen, halogen, a primary or secondary lower alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group or at least two carbon atoms each of which is a halogen atom. It is selected from the group consisting of a halohydrocarbon oxy group separating from an oxygen atom, and may be the same or different.

The PPE of the present invention has a reduced viscosity of 0.3 g as measured at 30 ° C. using a chloroform solution of 0.5 g / dl.
In the range of 15 to 0.70, more preferably 0.20 to 0.
A polymer or copolymer in the range of 60. The PPE of the present invention is specifically composed of poly (2,6-dimethyl-1,1).
4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro- 1,4-phenylene ether)
And so on.

As specific examples of the PPE of the present invention, 2,6
-Dimethylphenol and other phenols (for example,
2,3,6-trimethylphenol or 2-methyl-6
Polybutylene ether copolymer such as a copolymer with butylphenol). The PPE of the present invention
Poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol can be preferably used.

Most preferred in the PPE of the present invention is poly (2,6-dimethyl-1,4-phenylene ether). In the present invention, styrene, a styrene-based compound, α,
reacting one or more compounds selected from β-unsaturated carboxylic acids, esters of α, β-unsaturated carboxylic acids, and acid anhydrides of α, β-unsaturated carboxylic acids with the above PPE The resulting PPE derivative can also be used as PPE.

The method for producing PPE used in the present invention is not limited. As an example of the method for producing PPE used in the present invention, there is a method of oxidatively polymerizing 2,6-xylenol using a complex of a cuprous salt and an amine as a catalyst described in US Pat. No. 3,308,874. US Patent No. 33
06875, 3257357 and 32573
58 specification, JP-B-52-17880 and JP-A-Showa 50
The methods described in JP-A-51197 and JP-A-63-152628 are also preferable as a method for producing PPE.

Specific examples of the crystalline thermoplastic resin of the present invention include high-density polyethylene, low-density polyethylene,
Thermoplastic plastic materials such as linear low density polyethylene, polypropylene, syndiotactic polystyrene, polyethylene terephthalate, polybutylene terephthalate, wholly aromatic polyester, polyacetal, polyamide resin, polyetheretherketone, polyetherketone, and the like. A blend in which one or more plastic materials are mixed, and a blend in which an amorphous thermoplastic resin and a crystalline thermoplastic resin are mixed.

The thermoplastic resin (A) of the present invention may contain a desired additive depending on the purpose. The additives used in the thermoplastic resin (A) of the present invention include a heat stabilizer, an antioxidant,
V absorber, surfactant, lubricant, filler, flame retardant, pigment,
Dye, impact modifier, polymer additive, filler, glass fiber, carbon fiber, inorganic fiber, dialkyl peroxide, diacyl peroxide, peroxyester, peroxycarbonate, hydroperoxide,
And peroxyketal.

The carbon dioxide (B) of the present invention is a mixture containing carbon dioxide as a main component. That is, the carbon dioxide gas (B) of the present invention is prepared by converting carbon dioxide in a gas, a liquid, a solid, or a supercritical state, carbon dioxide in any state, or carbon dioxide in two or more kinds.
It is a mixture containing 0% by weight or more. The mixture containing carbon dioxide (B) in the thermoplastic resin (A) of the present invention refers to a mixture of the thermoplastic resin (A) in which gaseous carbon dioxide (B) is sorbed, and a mixture of the thermoplastic resin (A) ) In which carbon dioxide gas (B) is press-fitted, or any state in which the thermoplastic resin (A) and carbon dioxide gas (B) coexist.

The amount of carbon dioxide (B) contained in the mixture of the present invention is 0.3 to 20.0 parts by weight based on 100 parts by weight of the thermoplastic resin (A). In the present invention, when the amount of carbon dioxide (B) contained in 100 parts by weight of the thermoplastic resin is less than 0.3 parts by weight, the resin plasticizing effect of the carbon dioxide (B) is insufficient, so that the thermoplastic resin (A) ) Does not sufficiently decrease, shear heating during melt-kneading cannot be suppressed effectively, discoloration and carbonization occur due to thermal degradation, and the resulting thermoplastic resin kneaded product has problems in color tone and appearance. In the present invention, when the amount of carbon dioxide (B) contained in 100 parts by weight of the thermoplastic resin (A) exceeds 20.0 parts by weight, the state of the mixture is unstable, so that the process of the melt-kneading process is not controlled. It becomes difficult.

The melt kneading of the present invention is a step of plasticizing a thermoplastic resin by using a mixer, bringing the thermoplastic resin into a molten state, kneading, cooling and solidifying. The mixer, the type, the structure, and the configuration of the mixer of the present invention can be adopted as long as they can be melt-kneaded. Examples of the mixer of the present invention include a static mixer, a Banbury mixer, a single-screw extruder, a co-kneader, and a twin-screw extruder.

As the mixer of the present invention, a single screw extruder, a co-kneader and a twin screw extruder are preferable. As a mixer of the present invention, a co-kneader and a twin-screw extruder are more preferable. As the mixer of the present invention, a twin-screw extruder is very preferable. The shape of the thermoplastic resin kneaded product of the present invention is not limited. As the shape of the thermoplastic resin kneaded product of the present invention, a pellet shape can be preferably used. As a means for processing into a pellet, for example, when a twin-screw extruder is used as a mixer, a strand cutting method in which a melt-kneaded thermoplastic resin is formed into a strand and then cut using a cutter, The hot-cut method of cutting the thermoplastic resin with a cutter, and the underwater method of cutting the molten thermoplastic resin in water with a cutter are preferred.

