JPH0657047A - Thermoplastic resin composition and compatibilizer - Google Patents

Abstract

PURPOSE:To provide the resin composition excellent in impact resistance, delamination resistance and fluidity and useful for moldings, etc., by blending a vinyl chloride based resin, etc., with an olefin-based resin and a specific compatibilizer in a specific ratio. CONSTITUTION:The resin composition is obtained by blending 100 pts. wt. total amount of (A) 1-99 pts.wt. vinyl chloride-based resin and/or styrene-based resin and (B) 99-1 pts.wt. olefin-based resin such as PP with (C) 0.1-50 pts. wt. compatibilizer consisting of (i) 5-95 pts.wt. modified olefin-based polymer containing 0.05-50wt.% compound having a reactive group such as carboxyl group and (ii) 95-5 pts.wt. modified vinyl chloride-based polymer containing 0.05-50wt.% compound having a reactive group capable of reacting with the component (i), e.g. epoxy group, amino group or hydroxyl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition and a compatibilizer which are particularly excellent in surface layer peeling resistance, and more specifically provides a molded article which is excellent in impact resistance and surface layer peeling resistance. At the same time, it relates to a thermoplastic resin composition having excellent fluidity and a compatibilizing agent used for the composition.

[0002]

2. Description of the Related Art Recently, alloying polymers having different properties to modify a resin has been actively studied. For example, regarding the alloying of an olefin resin and a styrene resin or a vinyl chloride resin, a method of alloying with an ethylene-vinyl acetate copolymer (Japanese Patent Publication No. 60-36178) or a polyethylene-EPDM modified product is used. Method (JP-A-63-304039, JP-A-1-165640), and method of alloying with a block of polypropylene and styrene resin (JP-A-2-
199127, JP-A-2-199128, JP-A2-1
99129) has been reported.

[0003]

However, in the above-mentioned conventional method, the impact resistance is lowered, and
After molding under high shear such as injection molding, a surface layer peeling phenomenon occurs in which the surface layer of the molded product is separated from the molded product with a slight force, which is not suitable for practical use. An object of the present invention is to solve the above problems and provide a thermoplastic resin composition having excellent impact resistance, surface layer peeling resistance, and fluidity.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that vinyl chloride resin and / or styrene resin and olefin resin are
It is interesting to use a compatibilizer composed of a modified olefin polymer containing a compound having a reactive group and a modified vinyl chloride polymer containing a compound having a reactive group reactive with this reactive group. In addition, the inventors have found that the impact resistance does not decrease and the surface layer does not peel under high shear, and the present invention has been completed.

That is, the first aspect of the present invention comprises 1 to 99 parts by weight of a vinyl chloride resin (A) and / or styrene resin (B) and 99 to 1 parts by weight of an olefin resin (C).
Thermoplastic resin composition obtained by blending 0.1 to 50 parts by weight of the following compatibilizing agent (Y) with respect to 100 parts by weight in total of (A), (B) and (C): Compatibilizing agent (Y) : 0.05 to 5 compounds having a reactive group
Modified olefin polymer (D) 5-9 containing 0% by weight
A compatibilizer comprising 5 parts by weight and 95 to 5 parts by weight of a modified vinyl chloride polymer (E) containing 0.05 to 50% by weight of a compound having a reactive group reactive with the reactive group of (D). ,
The second aspect of the present invention is to use a compound having a reactive group in an amount of 0.05 to 5
Modified olefin polymer (D) 5-9 containing 0% by weight
A compatibilizer comprising 5 parts by weight and 95 to 5 parts by weight of a modified vinyl chloride polymer (E) containing 0.05 to 50% by weight of a compound having a reactive group reactive with the reactive group of (D). , Respectively.

The compatibilizing agent used in the present invention comprises a olefin polymer modified with a specific compound and a vinyl chloride polymer containing a compound having a reactive group that reacts with the specific compound. It is an essential component for the thermoplastic resin composition of the present invention to exhibit impact resistance and surface layer peeling resistance. That is, the compatibilizer (Y) of the present invention
Has an effect of improving the compatibility between resins which originally have no compatibility or poor compatibility, such as vinyl chloride resin and / or styrene resin and olefin resin.

