JPH0791415B2 - Method for producing partially crosslinked thermoplastic resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a novel thermoplastic resin composition. Specifically, by dynamically heat treating a thermoplastic resin using a carbon radical inducer,
The present invention relates to a method for producing a thermoplastic resin composition having a good balance of rigidity, impact resistance, flexibility and moldability.

[0002]

2. Description of the Related Art Thermoplastic resins are used in a wide range of industrial fields as materials having excellent moldability. The field of application has been expanded by blending and modifying these thermoplastic resins with different or homogeneous resins or fillers having various properties. In addition, various attempts have been made to dynamically heat-treat the mixture thus obtained to improve the effects of the above-mentioned blend, for example, improvement of impact resistance and heat resistance. As an example thereof, a method of dynamically heat treating a thermoplastic resin using an organic peroxide is known. However, the composition obtained by the method using an organic peroxide is desired to be improved in the following points, though it has advantages. For example, Japanese Patent Publication No. 53-34210 (= USP-3,80
6,558), a free radical generator typified by an organic peroxide is used. Therefore, when the thermoplastic resin is a non-crosslinked organic peroxide resin such as polypropylene resin. Although a composition having good fluidity during molding can be obtained, the organic peroxide remaining in the composition deteriorates the thermal stability and the weatherability, and the thermal decomposition of the organic peroxide abruptly occurs. As a result, the molecular cleavage reaction is unavoidable,
As a result, mechanical properties such as tensile yield strength, flexural strength and flexural modulus decrease. Further, when the composition is used for extrusion and blow molding, deterioration of drawdown resistance, roughening of parison and lack of elongation are problems. It has been pointed out that the gloss deteriorates even during injection molding, affecting the aesthetics of the product. On the other hand, for organic peroxide cross-linking type resins such as polyethylene resins, the flowability of the composition is significantly deteriorated, which makes moldability difficult,
It is difficult to handle because a very small amount of organic peroxide must be used. Furthermore, when organic peroxides are used, the stability and safety of the free radical generator during storage and dynamic treatment, and the thermal decomposition loss due to the adhesion to the heated machine inner wall, are always associated problems. Therefore, a solution is desired.

Further, the following method is known as a method for crosslinking a thermoplastic resin having a carbon-carbon unsaturated bond containing rubber. The first method uses a sulfur-based cross-linking agent and is disclosed in Japanese Patent Publication No. 55-18448 (= USP-4,1).
30, 535) have been proposed. However, the one that is dynamically heat-treated by adding a sulfur-based cross-linking agent that accompanies the generation of sulfur radicals not only produces an extremely bad odor at a normal kneading temperature, but the obtained composition also gives a bad odor. The offensive odor of this composition is regenerated during the plasticizing process during the molding process, significantly reducing the commercial value. In addition, since this composition has a deep yellow-red color, the degree of freedom in coloring the composition is limited, and bleeding of sulfur compounds may cause discoloration during long-term use, limiting the field of use. .

The second method is as follows.
No. 38 (US Application No. 84977; USP-4,
311 and 628) and Japanese Patent Publication No. 54-19421, there is proposed a cross-linking agent in which a halide is added to a halogenated phenol resin or a phenol formaldehyde resin. However, since the active halogen is liberated during the cross-linking reaction, the composition is The color changes to black and the freedom of coloring is lost.
In addition, it is difficult to say that the composition obtained by using these crosslinking agents has good fluidity.

As a third method, the above Japanese Patent Publication No. 54-1 is used.
Although cross-linking with a quinonedioxime compound is also proposed in Japanese Patent No. 9421, since quinonedioximes are dark purple, the degree of freedom in coloring the composition is greatly limited, and a pungent odor is generated during dynamic heat treatment. There's a problem. Further, the composition obtained by this method cannot be said to have good flow characteristics during molding.

As a fourth method, Japanese Patent Publication No. 55-466.
61 (= USP-4,104,210) and JP-B-55-18448 (= USP-4,130,
535) shows an example of a bismaleimide compound or a combination thereof with a thiazole compound. In the former, N, N'-m-phenylene bismaleimide is used for a highly unsaturated diene rubber, but a large amount of addition is required to obtain a predetermined cross-linking effect. There was a problem such as bleeding of the reaction component. In the latter case, the polypropylene / EPDM system has the same N,
Although N'-m-phenylene bismaleimide is used, it has reported extremely insufficient results regarding the modification effect by the dynamic heat treatment. Bismaleimide compounds are generally expensive, and the addition of a large amount causes a high cost. Although various crosslinking methods are known as described above, a method with higher efficiency is required.