As a method of releasing carbon dioxide gas, for example, when a twin-screw extruder is used as a mixer, the carbon dioxide gas is released to the atmosphere from the vent of the twin-screw extruder during melt-kneading, or a suction pump is used. There is a method of connecting and dissipating.
In this case, the amount of emission can be controlled by adjusting the gas pressure in the vent portion. In order to suppress the shear heat generation of the thermoplastic resin after the carbon dioxide gas is diffused, it is desirable that the place where the carbon dioxide gas is diffused is a vent in a portion close to the die.

In the present invention, it is not always necessary to emit all carbon dioxide from the mixture during melt-kneading as long as the foaming of the thermoplastic resin kneaded material can be substantially suppressed. In the present invention, the carbon dioxide gas remaining in the mixture during melt-kneading is, for example, when a twin-screw extruder is used as a mixer, is diffused from the die portion and the surface of the strand being cooled, and the thermoplastic resin kneaded material is removed. Does not foam. The carbon dioxide gas remaining in the thermoplastic resin kneaded material after cooling is naturally diffused when left in the air, and the thermoplastic resin kneaded material does not foam.

According to the method of the present invention, it is possible to suppress a very strong shearing heat generated when the thermoplastic resin solid which is the largest cause of discoloration and carbonization of the thermoplastic resin kneaded material in the melt kneading is melted. In the present invention, the color tone and appearance are improved at any temperature of the extruder at the time of melt-kneading, which is lower than the cylinder temperature at which the thermoplastic resin is usually melt-kneaded and which can be melt-kneaded. In the method for producing a thermoplastic resin kneaded product of the present invention, when the thermoplastic resin (A) is an amorphous thermoplastic resin, the processing temperature for melt kneading is equal to or lower than the glass transition temperature of the thermoplastic resin (A) + 150 ° C. When the temperature is above, a preferable thermoplastic resin kneaded material is obtained. In the method for producing a thermoplastic resin kneaded product of the present invention, when the thermoplastic resin (A) is a crystalline thermoplastic resin,
The processing temperature of the melt-kneading is the melting point of the thermoplastic resin (A) +10
When the temperature is 0 ° C. or lower, a preferable thermoplastic resin kneaded material is obtained.

The processing temperature of the melt-kneading of the present invention is the temperature of the mixer during the processing. The processing temperature of the melt-kneading of the present invention can be replaced by the set temperature of the mixer if there is no substantial difference. In the present invention, it is more preferable that the processing temperature of the melt-kneading is a temperature equal to or lower than the glass transition temperature of the thermoplastic resin (A) + 100 ° C. or the melting point + 70 ° C.

In the present invention, an extremely favorable effect is obtained when the processing temperature of the melt-kneading is a temperature equal to or lower than the glass transition temperature of the thermoplastic resin (A) + 50 ° C. or the melting point + 40 ° C. or lower. In the present invention, the thermoplastic resin (A)
As a method of containing carbon dioxide gas (B), a thermoplastic resin (A) is brought into contact with a carbon dioxide gas (B) at a pressure of 0.1 MPa to 15 MPa for 0.1 second or more before melt-kneading to obtain a thermoplastic resin (B). A method containing carbon dioxide (B) in A) is preferred.

In the present invention, as a method of containing carbon dioxide (B) in the thermoplastic resin (A), the carbon dioxide (B) having a pressure of 0.4 MPa to 10 MPa is mixed with the thermoplastic resin (A) before melt-kneading. Is more preferable. In the present invention, as a method of containing carbon dioxide gas (B) in the thermoplastic resin (A), the thermoplastic resin (A) is contacted with the carbon dioxide gas (B) at a pressure of 1 MPa to 5 MPa for 100 seconds or more before melt-kneading. It is very preferable to use the method.

In the present invention, as a method of containing carbon dioxide (B) in the thermoplastic resin (A), the thermoplastic resin (A) and carbon dioxide (B) in the melt-kneading process are injected from a cylinder of an extruder. A method can also be preferably adopted. in this case,
The injection pressure of carbon dioxide gas (B) must be equal to or higher than the resin pressure at the gas injection position of the extruder. When the carbon dioxide gas (B) is injected from a vent, it can be injected at a low pressure of about 0.1 MPa. 30M when pouring from the kneading part
A pressure of about Pa is required. In addition, it is important to keep the injection amount of carbon dioxide gas (B) constant, and a gas flow rate control such as using a plunger pump as a metering pump or measuring the gas flow rate and performing feedback control of the gas supply pressure is performed. Is preferred.

Regardless of the method in which the carbon dioxide gas (B) is mixed with the thermoplastic resin (A), the atmosphere near the hopper for supplying the resin to the extruder is preferably carbon dioxide gas. This is to prevent the high-temperature resin from coming into contact with oxygen to prevent the resin from being oxidized and degraded, and to remove nitrogen which impairs plasticization stability. In the present invention, when the glass transition temperature of the thermoplastic resin (A) is 110 ° C. to 250 ° C. such that a high resin temperature is required for extrusion kneading, the color tone and appearance of the thermoplastic resin kneaded product are remarkable. To be improved. The glass transition temperature of the amorphous thermoplastic resin of the present invention is the temperature-heat flow graph obtained when the temperature is increased at 20 ° C./min in the measurement of the thermoplastic resin with a differential scanning calorimeter (DSC). Defined by onset temperature.

