JPH09302174A - Thermoplastic resin composition for blow molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin composition which contains a specific graft copolymer containing rubber vinyl cyanide-based copolymer and vinyl copolymer in a specific proportion and is excellent in gloss, impact resistance and blow molding workability and useful as below molding resin parts for motor vehicles. SOLUTION: This composition contains (A) 10-50 pts.wt. of a graft copolymer containing rubber prepared by polymerizing 80-20 pts.wt. of a monomer mixture consisting of (ii) 5-50wt.% of a vinyl cyanide monomer, (iii) 10-90% of an aromatic vinyl monomer and (iv)1-80wt.% of an unsaturated carboxylic alkyl ester in the presence of (i) 20-80 pts.wt. of a rubber polymer, (B) 10-80 pts.wt. of a vinyl cyanide-based copolymer which is prepared from 15-55wt.% of the component (ii) and 85-45wt.% of the component (iii) and processes a reduced viscosity of 0.5-1.5dl/g and (C) 0-60wt.% of a vinyl copolymer prepared from 5-30wt.% of the component (ii), 75-45wt.% of the component (iii) and 0-60wt.% of (v) another vinyl monomer copolymerizable with these components, and the components A-C amount to 100 pts.wt. in total.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition for blow molding which has an excellent balance of impact resistance and blow molding processability and excellent gloss.

[0002]

2. Description of the Related Art Acrylonitrile-butadiene-styrene copolymer resin (ABS resin) has a good balance of impact resistance and moldability, and is widely used as a resin for injection molding. In recent years, a technique for obtaining a large hollow resin product by blow molding has attracted attention, and a resin composition suitable for blow molding has been developed also for ABS resin. However, since the molding pressure in the blow molding method is lower than that in the injection molding method, there is a problem that the glossiness of the obtained molded product is inferior.
Therefore, as in Japanese Patent Laid-Open No. 7-108534, there has been proposed a blow molding die provided with a heating means and a cooling means. However, such a blow molding die is not only expensive, but the glossiness of the obtained molded product cannot be said to be sufficient.

The present invention relates to a thermoplastic resin composition for blow molding which has an excellent balance of impact resistance and blow molding processability for obtaining a blow molded article having excellent gloss and excellent gloss.

[0004]

DISCLOSURE OF THE INVENTION As a result of intensive studies aimed at solving the above problems, the present inventors have found that a rubbery polymer having a specific particle size and a specific particle size distribution has a specific composition. By combining a rubber-containing graft copolymer with a vinyl cyanide-based copolymer or vinyl-based copolymer having a specific composition and reduced viscosity at a specific ratio, the impact resistance and blow molding processability are excellent and the gloss is excellent. The present invention has been accomplished by finding a thermoplastic resin composition excellent in blow molding for blow molding.

[0005]

That is, the object of the present invention is to have a weight average particle diameter of 0.15 to 0.25 μm,
Between 80% and 130% of the weight average particle size is 8% of all particles.
In the presence of 20 to 80 parts by weight of a rubbery polymer (a) having a particle size distribution of 0% by weight or more, 5 to 50% by weight of a vinyl cyanide-based monomer (b) and an aromatic vinyl-based monomer Rubber-containing graft copolymer (I) 10 obtained by polymerizing 80 to 20 parts by weight of a monomer mixture consisting of 10 to 90% by weight of the body (c) and 0 to 80% by weight of an unsaturated carboxylic acid alkyl ester (d). ˜50 parts by weight, vinyl cyanide-based monomer (b) 15-55% by weight and aromatic vinyl-based monomer (c) 85-45% by weight, and a reduced viscosity of 0.5-
Vinyl cyanide-based copolymer (I of 1.5 dl / g)
I) 10 to 80 parts by weight, vinyl cyanide monomer (b) 5 to 30% by weight, aromatic vinyl monomer (c) 7
A rubber-containing graft copolymer comprising 5 to 45% by weight and 0 to 50 parts by weight of a vinyl copolymer (III) comprising 0 to 60% by weight of another vinyl-based monomer (e) copolymerizable therewith. Polymer (I), vinyl cyanide copolymer (II)
It can be achieved by a thermoplastic resin composition for blow molding, wherein the total amount of the vinyl copolymer (III) and the vinyl copolymer (III) is 100 parts by weight.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The rubbery polymer (a) used in the rubber-containing graft copolymer (I) in the present invention includes:
Diene rubber, acrylic rubber, ethylene rubber, etc. Specific examples thereof include polybutadiene, poly (butadiene-styrene), poly (butadiene-acrylonitrile), polyisoprene, poly (butadiene-butyl acrylate), and poly ( Butadiene-methyl acrylate), poly (butadiene-methyl methacrylate), poly (butyl acrylate-methyl methacrylate), poly (butadiene-ethyl acrylate), ethylene-propylene rubber,
Examples thereof include ethylene-propylene-diene rubber, poly (ethylene-isobutylene), poly (ethylene-methyl acrylate) and the like. These rubbery polymers are used in one kind or in a mixture of two or more kinds. Among these rubbery polymers, polybutadiene, poly (butadiene-styrene), poly (butadiene-acrylonitrile), and ethylene-propylene rubber are particularly preferably used in terms of impact resistance.