The modified olefin polymer (D) used in the present invention is a modified olefin polymer having a reactive group. Such a modified olefin polymer can be produced by copolymerizing a compound having a reactive group capable of polymerizing with an olefin, for example, a compound having a vinyl group and also having another reactive group, with an olefin. In addition, after a polyolefin is produced by a usual polymerization method, a compound having a reactive group capable of polymerizing with an olefin, such as a vinyl group, on the polyolefin chain and a compound having another reactive group are grafted by a usual method. It may be introduced by polymerization. When copolymerizing or graft-polymerizing with an olefin, a polymerizable vinyl monomer other than the compound having a reactive group can be copolymerized. Examples of the reactive group include an epoxy group, a 1,2,3 tertiary amino group, an amide group, a carboxyl group, an acid anhydride, a hydroxyl group and the like, and these are used alone or in combination of two or more kinds. In order to make the reaction with the reactive group introduced into the modified vinyl chloride polymer (E) of the present invention more effective, a carboxyl group and an acid anhydride are preferable, and an acid anhydride is particularly preferable.

As the compound capable of introducing a reactive group, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, dimethylaminoethyl methacrylate, vinyl pyridine, t-butylaminoethyl methacrylate, acrylamide, methacrylamide, maleimide, acrylic acid, methacrylic acid, Maleic acid, maleic anhydride, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate,
2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, etc. are exemplified. The reactive group only needs to react with the modified vinyl chloride-based polymer (E) to produce a compatibilizing agent, and the compound containing the reactive group may have a pH of 0.
The amount is 05 to 50% by weight, preferably 0.1 to 30% by weight. If it is less than 0.05% by weight, the resistance to peeling of the surface layer is not exerted, and if it exceeds 50% by weight, the fluidity is greatly reduced.

The method for producing the copolymer of the olefin polymer and the compound capable of introducing a reactive group is not particularly limited, but the following two methods can be preferably used. The first production method is a graft modification method of an olefin polymer, and the second production method is a method of copolymerizing an olefin monomer and a compound capable of introducing a reactive group. The first production method is to radically add a composition comprising two components of an olefin polymer and a compound capable of introducing a reactive group, using a radical initiator. At this time, a solvent that dissolves or swells the olefin polymer, for example, tetralin, decalin, toluene, xylene, or chlorobenzene may be used. Specifically, there is a method in which a compound capable of introducing an olefin polymer and a reactive group is melt-kneaded using, for example, various conventionally known blenders such as an extruder, a heating roll, a Brabender, and a Banbury mixer. . The second production method is a method of copolymerizing an olefin monomer and a compound capable of introducing a reactive group. The copolymerization method is not particularly limited, but a general radical polymerization method,
In addition to the cationic polymerization method and the anionic polymerization method, a coordination polymerization method using a transition metal can also be used. The modified olefin polymer produced by radical addition of a compound capable of introducing a reactive group to the olefin polymer or copolymerization of an olefin monomer with a compound capable of introducing a reactive group is a graft copolymer or a block copolymer. And so on.

The olefin polymer used as the raw material of the modified olefin polymer used in the present invention is a homopolymer of various olefin monomers, or a random copolymer, block copolymer or graft copolymer of these olefin monomers,
Alternatively, a mixture of these homopolymers or copolymers can be used. For example, high density polyethylene, medium density polyethylene, low density polyethylene, ethylene and other α-
Copolymers with olefins, polypropylene, copolymers with propylene and other α-olefins, polybutene,
Polyolefins or oligomers such as poly-4-methylpentene-1, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer, butyl rubber, butadiene rubber, propylene-butene copolymer, ethylene-acrylic Examples thereof include polyolefin elastomers such as acid ester copolymers, which may be used alone or in combination of two or more. Among these, from the viewpoint of impact resistance and heat resistance, low density polyethylene,
Polypropylene, copolymers of propylene and other α-olefins and oligomers thereof are preferable, and polypropylene, copolymers of propylene and other α-olefins and oligomers thereof are particularly preferable.

The three-dimensional structure of the olefin polymer is not particularly limited, but from the viewpoint of heat resistance, the isotactic content is preferably 60% by weight or more, more preferably 70% by weight or more. The molecular weight of the olefin-based polymer is 500 to 60 on average in terms of impact resistance and fluidity.
000 is preferable, and 1000 to 50000 is more preferable. The number average molecular weight can be measured by GPC (gel permeation chromatography).