The glass transition temperature of the present invention is defined by the highest temperature among a plurality of onset temperatures when there are a plurality of onset temperatures. The melting point of the crystalline thermoplastic resin in the present invention is defined as the peak top temperature of a temperature-heat flow graph obtained by measuring with a differential scanning calorimeter (DSC) and heating at 20 ° C./min. Defined. In the present invention, when the thermoplastic resin is a modified polyphenylene ether resin, the effect of improving the color tone of the thermoplastic resin kneaded product is extremely remarkable.

The use of the kneaded thermoplastic resin of the present invention is not limited. The thermoplastic resin kneaded product of the present invention can be preferably applied in applications requiring a good color tone in the fields of electric / electronics, automobiles, various other industrial materials, and food / packaging. The thermoplastic resin kneaded product of the present invention,
Due to the resin plasticizing effect of carbon dioxide gas (B), problems such as discoloration and carbonization do not occur during melt-kneading, and the color tone and appearance are good. Further, since the carbon dioxide gas (B) does not remain in the thermoplastic resin kneaded material after processing, the heat resistance and mechanical properties of the thermoplastic resin kneaded material are the same as those of the thermoplastic resin (A) as the raw material. , Equivalent to mechanical properties. That is, the thermoplastic resin composition of the present invention is excellent in that the viscosity of the resin is reduced due to the plasticizing effect of the carbon dioxide gas during melt-kneading, and that the shear heat generation can be effectively suppressed, so that there is no thermal deterioration, and no discoloration or carbonization occurs. It has color tone and appearance.

Further, since no carbon dioxide gas remains in the thermoplastic resin kneaded product of the present invention, the thermoplastic resin exhibits the inherent heat resistance and mechanical properties. Therefore, when the thermoplastic resin kneaded product of the present invention is processed by various molding methods, a molded product having good color tone, appearance, heat resistance, and mechanical properties can be obtained, and is a product in various industrial fields which sufficiently meets the demands of the industrial world.・ Parts can be provided.

[0036]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail by way of examples. The present invention is not limited to the following examples as long as the gist is not exceeded. In the examples and comparative examples, the following thermoplastic resin (A) is used. A-1: Poly (2,6-dimethyl-1,4 having a reduced viscosity of 0.54 obtained by oxidative polymerization of 2,6-dimethylphenol.
-Phenylene ether) A-2: Poly (2,6-dimethyl-1,4, having a reduced viscosity of 0.31 obtained by oxidative polymerization of 2,6-dimethylphenol.
-Phenylene ether) A-3: Polyamide resin (Leona 1300S manufactured by Asahi Chemical Industry Co., Ltd.) A-4: Modified polyphenylene ether resin (Zylon 500H manufactured by Asahi Chemical Industry Co., Ltd.) A-5: Polyetherimide (GE Co., Ltd.) ULTEM10
00) A-6: Polyether sulfone (Victr manufactured by ICI)
ex-7p) A-7: ABS resin (Stylac IM15 manufactured by Asahi Kasei Kogyo Co., Ltd.) A-8: Polystyrene (Stylon G9305 manufactured by Asahi Kasei Kogyo Co., Ltd.) A-9: Polyacetal (Tenac manufactured by Asahi Kasei Kogyo Co., Ltd.) 3010) A-10: PMMA resin (Delpet 80N manufactured by Asahi Kasei Corporation)

In the examples and comparative examples, the following carbon dioxide gas (B) is used. B-1: Dry ice B-2: Carbon dioxide gas having a pressure of 0.07 MPa at a temperature of 35 ° C. B-3: Carbon dioxide gas having a pressure of 0.15 MPa at a temperature of 35 ° C. B-4: A pressure of 0.15 MPa at a temperature of 35 ° C. 3 MPa carbon dioxide gas B-5: carbon dioxide gas having a pressure of 0.5 MPa at a temperature of 35 ° C. B-6: carbon dioxide gas having a pressure of 0.8 MPa at a temperature of 35 ° C. B-7: a pressure of 1.2 MPa at a temperature of 35 ° C. Carbon dioxide gas B-8: Carbon dioxide gas having a pressure of 4 MPa at a temperature of 35 ° C. B-9: Carbon dioxide gas having a pressure of 6 MPa at a temperature of 35 ° C. B-10: Carbon dioxide gas having a pressure of 8 MPa at a temperature of 35 ° C. B-12: Temperature of 35 B-13: Carbon dioxide gas at a pressure of 15 MPa at a temperature of 35 ° C.

In Examples and Comparative Examples, the glass transition temperature and the melting point are evaluated by the following methods. The differential scanning calorimeter (DSC) was measured for the thermoplastic resin (A),
The onset temperature of the temperature-heat flow graph obtained when the temperature is raised at ° C./min is defined as the glass transition temperature. In addition, similarly, measurement with a differential scanning calorimeter (DSC) was performed, and the measurement was performed at 20 ° C. /
The peak top temperature of the temperature-heat flow graph obtained when the temperature is raised in minutes is defined as the melting point.

In Examples and Comparative Examples, the color tone and appearance of the molded article are evaluated by the following methods. Using an injection molding machine, a 50 * 80 * 3 mm flat molded product is molded from the thermoplastic resin kneaded product of the present invention, and the color of the flat molded product and the number of foreign substances are observed, and the color tone of the molded product is determined. Evaluate appearance. In Examples and Comparative Examples, the heat resistance and mechanical properties of the molded body are evaluated by the following methods. Using an injection molding machine, an ASTM standard test piece is injection-molded from the thermoplastic resin kneaded product of the present invention, and the heat distortion temperature (ASTM D-648: 1) is determined according to the ASTM standard.
8.6 kg load), tensile strength (ASTM D-638:
23 ° C.), flexural modulus (ASTM D-790: 23)
℃), Izod (with notch) impact strength (ASTM
D-256: 23 ° C.) to evaluate the heat resistance and mechanical properties of the molded article.