[0007]

DISCLOSURE OF THE INVENTION In view of the above points, the present invention has found a cross-linking reaction using a carbon radical inducer which does not have a runaway extreme cross-linking reaction which is a drawback of conventional organic peroxides. It is an object of the present invention to provide a thermoplastic resin composition in which conventional drawbacks have been improved by using this to crosslink a thermoplastic resin.

[0008]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies in view of the above-mentioned objects, and as a result, partially cross-linked polymers obtained by dynamically heat treating a thermoplastic resin in the presence of a carbon radical inducer. The present inventors have found that the thermoplastic resin composition obtained remarkably excellent results as compared with the case where a conventional crosslinking agent is used, and arrived at the present invention. That is, the present onset Ming, in the presence of the thermoplastic resin (A) material or a hydrogen donating compound including a charge transfer complex and a hydrogen accepting compound carbon radical inducing agent formed from a material containing (B), the dynamic heat treatment child
A partially crosslinked thermoplastic resin composition characterized by
It is a construction method .

The present invention will be described in detail below. First, the thermoplastic resin used in the present invention includes crystalline polypropylene, propylene / α-olefin / random copolymer, high-medium density polyethylene, polybutene-
1, poly-4-methylpentene-1, high-pressure low-density polyethylene, linear low-density polyethylene, extremely low-density polyethylene, ethylene-unsaturated carboxylic acid ester copolymer, ethylene-carboxylic acid unsaturated ester copolymer Polyolefin resin such as or polystyrene resin, polyacrylonitrile resin, polymethacrylate resin, polyamide resin, polyester resin, polycarbonate resin, polyphenylene resin, polyphenylene ether resin, polyphenylene sulfide resin, polyphenylene sulfone Examples of the resin include a resin and a polyacetal resin, or a mixture thereof.

Further, particularly as a rubber-like substance, ethylene / α
-Olefin copolymer rubber, ethylene / propylene random copolymer rubber, ethylene / propylene / diene random copolymer rubber, 1,2-polybutadiene, styrene / butadiene / styrene block copolymer rubber, styrene / isoprene / styrene block Copolymer rubber, natural rubber, nitrile rubber, isobutylene rubber, etc.
These may be used alone or as a mixture. Among them, ethylene / propylene random copolymer rubber and ethylene / propylene / diene random copolymer rubber are particularly preferable.

These two rubbers have excellent thermoplasticity as compared with other rubber-like substances, are easy to disperse by melt-kneading, and do not have a unique odor as compared with SBR, isoprene rubber, nitrile rubber or butadiene rubber. point,
Alternatively, since it is available in the form of pellets, it is easy to measure and handle when compounding, and there is a large degree of freedom in selection of the type of the composition manufacturing apparatus, which is advantageous in operation.

As the diene component of the above ethylene / propylene / diene random copolymer rubber, any of conventionally known ones such as ethylidene norbornene, 1,4-hexadiene and dicyclopentadiene can be used.

The method of the present invention can be used for a wide range of crosslinked thermoplastic resin compositions having various properties by changing the type and blending ratio of the thermoplastic resin. The thermoplastic resin used is arbitrarily selected from the above description. Examples thereof include a combination of polyolefin and a different thermoplastic resin, a combination of polyolefins, and a combination of polyolefin and a rubber-like substance. In this case, since the heterogeneous thermoplastic resin is melt-kneaded with the polyolefin resin or the rubber-like substance, the melting point or the softening point of the heterogeneous thermoplastic resin is selected from those relatively close to those of the polyolefin resin or the rubber-like substance. It is preferable.

In the case of polyolefin resins, polypropylene and ethylene (co) polymer are a preferable combination because they have an excellent balance of physical properties and can be obtained at low cost. Polypropylene has excellent heat resistance and rigidity, and ethylene (co) polymers are high-pressure low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, ethylene / unsaturated carboxylic acid ester copolymer. , Such as ethylene / carboxylic acid unsaturated ester copolymers, can be obtained in a wide range from those with high flexibility to those with high rigidity. Therefore, those obtained only from these polyolefin resins can deal with a wide range of physical properties. .