The modified vinyl chloride polymer (E) containing a compound having a reactive group reactive with the reactive group selected in the modified olefin polymer (D) is a vinyl compound having a reactive group and vinyl chloride. A polymer obtained by polymerizing a compound and another vinyl compound copolymerizable therewith, and a random copolymer, block copolymer or graft copolymer of the above vinyl compound, or a mixture of these copolymers. I don't care. The copolymerization method is not particularly limited, but a general radical polymerization method, a cationic polymerization method, an anionic polymerization method, or a coordination polymerization method using a transition metal can be used. The modified vinyl chloride polymer (E) is a polymer containing a vinyl chloride compound as a main component (50% by weight or more).

As the reactive group, epoxy group, 1, 2, 3
Primary amino group, amide group, carboxyl group, acid anhydride group,
Examples thereof include a hydroxyl group, and these are used alone or in combination of two or more. In order to make the reaction with the carboxyl group introduced into the modified olefin polymer (D) of the present invention more effective, a 1,2,3 tertiary amino group and a hydroxyl group are preferable, and a dimethylamino group is particularly preferable. As the compound capable of introducing a reactive group, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, dimethylaminoethyl methacrylate,
Vinyl pyridine, t-butylaminoethyl methacrylate, acrylamide, methacrylamide, maleimide,
Acrylic acid, methacrylic acid, maleic acid, maleic anhydride, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate and the like are exemplified. The reactive group of the modified vinyl chloride polymer (E) has only to react with the modified olefin polymer (D) to produce the compatibilizer (Y),
The compound containing a reactive group is 0.05 to 50% by weight, preferably 0.1 to 30% by weight. If it is less than 0.05% by weight, the resistance to peeling of the surface layer is not exerted, and if it exceeds 50% by weight, the fluidity is greatly reduced.

The modified vinyl chloride polymer (E) preferably has an average degree of polymerization of 400 to 1500, and more preferably 450.
What is -1000 is more preferable. Average degree of polymerization is 400
If it is less than 1, the impact resistance tends to decrease, and if it exceeds 1500, the fluidity tends to remarkably decrease. The modified vinyl chloride polymer (E) contains a copolymer in which 80% by weight or more is modified vinyl chloride, a graft copolymer in which 80% by weight or more is modified vinyl chloride, and a post-chlorination modified vinyl chloride, These may be used alone or in combination of two or more. The copolymer includes a monovinylidene compound such as ethylene, vinyl acetate, methyl methacrylate, butyl acrylate 20
It may be contained by weight or less.

The compatibilizer (Y) is a modified chlorinated polymer containing 5 to 95 parts by weight of the modified olefin polymer (D) and a compound having a reactive group reactive with the reactive group selected in (D). It is obtained by reacting 95 to 5 parts by weight of the vinyl polymer (E). Modified olefin polymer (D) 15 to 85 parts by weight, modified vinyl chloride polymer (E) 85 to 15 parts by weight are preferred, modified olefin polymer (D) 25 to 75 parts by weight, modified vinyl chloride polymer (D). Particularly preferred is 75 to 25 parts by weight of the combined (E). When the amount of the modified olefin polymer (D) is less than 5 parts by weight or more than 95 parts by weight, the compatibility between the thermoplastic resin compositions of the present invention cannot be improved and the surface layer peeling resistance is significantly deteriorated.

The method of producing the compatibilizing agent (Y) is not particularly limited, but the following method can be preferably used. A method for melt-kneading a modified olefin polymer (D) and a modified vinyl chloride polymer (E), wherein a selected reactive group of the modified olefin polymer (D) and a modified vinyl chloride polymer (E) are used. The reaction group selected in (D) above is reacted with a compound having a reactive reaction group. At this time, a solvent that dissolves or swells the olefin polymer, such as tetralin, decalin, toluene, xylene, or chlorobenzene may be used. Specifically, the modified olefin polymer (D) and the modified vinyl chloride polymer (E) are
For example, there is a method of melt kneading using various conventionally known blenders such as an extruder, a heating roll, a Brabender, and a Banbury mixer.

The vinyl chloride resin (A) used in the present invention preferably has an average degree of polymerization of 400 to 1500, more preferably 450 to 1000. If the average degree of polymerization is less than 400, the impact resistance decreases, and
If it exceeds 00, the fluidity tends to be remarkably reduced. Vinyl chloride resin (A) is a vinyl chloride homopolymer, 80
Copolymers containing more than wt% vinyl chloride and post-chlorinated polyvinyl chloride are included, and these may be used alone or in combination of two or more. The copolymer may contain 20% by weight or less of a monovinylidene compound such as ethylene, vinyl acetate, methyl methacrylate and butyl acrylate.