[0040]

Example 1 100 parts by weight of a thermoplastic resin (A-1) was placed in an autoclave provided with a gas inlet and sealed, and then (B-7) was supplied through the gas inlet, and the pressure in the autoclave was changed to ( After being equal to B-7), the mixture was allowed to stand for 2 hours to obtain a mixture (C-1-7) containing 2.8 parts by weight of carbon dioxide gas. The glass transition temperature of the thermoplastic resin (A-1) is 215 ° C. Using an intermeshing type twin-screw extruder “ZSK-25 extruder” manufactured by Welner, Germany with the cylinder temperature set to 280 ° C., the supply amount was 12 kg /
At time, the melt-kneading of (C-1-7) is performed. At this time, emission of carbon dioxide gas is observed from each of the extruder feed port and the extruder side vent port. After cooling the strand-shaped molten resin discharged from the extruder with water, a pellet-shaped thermoplastic resin kneaded product (D-1-7) without foaming by carbon dioxide gas is obtained using a strand cutter.

The flat plate obtained by molding (D-1-7) has a pale yellow color tone, and no foreign matter is observed. (D-1-
The physical properties of the molded article 7) are as follows: heat deformation temperature: 188 ° C., tensile strength: 760 kg / cm ² , flexural modulus: 26,000 k
g / cm ² , Izod strength 5.5 kg · cm / cm
It is.

[0042]

[Comparative Example 1] An intermeshing type twin screw extruder “ZSK-2” manufactured by Werner Co., Ltd., in which the cylinder temperature was set to 280 ° C.
5 extruder ", melt-kneading the thermoplastic resin (A-1) at a supply rate of 12 kg / hour, and kneading the thermoplastic resin (E-
Obtain 1). The flat plate obtained by molding (E-1) is brownish and many foreign substances are observed. The physical properties of the molded product (E-1) are as follows: heat deformation temperature: 186 ° C., tensile strength: 730 kg
/ Cm ² , the flexural modulus is 25,000 kg / cm ² , and the Izod strength is 4 kg · cm / cm.

[0043]

Example 2 The glass transition temperature of the thermoplastic resin (A-2) is 212 ° C. A stopper with a nozzle is attached to the side vent 1 immediately after the melting zone of the extruder, and the side vent 2 in front of the die is attached.
And an interlocking twin-screw extruder “ZSK-25” manufactured by Werner Co., Germany with the cylinder temperature set to 280 ° C.
The extruder is used to carry out the melt kneading of (A-2). (A-
2) was supplied from the feed port of the extruder at a supply rate of 12 kg / hour, and (B-9) was supplied from the nozzle of the side vent 1 to 0.60.
Press in at kg / hr. (A-2) The content of carbon dioxide is 5.0 parts by weight based on 100 parts by weight.

The emission of carbon dioxide gas is observed from the side vent 2 at atmospheric pressure. The gas to be released is led to a cooler, and the amount of carbon dioxide gas measured at room temperature is 0.58 kg / hour.
After cooling the strand-like molten resin discharged from the extruder without foaming with water, a kneaded thermoplastic resin (D-2-9) is obtained using a strand cutter. The flat plate obtained by molding (D-2-9) has a pale yellow color tone, and no foreign matter is observed on the flat plate. Physical properties of molded article (D-2-9), the thermal deformation temperature of 187 ° C., a tensile strength of 750 kg / cm ^2, a flexural modulus of 25,500kg / cm ^2, the Izod strength is 5 kg · cm / cm .

[0045]

Comparative Example 2 Melting and kneading of (A-2) were carried out under the same conditions as in Example 2 except that the press-in of (B-9) was stopped to obtain a thermoplastic resin kneaded product (E-2). The flat plate obtained by molding (E-2) is brownish and foreign matter is observed. (E-
The physical properties of the molded article 2) are as follows: heat deformation temperature: 184 ° C., tensile strength: 730 kg / cm ² , flexural modulus: 24,800 k
g / cm ² , Izod strength is 3.8 kg · cm / cm
It is.

[0046]

Example 3 The melting point of the thermoplastic resin (A-3) was 256.
° C. A side vent 1 immediately after the melting zone of the extruder was equipped with a stopper with a nozzle, a side vent 2 was opened in front of the die, and an intermeshing type twin-screw extruder manufactured by Werner Co. of Germany was set at a cylinder temperature of 280 ° C. The melt kneading of (A-3) is performed using a "ZSK-25 extruder". (A-3) is supplied from the feed port of the extruder at a supply rate of 12 kg / hour,
(B-9) from the nozzle of side vent 1 at 0.6 kg /
Press in at time. (A-3) The content of carbon dioxide is 5.0 parts by weight based on 100 parts by weight.

The emission of carbon dioxide from the side vent 2 is observed. After cooling the strand-like molten resin discharged from the extruder without foaming with water, a thermoplastic resin kneaded product (D-3-9) is obtained using a strand cutter. (D-3-
The flat plate obtained by molding 9) is white, and no foreign matter is observed on the flat plate. Physical properties of molded article (D-3-9), the thermal deformation temperature of 72 ° C., a tensile strength of 830 kg / cm ^2, a flexural modulus of 29,500kg / cm ^2, the Izod strength 4.8 kg · cm / cm It is.