Further, a combination in which a rubber-like substance is added to these polyolefin resins is also a preferable combination. It is possible to deal with a wider range of physical properties than those obtained by combining only polyolefin resins. For example, the effect of improving low temperature impact resistance is remarkable. The specific mixing ratio is preferably 20 to 100% by weight of the polyolefin resin and 0 to 80% by weight of the rubber-like substance. If the rubber-like substance exceeds 80% by weight, processing becomes difficult, which is not preferable.

In the present invention, a softener can be added during and / or after the heat treatment. As the softening agent, the same one as the so-called extender oil, which is used mainly for the purpose of improving the processability during the processing of rubber, the effect of increasing the amount or the dispersibility of the filler, is used. These are high boiling point petroleum components and are classified into paraffinic, naphthenic and aromatic types. In the present invention, not only these petroleum fractions but also synthetic oils such as liquid polyisobutene can be used.

In the present invention, the carbon radical inducer added as an essential component during the dynamic heat treatment is formed of a substance containing a charge transfer complex or a substance containing a hydrogen donating compound and a hydrogen accepting compound. Say.

First, the combination of compounds forming a charge-transfer complex is one in which the charge is transferred from one compound to the other by forming the complex to radically cleave the unsaturated bond. The compound used for this purpose may have any difference in the electron density of the unsaturated bond, and various combinations are known as intercopolymers. In the present invention, maleimide compounds (for example, N, N'-m-phenylene bismaleimide, N, N'-ethylene bismaleimide), unsaturated carboxylic acid derivatives (for example, maleic anhydride) are used as compounds having a low electron density of unsaturated bonds. , Ethylene glycol dimethacrylate) are preferably used. The bismaleimide-based compound that is not involved in radical formation is preferable because it plays a role as a general crosslinking aid. Further, the unsaturated carboxylic acid derivative, which was not involved in the radical formation, is graft-reacted with the thermoplastic resin to newly act as an adhesive or a compatibilizer. Therefore, when expecting the effect, it is especially preferable to use an unsaturated carboxylic acid derivative. As a compound which forms a charge transfer complex with these compounds, those having a high electron density of unsaturated bonds are used. Examples thereof include styrene, α-methylstyrene, trans-stilbene, vinylferrocene, 4-vinylpyridine, 2-isopropenylnaphthalene, N-vinylcarbazole, N-vinylindole and indole. Also furan, 3,4-dihydro-2-
Cyclic vinyl ether represented by pyran, 4H-chromene, furfuryl alcohol, furfuryl aldehyde, benzofuran, furan derivative represented by furfuryl acetate, n-octadecyl vinyl ether, linear vinyl ether compound represented by ethyl vinyl ether, ketene Acetal, isopropenyl acetate, 1-amino-1
-Enol ethers of carbonyl compounds such as ketones, esters, lactones, aldehydes, amides, lactams represented by methoxyethylene, enol esters, allyl acetate, vinyl acetate, 1,2-dimethoxyethylene, p-dioxene, 2-chloroethyl Vinyl ether, 2-phenylalkenyl ether, heptafluoroisopropyl alkenyl ether, ethyl vinyl sulfide, styryl alkenyl thioether, p-oxadiene, cyclopentene, cyclohexene, divinyl ether, butadiene, isoprene, 1,3-pentadiene, 1,4-pentadiene, Examples thereof include dimethyldivinylsilane. Further, in the present invention, it is preferable that the complex does not form a mutual copolymer and exists as a radical.

Secondly, the combination of the hydrogen-donating compound and the hydrogen-accepting compound is a compound in which a hydrogen atom is transferred from the former to the latter and both are radicalized. The hydrogen-donating compound is a compound capable of resonance-stabilizing itself even after releasing hydrogen radicals, and is characteristically reacted for 30 minutes under a predetermined amount of the compound at 350 ° C., 50 atmospheric pressure (under N ₂ ) and no catalyst. , That in which the amount of hydrogen transferred from the compound to anthracene of the hydrogen acceptor is at least 0.1 (hydrogen atom / mol anthracene), octahydrophenanthrene, octahydroanthracene, tetralin, indene, tetrahydrofuran, 2,3- Examples include dihydrobenzofuran and fluorene. Among these, octahydrophenanthrene, octahydroanthracene, tetralin, indene, fluorene and the like are easily available, and they are excellent in that the final composition is not colored and does not decompose the ester or amide. The hydrogen-accepting compound is a compound having a small resonance stabilization when it becomes a radical by adding the hydrogen radical, and a compound generally used as a crosslinking aid at the time of rubber crosslinking using a peroxide is used. Specifically, trimethylolpropane trimethacrylate, ethylene glycol di (meth) acrylate, triallyl (iso)
Polyfunctional vinyl monomers typified by cyanurate and diallyl phthalate can be mentioned. However, in the present invention, a maleimide compound (for example, N, N'-m-phenylene bismaleimide, N, N'-ethylene bismaleimide), an unsaturated carboxylic acid derivative (for example, maleic anhydride) is used because of its high reactivity as a radical. , Ethylene glycol dimethacrylate) are preferably used. These inducers may be used alone or in combination.