Styrenic resin (B) used in the present invention
As, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene-α-methylstyrene copolymer, acrylonitrile-methylmethacrylate-styrene-α-methylstyrene copolymer, ABS
Resin, AS resin, MABS resin, MBS resin, AAS resin, AES resin, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, acrylonitrile-methylmethacrylate-butadiene-styrene-α-
Methyl styrene copolymer, styrene-maleic anhydride copolymer, styrene-maleimide copolymer, styrene-N
-Substituted maleimide copolymer, acrylonitrile-styrene-N-substituted maleimide copolymer, acrylonitrile-
Butadiene-styrene-β-isopropenylnaphthalene copolymer, acrylonitrile-methyl methacrylate-
Examples thereof include a butadiene-styrene-α-methylstyrene-maleimide copolymer and the like, and these may be used alone or in combination of two or more. Preferably, a resin compatible with the vinyl chloride resin is preferable because it does not lower the peeling resistance of the surface layer.

When impact resistance is required, a vinyl cyanide compound, an aromatic vinyl compound, an alkylmethacrylate compound, and 40% to 90% by weight of a rubber-like polymer can be copolymerized with the styrene resin (B). A mixture of one or more compounds selected from the group consisting of
The graft copolymer obtained by polymerizing 10% by weight is 0-70.
It is preferable to suitably use the styrene-based resin contained in parts by weight. As the rubber-like polymer, polybutadiene rubber,
Examples thereof include styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR) and butyl acrylate rubber. As a vinyl cyanide compound,
Acrylonitrile, methacrylonitrile and the like are exemplified,
Examples of the aromatic vinyl compound include styrene, methylstyrene, chlorostyrene, α-methylstyrene, and the like, and examples of the alkyl methacrylate compound include methyl methacrylate, ethyl methacrylate and the like. The above polymers and compounds are used alone or in combination of two or more.

As the styrene resin (B), those having the following composition are particularly preferable. That is, the composition of the methyl ethyl ketone soluble component is 1 with the vinyl cyanide compound and / or the alkyl methacrylate compound as the copolymerization component.
0 to 60% by weight, preferably 15% by weight or more, and a reduced viscosity of 0.2 to 0.9 dl / g (dimethylformamide solution, 30 ° C., concentration 0.3 g / dl), more preferably 0.25 to It is 0.8 dl / g. If the vinyl cyanide compound and / or the alkyl methacrylate compound is less than 10% by weight as a copolymerization component, the peeling resistance to the surface layer decreases,
When it exceeds the weight%, the fluidity tends to decrease. Also,
If the reduced viscosity is less than 0.2 dl / g, the impact resistance will decrease,
If it exceeds 0.9 dl / g, the fluidity tends to decrease and the thermal stability during molding tends to deteriorate. Further, when heat resistance is required, the composition of the methyl ethyl ketone soluble component is preferably a styrene resin having an α-methylstyrene content of 30% by weight or more.

The olefin resin (C) used in the present invention includes high density polyethylene, medium density polyethylene, low density polyethylene, copolymers of ethylene and other α-olefins, polypropylene, propylene and other α-olefins. Copolymers with olefins, polybutene, polyolefins or oligomers such as poly-4-methylpentene-1, ethylene-propylene rubber, ethylene-
Examples include polyolefin elastomers such as propylene-diene rubber, ethylene-vinyl acetate copolymer, butyl rubber, butadiene rubber, propylene-butene copolymer, ethylene-acrylic acid ester copolymer, and these alone or in combination of two or more. Used in combination. Among these, from the viewpoint of impact resistance and heat resistance, low density polyethylene,
Polypropylene and copolymers of propylene and other α-olefins are preferable, and polypropylene and copolymers of propylene and other α-olefins are particularly preferable. The three-dimensional structure of the olefin resin (C) is not particularly limited, but from the viewpoint of heat resistance, the isotactic content is preferably 60% by weight or more, more preferably 70% by weight.
That is all. The molecular weight of the olefin resin (C) is 5,000 to 1 on a weight average basis in terms of impact resistance and fluidity.
000000 is preferable, and 10,000 to 700,000 is more preferable. Regarding the polymerization of vinyl chloride resin (A), styrene resin (B) and olefin resin (C),
Any known polymerization method can be used, and there is no particular limitation on the type and operation thereof. After completion of the polymerization, the desired powdery or granular polymer is obtained by a known method.