[0048]

Comparative Example 3 Melting and kneading of (A-3) were carried out under the same conditions as in Example 3 except that the press-in of (B-9) was stopped to obtain a thermoplastic resin kneaded product (E-3). The flat plate obtained by molding (E-3) is pale yellow, and a small amount of foreign matter is observed.
The physical properties of the molded product (E-3) were as follows: heat deformation temperature: 70 ° C., tensile strength: 830 kg / cm ² , flexural modulus: 29,00
0 kg / cm ² , Izod strength is 4.0 kg · cm /
cm.

[0049]

Example 4 Side vent 1 immediately after the melting zone of the extruder
Was attached with a stopper with a nozzle, a side vent 2 in front of the die was opened, and an interlocking twin-screw extruder “ZSK-25 extruder” manufactured by Werner Co., Germany, in which the cylinder temperature was set to 280 ° C. ( The melt-kneading of A-4) is performed. The glass transition temperature of the thermoplastic resin (A-4) is 153 ° C. (A-
4) was supplied from the feed port of the extruder at a supply rate of 12 kg / hour, and (B-9) was supplied from the nozzle of the side vent 1 to 0.6 k.
g / h. (A-4) With respect to 100 parts by weight,
The content of carbon dioxide is 5.0 parts by weight.

The emission of carbon dioxide gas is observed from the side vent 2. After cooling the strand-shaped molten resin discharged from the extruder without foaming with water, a thermoplastic resin kneaded product (D-4-9) is obtained using a strand cutter. (D-4-
The flat plate obtained by molding 9) is pale yellow, and no foreign matter is observed on the flat plate. The physical properties of the molded product (D-4-9) are as follows: heat deformation temperature: 125 ° C., tensile strength: 520 kg / cm ² , flexural modulus: 24,500 kg / cm ² , Izod strength: 15.5 kg · cm / cm It is.

[0051]

Comparative Example 4 Melting and kneading of (A-4) were carried out under the same conditions as in Example 4 except that the press-in of (B-9) was stopped to obtain a thermoplastic resin kneaded product (E-4). The flat plate obtained by molding (E-4) is pale yellow, and a small amount of foreign matter is observed.
The physical properties of the molded product (E-4) are as follows.
Tensile strength 500 kg / cm ² , flexural modulus 24.3
00kg / cm ² , Izod strength 14.4kg ・ c
m / cm.

[0052]

Example 5: Side vent 1 immediately after the melting zone of the extruder
, A side vent 2 in front of the die was opened, and an interlocking twin-screw extruder “ZSK-25 extruder” manufactured by Werner Co., Germany, in which the cylinder temperature was set to 300 ° C. ( The melt-kneading of A-5) is performed. The glass transition temperature of the thermoplastic resin (A-5) is 225 ° C. (A-
5) was supplied from the feed port of the extruder at a supply rate of 12 kg / hour, and (B-9) was supplied from the nozzle of the side vent 1 to 0.6 k / h.
g / h. (A-5) With respect to 100 parts by weight,
The content of carbon dioxide is 5.0 parts by weight.

The emission of carbon dioxide gas is observed from the side vent 2. After cooling the strand-shaped molten resin discharged from the extruder without foaming with water, a kneaded thermoplastic resin (D-5-9) is obtained using a strand cutter. (D-5
The flat plate obtained by molding 9) is yellow-brown, and no foreign matter is observed on the flat plate. The physical properties of the molded product (D-5-9) were such that the heat distortion temperature was 202 ° C, the tensile strength was 1070 kg / cm ² ,
The flexural modulus is 33,500 kg / cm ² and the Izod strength is 5.5 kg · cm / cm.

[0054]

Comparative Example 5 Melting and kneading of (A-5) were carried out under the same conditions as in Example 5 except that the press-in of (B-9) was stopped to obtain a thermoplastic resin kneaded product (E-5). The flat plate obtained by molding (E-5) is brown, and a large amount of foreign matter is observed.
The physical properties of the molded product (E-5) are as follows:
Tensile strength is 1040 kg / cm ² , flexural modulus is 33,
000kg / cm ² , Izod strength 4.5kg ・ c
m / cm.

[0055]

Embodiment 6 Side vent 1 immediately after the melting zone of the extruder
, A side vent 2 in front of the die was opened, and an interlocking twin-screw extruder “ZSK-25 extruder” manufactured by Werner Co. of Germany, in which the cylinder temperature was set to 320 ° C. ( The melt kneading of A-6) is performed. The glass transition temperature of the thermoplastic resin (A-6) is 225 ° C. (A-
6) was supplied from the feed port of the extruder at a supply rate of 12 kg / hour, and (B-9) was supplied from the nozzle of the side vent 1 to 0.6 k / h.
g / h. (A-6) With respect to 100 parts by weight,
The content of carbon dioxide is 5.0 parts by weight.

The emission of carbon dioxide from the side vent 2 is observed. After cooling the strand-shaped molten resin discharged from the extruder without water with water, a kneaded thermoplastic resin (D-6-9) is obtained using a strand cutter. (D-6
The flat plate obtained by molding 9) is pale yellow, and no foreign matter is observed on the flat plate. The physical properties of the molded product (D-6-9) are as follows: heat deformation temperature: 205 ° C., tensile strength: 900 kg / cm ² , flexural modulus: 27,500 kg / cm ² , Izod strength: 9.5 kg · cm / cm It is.