In particular, a combination of (B1) a compound having an unsaturated bond having a high electron density or a hydrogen-donating compound and (B2) a compound having an unsaturated bond having a low electron density or a hydrogen-accepting compound are used in combination. Is a preferred combination. More specifically, among (B1), compounds selected from (α) ether compounds, (β) tetrahydroaromatic compounds, (γ) cyclopentane compounds, and among (B2) (δ) bismaleimide compounds. Compounds selected from the compounds and (ε) polyol unsaturated ester compounds are highly active and are particularly preferred.

The ether compound (α) may be linear or cyclic, and may further have a substituent. Specific examples include 1,3-dioxolane, 1,
Cyclic ethers such as 4-dioxane, ethyl ether,
Linear ethers such as isopropyl ether, 3,4-
Non-aromatic cyclic vinyl ether represented by dihydro-2-pyran, 4H-chromene, furfuryl alcohol,
Furfuryl aldehyde, benzofuran, furan derivative represented by furfuryl acetate, n-octadecyl vinyl ether, linear vinyl ether compound represented by ethyl vinyl ether, ketene acetal, isopropenyl acetate, vinyl acetate, 1-amino-1-methoxy These are enol ethers and enol esters of carbonyl compounds such as esters represented by ethylene, lactones, aldehydes, amides and lactams. These may have a substituent, and a substituent by an alkyl group and other various elements,
Substituted derivatives with functional groups are used. Moreover, these may be individual or a mixture. Preferred is vinyl or alkenyl ether.

The tetrahydroaromatic compound (β) is
It means that at least one aromatic ring is tetrahydrogenated. The term "tetrahydroaromatic compound" used herein means a compound containing one or more aromatic rings and at least one aromatic ring being tetrahydrolated. The aromatic ring as used herein is a definition of aromaticity (for example, translated by Toshio Goto, "Basics of Organic Chemistry," pages 105-106, Tokyo Kagaku Dojin (1976) [Richard S. Mon.
-Son & John C. Shelton: Fun
DAMENTALS OF ORGANIC CHEM
istry, MacGraw-Hill, Inc. (1
974)] indicates a ring structure having 4n + 2 (n is an integer) number of π-electrons, and includes, for example, benzene and naphthalene. Also, Piran etc. are excluded. Therefore, the tetrahydroaromatic compound used in the present invention also includes a tetrahydro derivative of naphthalene. Further, the tetrahydroaromatic compound used in the present invention may have a substituent, and a substitution product by an alkyl group and various elements and a substitution derivative by a functional group are used. Such tetrahydroaromatic compounds can be arbitrarily synthesized by applying known chemical reactions, but if the currently available ones are exemplified, 1,2,3,4-tetrahydronaphthalene, tetrahydrobenzene, and tetrahydrofuran are Can be mentioned. It may also be a polymer of these compounds.

The cyclopentane compound (γ) means a compound containing at least one or more cyclopentane, cyclopentene or cyclopentadiene skeleton, that is, a 5-membered ring compound in which a ring is constructed only from carbon atoms. Specifically, cyclopentane, cyclopentene,
This includes cyclopentadiene, dicyclopentadiene, indene, indane, fluorene and the like. These may of course have substituents, and substitution products with alkyl groups and various elements and substitution derivatives with functional groups are used. These may be used alone or as a mixture. Of course, these compounds may have a substituent.

The bismaleimide compound (δ) is preferably ethylene bismaleimide and N, N'-m-phenylene bismaleimide.

Polyol unsaturated ester compound (ε)
Examples thereof include higher esters of methacrylic acid represented by trimethylolpropane trimethacrylate and ethylene glycol dimethacrylate. In addition to the listed (δ) or (ε) components, divinylbenzene,
Polyfunctional vinyl monomers typified by triallyl isocyanurate and diallyl phthalate can also be used. You may use these in combination of 2 or more types.