The thermoplastic resin composition of the present invention comprises vinyl chloride resin (A) and / or styrene resin (B) 1-9.
0.1 to 50 parts by weight of the compatibilizer (Y) based on 100 parts by weight of (A), (B) and (C), which is composed of 9 parts by weight and 99 to 1 parts by weight of the olefin resin (C). It is made by blending. The ratio of (A), (B), and (C) is (A) and /
Alternatively, (B) 10 to 99 parts by weight, (C) 90 to 1 parts by weight are preferable, (A) and / or (B) 10 to 70 parts by weight,
(C) 90 to 30 parts by weight is more preferable. (A),
The ratio of (B) is (A) 0 to 100% by weight, (B) 10
It is applicable to 0 to 0% by weight. That is, impact resistance and surface layer peeling resistance can be improved by using the vinyl chloride resin (A) or the styrene resin (B) alone and the olefin resin (C). The compatibilizer (Y) is 0.1 to 50 parts by weight based on 100 parts by weight of (A), (B) and (C) in total, and 1
-25 parts by weight is preferred. If it is less than 0.1 part by weight, the effect of improving the surface layer peeling resistance is not exerted, and if it exceeds 50 parts by weight, impact resistance and molding processability are impaired.

Further, the thermoplastic resin composition of the present invention comprises
Each powder or pellet obtained by each method is blended and kneaded by a known method to obtain a target product. Further, the thermoplastic resin composition of the present invention is a well-known antioxidant, heat stabilizer, lubricant, and, if necessary, UV absorber, pigment, antistatic agent, flame retardant and flame retardant. Auxiliary agents and the like can be used together. In particular, styrene-based resins, phenolic antioxidants used for olefin-based resins, phosphite-based stabilizers, tin-based stabilizers incorporated in vinyl chloride-based resins, and various fatty acid esters, metal soaps, internal and external lubricants such as wax And the like can be used to improve the performance of the thermoplastic resin composition of the present invention as a resin for injection molding.

[0024]

EXAMPLES The present invention will now be described in more detail with reference to specific examples, but these examples do not limit the present invention. In the following description, “parts” means parts by weight,
"%" Indicates% by weight.

Reference Example 1: Modified vinyl chloride polymer (E-
Production of 1) 250 parts of water was added to an autoclave equipped with a stirrer and a cooler.
Parts, 0.1 parts of methyl cellulose, 0.1 parts of di-t-butylperoxytrimethyl adipate and 0.05 parts of 2-mercaptoethanol, and after replacing the internal air with nitrogen, 95 parts of vinyl chloride and 5 parts of methacrylic acid. After the polymerization was carried out at 50 ° C. for 8 hours, the unreacted monomer was recovered and the polymerization was terminated when the pressure was reduced from the steady pressure by 2 kg / cm ² . The obtained polymer slurry was dehydrated and dried to obtain a modified vinyl chloride polymer (E-1).

Reference Example 2: Modified vinyl chloride polymer (E-
2) Production 250 parts of water in an autoclave equipped with a stirrer and a cooler.
Parts, 0.1 parts of methyl cellulose, 0.1 parts of di-t-butylperoxytrimethyl adipate and 0.05 parts of 2-mercaptoethanol were charged, and after replacing the internal air with nitrogen, 90 parts of vinyl chloride and 5 parts of methacrylic acid. Part, and a monomer mixture consisting of 5 parts of butyl acrylate were charged at 50 ° C.
After 8 hours of polymerization, the unreacted monomer was recovered and the polymerization was terminated when the pressure was reduced from the steady pressure by 2 kg / cm ² . The obtained polymer slurry was dehydrated and dried to obtain a modified vinyl chloride polymer (E-2).

Reference Example 3: Modified vinyl chloride polymer (E-
3) Production In an autoclave equipped with a stirrer and a condenser, water 250
Parts, 0.1 parts of methyl cellulose, 0.1 parts of di-t-butylperoxytrimethyl adipate and 0.05 parts of 2-mercaptoethanol were charged, and after replacing the internal air with nitrogen, 100 parts of vinyl chloride were charged at 50 ° C. After 8 hours of polymerization, the unreacted monomer was recovered and the polymerization was terminated when the pressure was reduced from the steady pressure by 2 kg / cm ² . The obtained polymer slurry is dehydrated and dried to give a modified vinyl chloride polymer (E-
3) was obtained.