[0057]

Comparative Example 6 Melting and kneading of (A-6) were carried out under the same conditions as in Example 6 except that the press-in of (B-9) was stopped to obtain a thermoplastic resin kneaded product (E-6). The flat plate obtained by molding (E-6) is pale yellow, and a small amount of foreign matter is observed.
The physical properties of the molded product (E-6) are as follows:
Tensile strength 850 kg / cm ² , flexural modulus 26.3
00 kg / cm ² , Izod strength is 8.6 kg · cm
/ Cm.

[0058]

Example 7: Side vent 1 immediately after the melting zone of the extruder
, A side vent 2 in front of the die was opened, and an interlocking twin-screw extruder “ZSK-25 extruder” manufactured by Werner Co. of Germany, in which the cylinder temperature was set to 240 ° C. ( The melt-kneading of A-7) is performed. The glass transition temperature of the thermoplastic resin (A-7) is 115 ° C. (A-
7) was supplied from the feed port of the extruder at a supply rate of 12 kg / hour, and (B-9) was supplied from the nozzle of the side vent 1 to 0.6 k / h.
g / h. (A-7) With respect to 100 parts by weight,
The content of carbon dioxide is 5.0 parts by weight.

The emission of carbon dioxide from the side vent 2 is observed. After cooling the strand-shaped molten resin discharged from the extruder without foaming with water, a kneaded thermoplastic resin (D-7-9) is obtained using a strand cutter. (D-7-
The flat plate obtained by molding 9) is white, and no foreign matter is observed on the flat plate. The physical properties of the molded product (D-7-9) were as follows: heat deformation temperature: 93 ° C., tensile strength: 460 kg / cm ² , flexural modulus: 27,500 kg / cm ² , Izod strength: 3
It is 2 kg · cm / cm.

[0060]

Comparative Example 7 Melting and kneading of (A-7) were carried out under the same conditions as in Example 7 except that the press-in of (B-9) was stopped to obtain a kneaded thermoplastic resin (E-7). The flat plate obtained by molding (E-7) is white, and a small amount of foreign matter is observed.
The physical properties of the molded product (E-7) were as follows: heat deformation temperature: 90 ° C., tensile strength: 450 kg / cm ² , flexural modulus: 2700
0 kg / cm ² , Izod strength 27 kg · cm / c
m.

[0061]

Example 8: Side vent 1 immediately after the melting zone of the extruder
Was fitted with a nozzle, a side vent 2 was opened in front of the die, and an interlocking twin-screw extruder “ZSK-25 extruder” manufactured by Werner Co., Germany, in which the cylinder temperature was set to 220 ° C. ( The melt kneading of A-8) is performed. The glass transition temperature of the thermoplastic resin (A-8) is 108 ° C. (A-
8) was supplied from the feed port of the extruder at a supply rate of 12 kg / hour, and (B-9) was supplied from the nozzle of the side vent 1 to 0.6 k / h.
g / h. (A-8) For 100 parts by weight,
The content of carbon dioxide is 5.0 parts by weight.

The emission of carbon dioxide from the side vent 2 is observed. After cooling the strand-shaped molten resin discharged from the extruder without water with water, a kneaded thermoplastic resin (D-8-9) is obtained using a strand cutter. (D-8-
The flat plate obtained by molding 9) is colorless and transparent, and no foreign matter is observed on the flat plate. The physical properties of the molded product (D-8-9) were as follows: heat deformation temperature: 89 ° C., tensile strength: 550 kg / cm ² , flexural modulus: 34,500 kg / cm ² , Izod strength: 1.8 kg · cm / cm It is.

[0063]

Comparative Example 8 Melting and kneading of (A-8) were carried out under the same conditions as in Example 8 except that the press-in of (B-9) was stopped to obtain a thermoplastic resin kneaded product (E-8). The plate obtained by molding (E-8) is transparent with a slight yolk, and a small amount of foreign matter is observed. The physical properties of the molded product (E-8) are as follows: heat deformation temperature: 87 ° C., tensile strength: 530 kg / cm ² , flexural modulus: 33,300 kg / cm ² , Izod strength: 1.6 kg · cm / cm .

[0064]

Example 9 Side vent 1 immediately after the melting zone of the extruder
Was fitted with a nozzle, a side vent 2 was opened in front of the die, and an interlocking twin-screw extruder “ZSK-25 extruder” manufactured by Werner Co., Germany, in which the cylinder temperature was set to 220 ° C. ( The melt-kneading of A-9) is performed. The melting point of the thermoplastic resin (A-9) is 178 ° C. (A-9) was fed from the feed port of the extruder at a feed rate of 12 kg / hour, and (B-
9) from the nozzle of the side vent 1 at a pressure of 0.6 kg / hour. (A-9) The content of carbon dioxide is 5.0 parts by weight based on 100 parts by weight.

The emission of carbon dioxide from the side vent 2 is observed. After cooling the strand-like molten resin discharged from the extruder without foaming with water, a kneaded thermoplastic resin (D-9-9) is obtained using a strand cutter. (D-9-
The flat plate obtained by molding 9) is white, and no foreign matter is observed on the flat plate. The physical properties of the molded product (D-9-9) are as follows: heat deformation temperature: 127 ° C., tensile strength: 710 kg / cm ² , flexural modulus: 28,500 kg / cm ² , Izod strength: 11.5 kg · cm / cm It is.