In the present invention, the mixture of the components obtained as described above is dynamically heat treated to obtain a resin composition. The dynamic heat treatment means that the mixture is melt-kneaded to increase the boiling xylene insoluble content in the composition after kneading as compared with the value before kneading. The effect of the present invention is achieved by this heat treatment. Generally, as the boiling xylene insoluble content increases, various effects such as impact resistance are greatly improved. The temperature of the dynamic heat treatment is within the temperature range above the melting point or softening point of the thermoplastic resin and below the decomposition point. Further, in melt-blending, it is preferable to use a mixer that gives a high shear rate so that radicals are easily generated in the mixture.

The main factor for increasing the boiling xylene insoluble content is the amount of the above-mentioned carbon radical inducer added, and the amount of these additives can be arbitrarily selected. That is, an appropriate addition amount is used depending on the kind of the carbon radical inducer or the apparatus and conditions of the melt kneading. If added excessively, bleeding of the added component, coloration of the composition or increase in cost, etc.
The amount to be added may be limited in consideration of these factors. The practical addition amount is usually 100% for all carbon radical inducers.
0.01 to 7 parts by weight, preferably 0.0
5 to 5 parts by weight.

As a method for carrying out the dynamic heat treatment, conventionally known ones such as an open type mixing roll, a non-open type Banbury mixer, an extruder, a kneader and a twin screw extruder can be used. The conditions for carrying out the present invention with the above composition are preferably a kneading temperature of 120 to 350 ° C. and a heat treatment time of 20 seconds to 20 minutes. It may also be carried out in a solvent.

In addition, if necessary, stabilizers, antioxidants, ultraviolet absorbers, lubricants, foaming agents, antistatic agents, dyes, pigments, glass fibers, carbon fibers, inorganic fillers, flame retardants are added to the composition of the present invention. And the like can be appropriately mixed.

[0031]

INDUSTRIAL APPLICABILITY The present invention can suppress the extreme crosslinking reaction, which is a drawback of conventional crosslinking agents, by dynamically heat-treating a thermoplastic resin using a carbon radical inducer. It was possible to produce desired partially cross-linked products from the process to polar cross-linking, and it was possible to remarkably improve the physical properties.

[0032]

EXAMPLES AND COMPARATIVE EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention. Examples 1 to 21, Comparative Examples 1 to 21 (A) As a thermoplastic resin, a polypropylene resin, a low density polyethylene resin, a high density polyethylene resin, a linear low density polyethylene resin, an extremely low density polyethylene resin, Ethylene / propylene / random copolymer rubber, ethylene / ethyl acrylate copolymer, and polyamide resin were used.

Method for Producing Composition 3 parts by weight of carbon radical inducer (B1) selected from (α), (β) and (γ) based on 100 parts by weight of the above-mentioned thermoplastic resin (A), carbon 2 parts by weight of the radical inducer (B2) selected from (δ) and (ε) were mixed (the combination of the types is summarized in Table 1), and the resulting mixture was treated with Laboplast mill (20R200 type). , Toyo Seiki Co., Ltd.). The reaction time was 5 minutes, 60 revolutions and the reaction temperature was 230 ° C., and the torque during melt kneading was observed. After the reaction was completed, the boiling xylene insoluble content was measured. In addition, the obtained composition was applied to a 40 mmφ extruder (L / D =
20) spiral die (diameter 125mm, lip 2m
m), a blow ratio of 1.8, and a processing temperature of 200 ° C., a film having a thickness of 30 μ was formed, and its physical properties were measured. Table 2 shows these results. The comparative example is a case where the kneading was performed without using the carbon radical inducer, and the torque was expressed as an increase (↑) and an unchanged (→) in comparison with the comparative example.

Test / measurement method (tensile yield strength) According to ASTM D882.