Reference Example 4: Preparation of Compatibilizer (Y-1 to Y-3) Modified olefin polymer (polypropylene manufactured by Mitsui Petrochemical Co., Ltd .: 100 parts of polyprohypol J-600 and 1 part of maleic anhydride were extruded). 50 parts by mass) and the modified vinyl chloride-based polymers (E-1,
50 parts of E-2 or E-3) was dry blended with a Henschel super mixer and set to 160 to 200 ° C. 2
It is supplied to a shaft extruder, melt-kneaded, pelletized, and each of the compatibilizers Y-1 to Y-3 (that is, E-1 to Y-).
1, E-2 to Y-2, E-3 to Y-3) were obtained.

Reference Example 5: Preparation of compatibilizer (Y-4) 50 parts of an olefin polymer (polypropylene: AH561 manufactured by Union Polymer Co., Ltd.) and 50 parts of a vinyl chloride polymer (E-1) were mixed with a Henschel super mixer. Dry blend, supply to a twin-screw extruder set at 160 ° C to 200 ° C, melt-knead, pelletize, and compatibilizer (Y
-4) was obtained.

Examples 1 to 5 and Comparative Examples 1 to 8 Vinyl chloride resins (A-1, A-2) having the composition shown in Table 1 polymerized by a known suspension polymerization method and olefin resins shown in Table 3 The resin (C-1, C-2) and the compatibilizer (Y-1 to Y-4) and the stabilizer (dibutyl tin malate) prepared in Reference Examples 4 and 5 (2 parts) were mixed at the composition ratio shown in Table 4 in Henschel. The components were blended using a mixer, and these components were melt-kneaded at 160 to 210 ° C. with a twin-screw extruder and pelletized to obtain pellets of a thermoplastic resin composition.

Examples 6 to 8 and Comparative Examples 9 to 12 Styrene resins (B-1 and B-2) having the compositions shown in Table 2 and olefin resins (shown in Table 3) polymerized by a known emulsion polymerization method. C-1) and the compatibilizing agents (Y-1 to Y-4) prepared in Reference Examples 4 and 5 were blended in a composition ratio shown in Table 5 using a Henschel mixer, and these were mixed in a twin-screw extruder. The components were melt-kneaded at 200 to 250 ° C and pelletized to obtain pellets of the thermoplastic resin composition. The reduced viscosity was measured by the following method. (Reduced viscosity) Dissolved in styrene resin N, N-dimethylformamide at a concentration of 0.3 g / dl to give a polymer solution, and according to JIS-K6721, a Ubbelohde viscometer (Shibayama Chemical Instruments The transit time (t) is measured using an automatic capillary viscosity measuring device manufactured by Seisakusho Co., Ltd. On the other hand, for the solvent N, N-dimethylformamide, the passage time (t ₀ ) at 30 ° C. was measured using the same apparatus, and the reduced viscosity (η red) was calculated by the following formula. η red = (t / t ₀ −1) / C where C means the concentration (g / dl) of the polymer solution.

Examples 9 to 12 and Comparative Examples 13 to 16 Vinyl chloride resins (A-1, A-) having the compositions shown in Table 1.
2) and the styrene resin (B-3) having the composition shown in Table 2, the olefin resin (C-1) shown in Table 3 and Reference Example 4,
The compatibilizer (Y-1 to Y-4) prepared in 5 and the stabilizer (dibutyl tin malate) (2 parts) were blended in a composition ratio shown in Table 6 by using a Henschel mixer. Were melt-kneaded at 170 to 220 ° C. and pelletized to obtain a thermoplastic resin composition pellet.

Next, using the pellets produced by the above-mentioned method, the nozzle temperature was set to Examples 1 to 5, 9 to 12 and Comparative Examples 1 to 8 and 13 to 16 by a 5 ounce injection molding machine.
180 ° C., 23 in Examples 6 to 8 and Comparative Examples 9 to 12.
The test piece required for the following test was molded at 0 ° C.
Various physical properties of each test piece were measured according to the methods described below. The results are shown in Tables 7 and 8.