[0066]

Comparative Example 9 Melting and kneading of (A-9) were carried out under the same conditions as in Example 9 except that the press-in of (B-9) was stopped to obtain a thermoplastic resin kneaded product (E-9). The plate obtained by molding (E-9) is milky white, and a small amount of foreign matter is observed.
The physical properties of the molded product (E-9) are as follows:
Tensile strength is 680 kg / cm ² , flexural modulus is 27.3
00kg / cm ² , Izod strength 10.4kg ・ c
m / cm.

[0067]

Example 10 A side vent 1 immediately after a melting zone of an extruder was fitted with a stopper with a nozzle, a side vent 2 in front of a die was opened, and a mutual bite made by German Werner Co., Ltd. was set at a cylinder temperature of 240 ° C. The melt-kneading of (A-10) is performed using a mold twin-screw extruder “ZSK-25 extruder”. The glass transition temperature of the thermoplastic resin (A-10) is 120 ° C.
(A-10) was supplied at a feed rate of 12 kg /
(B-9) is injected from the nozzle of the side vent 1 at a pressure of 0.6 kg / hour. (A-10) The content of carbon dioxide is 5.0 parts by weight based on 100 parts by weight.

The emission of carbon dioxide from the side vent 2 is observed. After cooling the strand-like molten resin discharged from the extruder without foaming with water, a kneaded thermoplastic resin (D-10-9) is obtained using a strand cutter. (D-1
The flat plate obtained by molding 0-9) is colorless and transparent, and no foreign matter is observed on the flat plate. The physical properties of the molded product (D-10-9) were such that the heat distortion temperature was 103 ° C and the tensile strength was 760 kg / c.
m ² , flexural modulus is 34,500 kg / cm ² , and Izod strength is 1.7 kg · cm / cm.

[0069]

Comparative Example 10 Melting and kneading of (A-10) were conducted under the same conditions as in Example 10 except that the press-in of (B-9) was stopped to obtain a thermoplastic resin kneaded product (E-10). (E-1
The flat plate obtained by molding 0) is colorless and transparent, and a small amount of foreign matter is observed. Physical properties of the molded product (E-10) are as follows: heat deformation temperature: 99 ° C., tensile strength: 740 kg / cm ² , flexural modulus: 33,500 kg / cm ² , and Izod strength: 1.6 kg · cm / cm. .

[0070]

Embodiment 11 Carbon dioxide was added in the same manner as in Embodiment 1 except that (B-12) was used instead of (B-7).
A mixture (C-1-12) containing 8 parts by weight of sorbed product is obtained. The cylinder temperature at the extruder feed port and in the vicinity was 53
° C and the other cylinder temperature was set to 270 ° C, and the melt kneading of (C-1-12) was performed in the same manner as in Example 1 to obtain a thermoplastic resin kneaded product (D-1-12).
Get. At this time, emission of carbon dioxide gas is observed from each of the extruder feed port and the extruder side vent port, and the melt-kneading becomes unstable. The flat plate obtained by molding (D-1-12) has a pale yellow color tone, and no foreign matter is observed. (D
The physical properties of the molded product of (1-1-12) are such that the heat distortion temperature is 189.
° C, tensile strength 780 kg / cm ² , flexural modulus 2
6,200kg / cm ² , Izod strength 5.2kg
Cm / cm.

[0071]

Comparative Example 11 Carbon dioxide was added in the same manner as in Example 1 except that (B-13) was used instead of (B-7).
A mixture (C-1-13) containing 5 parts by weight of sorbed product is obtained. The cylinder temperature at the extruder feed port and in the vicinity was 53
° C and the other cylinder temperature was set to 270 ° C, but the melt kneading of (C-1-13) was attempted in the same manner as in Example 1, but carbon dioxide gas was violently diffused from the feed port of the extruder. Melt kneading is difficult.

[0072]

Example 12 A mixture (C-1-) containing 0.7 parts by weight of carbon dioxide in the same manner as in Example 1 except that (B-3) was used instead of (B-7) 3) and a thermoplastic resin kneaded product (D-1-3) is obtained. The flat plate obtained by molding (D-1-3) was brown, and no foreign matter was observed. The physical properties of the molded article (D-1-3) are as follows.
87 ° C., tensile strength 740 kg / cm ² , flexural modulus 25,200 kg / cm ² , Izod strength 5.1 k
g · cm / cm.

[0073]

Comparative Example 12 In the same manner as in Example 1 except that (B-2) was used instead of (B-7), a mixture (C-1-) containing 0.3 parts by weight of carbon dioxide and sorbed therein was contained. 2) and a thermoplastic resin kneaded product (D-1-2) is obtained. The plate obtained by molding (D-1-2) is brownish, and foreign matter is observed.
The physical properties of the molded product of (D-1-2) are as follows.
° C, tensile strength 730 kg / cm ² , flexural modulus 2
5,200kg / cm ² , Izod strength 4.2kg
Cm / cm.

[0074]

Example 13 The procedure of Example 2 was repeated, except that (B-4) was used in place of (B-9) and press-fitting was performed at 0.12 kg / hour. A mixture having a carbon dioxide content of 1.0 part by weight is extruded to obtain a thermoplastic resin kneaded product (D-2-4). The flat plate obtained by molding (D-1-3) was brown, and no foreign matter was observed.
The physical properties of the molded product of (D-1-3) are as follows.
° C, tensile strength 745 kg / cm ² , flexural modulus 2
5,000kg / cm ² , Izod strength 5kg ・ c
m / cm.