(Boiling xylene insoluble matter) 20 mm × 50 m
A m × 0.2 mm film was press-molded, put in a wire mesh of 120 mesh, and immersed in boiling xylene for 5 hours. The weight before and after the immersion was measured, and the boiling xylene insoluble matter was calculated from the following formula:

Examples 22 to 46, Comparative Examples 22 to 49 Polypropylene type resin, high density polyethylene, linear low density polyethylene type resin, polystyrene type resin, polyamide type resin, polyester type resin, ethylene / propylene / random copolymer weight A mixture of coalesced rubbers was used. Unless otherwise specified, the test pieces were obtained by injection-molding and used. A method for producing the composition,
The manufacturing conditions and test methods for injection-molded test pieces are as follows:

Method for Producing Composition 1) The above-mentioned thermoplastic resins were prepared in a predetermined mixing ratio and mixed with a Henschel mixer. 2) A predetermined amount of carbon radical inducer (B1) and carbon radical inducer (B2) were added to the mixture obtained above, and a twin-screw continuous kneading extruder (30 mmφ, manufactured by Plastic Engineering Laboratory Co., Ltd.) was used. The resin was melt-kneaded at a resin temperature of 180 to 260 ° C. and a rotation speed of 200 rpm, and a dynamic heat treatment was performed.

Injection molding conditions Molding machine IS-90B (manufactured by Toshiba Machine Co., Ltd.) Injection pressure 1,000 kg / cm ² Molding temperature 180-260 ° C Mold temperature 50 ° C

Test / Measurement Method (MFR) JIS K6760, JIS K6758,
According to JIS K7210.

(Tensile Fracture Strength) and (Tensile Fracture Elongation) JIS K6760, JIS K6758, JIS K
7113, ASTM D882.

(Flexural Modulus) JIS K6758, JI
According to SK7203.

(Vicat softening temperature) JIS K676
0, according to JIS K6758, JIS K7206.

(Izod impact value) JIS K675
8. According to JIS K7110.

(Crystallization temperature) It was measured as an index of the cycle time during injection molding. Since the higher the crystallization temperature, the faster the crystallization rate, it can be considered that the cycle time in injection molding can be shortened. The differential scanning calorific value system (SSC / 5
Approximately 1 sample using 80 type, Seiko Denshi Kogyo Co., Ltd.
After holding 0 mg at 210 ° C for 5 minutes, cooling rate is 10 ° C
The temperature showing the maximum of the exothermic curve obtained when the temperature was lowered at / min was defined as the crystallization temperature. The results are shown in Tables 3-5. In addition, the compounding ratio of the carbon radical inducer in Tables 3 to 5 is a value when the total amount of the thermoplastic resin is 100 parts by weight (the same applies to each table below).

Examples 47 to 54, Comparative Examples 50 to 56 Ultra low density polyethylene 70 to 90 was used as the thermoplastic resin.
Used by weight%. Unless otherwise specified, the test pieces were 100 mm x 200 mm x 2 m obtained by injection molding.
A flat plate having a size of m was punched out and used.
The method for producing the composition is the same as that described above, but in the melt-kneading step of the production method 2), the resin temperature is 150 to 22.
A mineral oil-based or synthetic oil-based softening agent was added from a reciprocating metering pump connected to the vent port when the range of 0 ° C was used. The test method is as follows:

Test / measurement method (high load MFR) According to JIS K7210. Temperature 23
Use 0 ℃, load 10kg.

(Tensile Fracture Strength) and (Tensile Fracture Elongation) According to JIS K6301. Tensile speed 200mm / m
in.

[0048] (durometer _hardness, H D A) ISO 8
According to 68.

(Permanent elongation) In accordance with JIS K6301. 100% stretch, use No. 3 dumbbell.

(Vicat softening temperature) JIS K7206
According to. Uses a load of 250g.

(Embrittlement temperature) JIS K6760, JI
According to SK7216.

(Abrasion resistance) According to JIS K7204 (using Taber type abrasion tester). Load 1.000g,
1,000 continuous rotations. The results are shown in Table 6. The blending ratio of the softening agent in Table 6 is 1 part by weight of the total resin.
The value is set to 00 parts by weight (the same applies to each table below).

Examples 55 to 62, Comparative Examples 57 and 58 Polypropylene resin, low density polyethylene resin, extremely low density polyethylene resin, ethylene / ethyl acrylate copolymer resin and ethylene / propylene / random copolymer rubber A mixture selected from was used. The method for producing the composition, the method for producing the test piece, and the conditions for producing the test piece by injection molding are the same as those in Examples 47 to 54. The test method is as follows:

Test / Measurement Method (Spiral Flow) A sample having a constant spiral cavity was injection-molded with a sample under the following molding conditions.
The melt flowability of the samples was tested by measuring the length of the molded spiral.