As for the surface layer releasability of the molded product, the releasability from the gate portion of a flat plate molded product having a thickness of 2.0 mm was evaluated. Evaluation was made by a visual 5-point method, the highest being 5 points and the lowest being 1 point.
That is, the evaluation shows that the larger the number, the more excellent the resistance to surface peeling. Impact strength is ASTM D-256
Evaluated by Izod impact test based on the standard (23 ℃,
Unit: kg · cm / cm ² ). The fluidity was evaluated by the flow distance in a mosquito coiled incense mold having a thickness of 3 mm and a width of 10 mm (unit: mm) using the above molding machine. From the results shown in Tables 7 and 8, it is understood that the thermoplastic resin composition of the present invention is excellent in impact resistance, surface layer peeling resistance, and fluidity.

[0035]

[Table 1]

[0036]

[Table 2] * Styrene resin with a rubber content of 20% MEK: methyl ethyl ketone AN: acrylonitrile MMA: methyl methacrylate αS: α-methylstyrene

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

[0040]

[Table 6]

[0041]

[Table 7]

[0042]

[Table 8]

[0043]

INDUSTRIAL APPLICABILITY As described above, the resin composition containing the compatibilizing agent of the present invention provides a molded article excellent in impact resistance and surface layer peeling resistance and is excellent in fluidity. .

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Claims (13)

[Claims] 1. A vinyl chloride resin (A) and / or a styrene resin (B) 1 to 99 parts by weight and an olefin resin (C) 99 to 1 parts by weight, (A), (B),
Based on 100 parts by weight of the total of (C), the following compatibilizer (Y)
Thermoplastic resin composition prepared by blending 0.1 to 50 parts by weight: Compatibilizer (Y): 0.05 to 5 compound having reactive group
Modified olefin polymer (D) 5-9 containing 0% by weight
A compatibilizer comprising 5 parts by weight and 95 to 5 parts by weight of a modified vinyl chloride polymer (E) containing 0.05 to 50% by weight of a compound having a reactive group reactive with the reactive group of (D). . 2. The thermoplastic resin composition according to claim 1, wherein the reactive group contained in the modified olefin polymer (D) is a carboxyl group and / or an acid anhydride. 3. The modified vinyl chloride polymer (E) contains at least one reactive group selected from the group consisting of an epoxy group, an amino group, a dimethylamino group and a hydroxyl group. The thermoplastic resin composition described. 4. The thermoplastic resin composition according to claim 1, wherein the vinyl chloride resin (A) has an average degree of polymerization of 400 to 1500. 5. The composition of the methyl ethyl ketone soluble component of the styrene-based resin (B) is 10 using a vinyl cyanide compound and / or an alkyl methacrylate compound as a copolymerization component.
-60% by weight, reduced viscosity 0.2-0.9 dl / g
(Dimethylformamide solution, 30 ° C., concentration 0.3 g /
dl), The thermoplastic resin composition according to claim 1. 6. The styrene resin (B) is selected from the group consisting of 40 to 90% by weight of a rubbery polymer, a vinyl cyanide compound, an aromatic vinyl compound, an alkyl methacrylate compound and a monomer copolymerizable therewith. A graft copolymer obtained by polymerizing 60 to 10% by weight of a mixture of at least one selected compound is contained in an amount of 0 to 70 parts by weight.
The thermoplastic resin composition according to item 5. 7. The thermoplastic resin composition according to claim 1, wherein the composition containing the methyl ethyl ketone-soluble component of the styrene resin (B) has an α-methylstyrene content of 30% by weight or more. 8. The thermoplastic resin composition according to claim 1, wherein the olefin resin (C) is a propylene polymer. 9. The thermoplastic resin composition according to claim 1, wherein the olefin resin (C) has a weight average molecular weight of 5,000 to 1,000,000. 10. The thermoplastic resin composition according to claim 1, which is an injection molding resin. 11. A compound having a reactive group is added in an amount of 0.05 to 5
Modified olefin polymer (D) 5-9 containing 0% by weight
A compatibilizer comprising 5 parts by weight and 95 to 5 parts by weight of a modified vinyl chloride polymer (E) containing 0.05 to 50% by weight of a compound having a reactive group reactive with the reactive group of (D). . 12. The compatibilizer according to claim 11, wherein the reactive group contained in the modified olefin polymer (D) is a carboxyl group and / or an acid anhydride. 13. The modified vinyl chloride polymer (E) contains at least one reactive group selected from the group consisting of an epoxy group, an amino group, a dimethylamino group and a hydroxyl group. The compatibilizer described.