[0075]

Comparative Example 13 Extrusion of (A-2) was carried out in the same manner as in Example 13 except that (B-2) was used instead of (B-9). No carbon dioxide is introduced into the extruder, and no emission of carbon dioxide from the side vent is observed. The flat plate obtained by molding the obtained thermoplastic resin kneaded material is brownish and many foreign substances are observed.

[0076]

Example 14 100 parts by weight of the thermoplastic resin (A-3) and 5 parts by weight of (B-1) were sealed in an autoclave and allowed to stand for 24 hours, and 2.4 parts by weight of carbon dioxide was absorbed and contained. A mixture (C-3-1) is obtained. The melt-kneading of (C-3-1) is performed using an interlocking twin-screw extruder “ZSK-25 extruder” manufactured by Welner, Germany with the cylinder temperature set to 280 ° C. Emission of carbon dioxide gas is observed from the feed port and the side vent 2. After cooling the strand-shaped molten resin having no foam discharged from the extruder with water, a kneaded thermoplastic resin (C-3-1) is obtained using a strand cutter. The flat plate obtained by molding (C-3-1) is white,
No foreign matter is observed on the flat plate. The physical properties of the molded product of (D-3-1) were such that the heat distortion temperature was 71 ° C and the tensile strength was 830 kg /.
cm ² , the flexural modulus is 29,200 kg / cm ² , and the Izod strength is 4.6 kg · cm / cm.

[0077]

Example 15 100 parts by weight of a thermoplastic resin (A-4) was sealed in an autoclave, and (B-
After supplying 5), the mixture is allowed to stand for 4 hours to obtain a mixture (C-4-5) containing 1.4 parts by weight of carbon dioxide gas and a thermoplastic resin kneaded product (D-4-5). The flat plate obtained by molding (D-4-5) is pale yellow, and no foreign matter is observed on the flat plate. The physical properties of the molded product (D-4-5) are as follows.
23 ° C., tensile strength 515 kg / cm ² , flexural modulus 24,400 kg / cm ² , Izod strength 15.6
kg · cm / cm.

[0078]

Example 16 100 parts by weight of a thermoplastic resin (A-5) were sealed in an autoclave, and (B-
After supplying 6), the mixture is allowed to stand for 4 hours to obtain a mixture (C-5-6) containing 1.2 parts by weight of carbon dioxide and containing a kneaded thermoplastic resin (D-5-6). The flat plate obtained by molding (D-5-6) is yellow, and no foreign matter is observed on the flat plate. The physical properties of the molded product (D-5-6) are as follows.
03 ° C., tensile strength 1060 kg / cm ² , flexural modulus 33,200 kg / cm ² , Izod strength 5.1
kg · cm / cm.

[0079]

Example 17 A mixture (C-1-) containing 6.8 parts by weight of carbon dioxide in the same manner as in Example 1 except that (B-8) was used instead of (B-7) 8) is obtained. Melt kneading of (C-1-8) was performed in the same manner as in Example 1 except that the temperature of the cylinder at the feed port of the extruder and the vicinity thereof was set to 53 ° C., and the other cylinder temperatures were set to 270 ° C. A kneaded plastic resin (D-1-8) is obtained. At this time, emission of carbon dioxide gas is observed from each of the extruder feed port and the extruder side vent port. The flat plate obtained by molding (D-1-8) has a pale yellow color tone, and no foreign matter is observed. The physical properties of the molded product (D-1-8) are as follows: heat deformation temperature: 189 ° C., tensile strength: 770 kg / cm ² , flexural modulus: 25,400 kg / cm ² , Izod strength: 5.
It is 5 kg · cm / cm.

[0080]

Example 18 A thermoplastic resin kneaded product (D-5-9) was prepared in the same manner as in Example 5 except that (B-9), which was press-fit from the nozzle of the side vent 1, was changed to (B-10). obtain. The flat plate obtained by molding (D-5-9) is yellow-brown, and no foreign matter is observed on the flat plate. The physical properties of the molded product (D-5-9) were such that the heat distortion temperature was 203 ° C and the tensile strength was 107.
0 kg / cm ² , flexural modulus 33,300 kg / c
m ² , and Izod strength is 5.3 kg · cm / cm.

Claims (5)

[Claims] In a melt kneading process of a thermoplastic resin,
0.3 to 2 with respect to 100 parts by weight of the thermoplastic resin (A)
A thermoplastic resin characterized in that a mixture containing 0.0 parts by weight of carbon dioxide (B) is melt-kneaded, and carbon dioxide (B) is diffused during the melt-kneading to obtain a thermoplastic resin kneaded product without foaming. A method for producing a resin kneaded material. 2. The thermoplastic resin (A) is an amorphous thermoplastic resin, and the processing temperature for melt-kneading is a temperature not higher than the glass transition temperature of the thermoplastic resin (A) + 150 ° C. Item 4. The method for producing a thermoplastic resin kneaded product according to Item 1. 3. The thermoplastic resin (A) is a crystalline thermoplastic resin, and the processing temperature for melt-kneading is a temperature equal to or lower than the melting point of the thermoplastic resin (A) + 100 ° C. Production method of kneaded thermoplastic resin. 4. A thermoplastic resin kneaded product produced by the method according to claim 2, wherein the glass transition temperature of the thermoplastic resin (A) is 110 ° C. to 250 ° C. Molded thermoplastic resin. 5. The thermoplastic resin kneaded product produced by the method according to claim 2, wherein the thermoplastic resin (A) is a modified polyphenylene ether resin, and the heat molded using the kneaded product. Plastic molded article.