Conditions for injection molding Molding machine IS-90B (manufactured by Toshiba Machine Co., Ltd.) Injection pressure 1,000 kg / cm ² Molding temperature 230 ° C Stroke 25 mm Injection time 15 sec Curing time 10 sec Interval time 3 sec Mold Archimedes type , Temperature 50 ℃

(Bending strength) JIS K6758, JIS
According to K7203.

(Durometer hardness, H _D D) JIS K
6760, according to JIS K7215.

(Surface Roughness and Elongation of Parison) The parison was molded with the extruder for blow molding in the same manner as described above, and the surface and the state of elongation were visually evaluated. The evaluation was made in the following three stages: ◎ Very good, ○ good, × bad. The results are shown in Table 6.

Thermoplastic resin used in the present invention, thermoplastic resin such as carbon radical inducer (A) A1. Ultra-low density polyethylene Nisseki Softlex D9
010 MFR 0.9 manufactured by Nippon Petrochemical Co., Ltd. A2. Ultra-low density polyethylene Nisseki Softlex D9
005 MFR 0.5 manufactured by Nippon Petrochemical Co., Ltd. A3. Ultra-low density polyethylene Nisseki Softlex D9
550 MFR 5.0 manufactured by Nippon Petrochemical Co., Ltd. A4. Polypropylene Nisseki Polypro J120G MFR 1.5 manufactured by Nippon Petrochemical Co., Ltd. A5. Polypropylene Nisseki Polypro J130G MFR 4.0 manufactured by Nippon Petrochemical Co., Ltd. A6. Polypropylene Nisseki Polypro J150G MFR 8.0 manufactured by Nippon Petrochemical Co., Ltd. A7. Polypropylene Nisseki Polypro J160G MFR 14 manufactured by Nippon Petrochemical Co., Ltd. A8. Polypropylene Nisseki Polypro J170G MFR 30 manufactured by Nippon Petrochemical Co., Ltd. A9. Polypropylene Nisseki Polypro J420G MFR 1.5 manufactured by Nippon Petrochemical Co., Ltd. A10. Polypropylene Nisseki Polypro J630G MFR 4.0 manufactured by Nippon Petrochemical Co., Ltd. A11. Polypropylene Nisseki Polypro J650G MFR 8.0 manufactured by Nippon Petrochemical Co., Ltd. A12. Polypropylene Nisseki Polypro J871M MFR 23 manufactured by Nippon Petrochemical Co., Ltd. A13. Polypropylene Nisseki Polypro J880G MFR 40 manufactured by Nippon Petrochemical Co., Ltd. A14. Linear low density polyethylene Nisseki Linirex AF1210 MFR 0.8 manufactured by Nippon Petrochemical Co., Ltd. A15. Linear low-density polyethylene Nisseki Linirex AJ5610 MFR 10 manufactured by Nippon Petrochemical Co., Ltd. A16. Linear low-density polyethylene Nisseki Linirex AJ6820 MFR 30 manufactured by Nippon Petrochemical Co., Ltd. A17. Linear low density polyethylene Nisseki Linirex AJ6285 MFR 32 manufactured by Nippon Petrochemical Co., Ltd. A18. Low-density polyethylene Nisseki Lexron F102 MFR 0.25 manufactured by Nippon Petrochemical Co., Ltd. A19. Low-density polyethylene Nisseki Lexron F22 MFR 1.0 manufactured by Nippon Petrochemical Co., Ltd. A20. Low density polyethylene Nisseki Lexron F312 MFR 2.0 manufactured by Nippon Petrochemical Co., Ltd. A21. Low-density polyethylene Nisseki Lexron F504 MFR 9.5 manufactured by Nippon Petrochemical Co., Ltd. A22. Ethylene-ethyl acrylate copolymer Nisseki Lexron EEA A3050 MFR 3.0
A23. Made by Nippon Petrochemical Co., Ltd. Ethylene / ethyl acrylate copolymer Nisseki Lexron EEA A3100 MFR 3.0
A24. Made by Nippon Petrochemical Co., Ltd. Ethylene / ethyl acrylate copolymer Nisseki Lexron EEA A3150 MFR 3.0
A25. Made by Nippon Petrochemical Co., Ltd. Ethylene / ethyl acrylate copolymer Nisseki Lexron EEA A4250 MFR 5.0
A26. Made by Nippon Petrochemical Co., Ltd. High Density Polyethylene Nisseki Staflen E809
(M) MFR 0.9 manufactured by Nippon Petrochemical Co., Ltd. A27. High Density Polyethylene Nisseki Staflen E750
(C) MFR 5.3 manufactured by Nippon Petrochemical Co., Ltd. A28. High Density Polyethylene Nisseki Staflen E807
(F) MFR 0.6 manufactured by Nippon Petrochemical Co., Ltd. A29. Ethylene / propylene-random copolymer rubber EP02P ML _{1 + 4} = 24 manufactured by Nippon Synthetic Rubber Co., Ltd. A30. Ethylene / propylene-random copolymer rubber EP07P ML _{1 + 4} = 70 manufactured by Nippon Synthetic Rubber Co., Ltd. A31. Ethylene / propylene / diene random copolymer rubber EP57P ML _{1 + 4} = 88 manufactured by Nippon Synthetic Rubber Co., Ltd. A32.6-nylon CM1021 manufactured by Toray Co., Ltd. A33. Polystyrene Topolex 525 manufactured by Mitsui Toatsu Chemicals, Inc. A34. Polybutylene terephthalate PBT310
Toray Industries, Ltd. carbon radical inducer (B1, compound having unsaturated bond with high electron density or hydrogen donating compound) α. Ether compound α-1. Dihydropyran manufactured by Tokyo Kasei KK α-2. Isopropenyl acetate manufactured by Tokyo Chemical Industry Co., Ltd. β. Tetrahydroaromatic compound β-1.1,2,3,4-tetrahydronaphthalene Tokyo Chemical Co., Ltd. β-2. Tetrahydrobenzene Tokyo Chemical Co., Ltd. β-3. Tetrahydrofuran Tokyo Chemical Co., Ltd. γ. Cyclopentane compound γ-1. Indene carbon radical inducer (B2, compound having unsaturated bond with low electron density or hydrogen accepting compound) δ. Bismaleimide compound δ-1. N, N′-m-phenylene bismaleimide Barnock PM Ouchi Shinko Chemical Co., Ltd. ε. Polyol unsaturated ester compound ε-1. Ethylene glycol dimethacrylate Tokyo Kasei Co., Ltd. Softener (C) Super Oil C Nippon Oil Co., Ltd. Organic peroxide (D) α, α'-pis- (t-putylperoxy) -m-diisopropylbenzene Perbutyl Made by Nippon Oil & Fat Co., Ltd.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

[Table 11]

[Table 12]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C08L 23:02 33:00 77:00 (56) References JP-A-60-49052 (JP , A) JP 63-99251 (JP, A) JP 63-286445 (JP, A) JP 64-62338 (JP, A)

Claims (9)

[Claims] 1. A thermoplastic resin (A) is dynamically heat treated in the presence of a charge transfer complex or a carbon radical inducer (B) formed from a hydrogen donating compound and a hydrogen accepting compound.
Of a partially crosslinked thermoplastic resin composition, characterized in that
Manufacturing method. 2. The carbon radical inducer (B) is (B1) a compound having an unsaturated bond having a high electron density or a hydrogen donating compound (α) ether compound (β) tetrahydroaromatic compound (γ) cyclo At least one selected from pentane compounds and (B2) at least one selected from (δ) bismaleimide compounds (ε) polyol unsaturated ester compounds as a compound having an unsaturated bond having a low electron density or a hydrogen accepting compound The method of claim 1, wherein the method is formed from seeds . 3. A carbon radical inducer (B1) (B2)
Was blended in an amount of 0.01 to 7 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A), respectively . 4. The method according to claim 1, wherein the thermoplastic resin (A) comprises a polyolefin resin and a different thermoplastic resin . 5. The method according to claim 1, wherein the thermoplastic resin (A) comprises a polyolefin resin and a rubber-like substance . 6. The method according to claim 1, wherein the thermoplastic resin is a mixture of at least two kinds selected only from polyolefin resins . 7. The method according to claim 1, wherein the polyolefin resin contains at least one selected from the group consisting of polypropylene and ethylene (co) polymer . 8. The method according to claim 5, wherein the rubber-like substance comprises an ethylene / propylene random copolymer rubber and / or an ethylene / propylene / diene random copolymer rubber . 9. The method according to claim 1, wherein 1 to 100 parts by weight of a softening agent is added to 100 parts by weight of the thermoplastic resin (A) .