Specific examples of vinyl cyanide monomer (b) used in the rubber-containing graft copolymer (I), vinyl cyanide copolymer (II) and vinyl copolymer (III) in the present invention. Examples thereof include acrylonitrile and methacrylonitrile, and one kind or two or more kinds can be used. Among them, acrylonitrile is particularly preferred in view of impact resistance.

Specific examples of the aromatic vinyl monomer (c) used in the rubber-containing graft copolymer (I), vinyl cyanide copolymer (II) and vinyl copolymer (III) in the present invention. Examples thereof include styrene, α-methylstyrene, orthomethylstyrene, paramethylstyrene, para-t-butylstyrene, halogenated styrene, and the like, and one or more kinds can be used. Styrene and α-methylstyrene are particularly preferable, and styrene is more preferable.

The unsaturated carboxylic acid alkyl ester (d) used for the rubber-containing graft copolymer (I) in the present invention is an acrylate and / or methacrylic acid having an alkyl group or a substituted alkyl group having 1 to 6 carbon atoms. Acid esters are suitable, and one or more kinds can be used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic N-hexyl acid, cyclohexyl (meth) acrylate, (meth)
Chloromethyl acrylate and (meth) acrylic acid 2-
Chloroethyl and the like can be mentioned, and among them, methyl (meth) acrylate can be preferably used.

The vinyl-based copolymer (II
Specific examples of the other copolymerizable vinyl-based monomer (e) used in I) include unsaturated carboxylic acids such as acrylic acid and methacrylic acid; methyl acrylate, methyl methacrylate, butyl acrylate and the like ( (Meth) acrylic acid esters; (meth) acrylamides such as acrylamide, methacrylamide, N-methylacrylamide, maleimides such as maleimide, N-methylmaleimide, N-phenylmaleimide and maleic anhydride, citraconic anhydride, aconit anhydride Examples thereof include unsaturated carboxylic acid anhydrides such as acids, and among them, methyl methacrylate and N-phenylmaleimide are preferable in view of blow molding processability.

The weight average particle diameter of the rubber-like polymer (a) in the rubber-containing graft copolymer (I) of the present invention is required to be 0.15 to 0.25 μm, particularly 0.17 to 0. It is preferably in the range of 0.22 μm.
Here, the impact strength of the thermoplastic resin composition for blow molding obtained when it is less than 0.15 μm is low and is 0.25 μm.
If it exceeds, the glossiness will decrease. Further, it is necessary to have a particle size distribution in which 80% by weight or more of all particles fall between 70% and 130% of the weight average particle size.
If the particle size distribution is broad, the glossiness of the obtained thermoplastic resin composition for blow molding decreases, and it is more preferably 85% by weight or more.

The content of the rubbery polymer (a) in the rubber-containing graft copolymer (I) must be 20 to 80 parts by weight. If the amount is less than 20 parts by weight, the resulting blow molding thermoplastic resin composition has poor blow moldability, and
If the amount exceeds the weight part, the impact strength is low, which is not preferable. Above all, 30 to 70 parts by weight is preferable.

The vinyl cyanide monomer (b) in the monomer mixture of the rubber-containing graft copolymer (I)
Is required to be 5 to 50% by weight. If the amount is less than 5% by weight, the resulting thermoplastic resin composition for blow molding has an undesirably low impact strength. If it exceeds 50% by weight,
Blow molding processability is poor, which is not preferable. Above all, 10
45% by weight is preferred.

The proportion of the aromatic vinyl monomer (c) in the monomer mixture in the rubber-containing graft copolymer (I) must be 10 to 90% by weight. If the content is less than 10% by weight, the blow molding processability of the obtained thermoplastic resin composition for blow molding is poor, which is not preferable. On the other hand, if it exceeds 90% by weight, the impact strength is undesirably low. Above all 15
85% by weight is preferred.

The unsaturated carboxylic acid alkyl ester (d) in the monomer mixture in the rubber-containing graft copolymer (I) must be 80% by weight or less. If it exceeds 80% by weight, the resulting thermoplastic resin composition for blow molding has an undesirably low impact strength. Above all, 75% by weight
The following is preferred.

The graft ratio of the rubber-containing graft copolymer (I) is not particularly limited, but is preferably 10 to 100% by weight. The reduced viscosity of the copolymer of the graft component is not particularly limited, but is preferably 0.2 to 1.0 dl / g from the viewpoint of impact resistance.

In the present invention, the vinyl cyanide copolymer (II) is a vinyl cyanide monomer (b) 15 to 55.
% By weight, 85 to 45% by weight of an aromatic vinyl monomer (c)
It is necessary to Vinyl cyanide monomer (b) is 1
If it is less than 5% by weight, impact resistance of the blow molding thermoplastic resin composition using the obtained copolymer is insufficient, and if it exceeds 55% by weight, the blow molding thermoplastic resin composition. It is not preferable because the blow molding processability is deteriorated. Further, the aromatic vinyl monomer (c) is 45% by weight.
When it is less than 1, the blow molding processability of the obtained blow molding thermoplastic resin composition is deteriorated, and when it exceeds 85% by weight, the impact resistance of the blow molding thermoplastic resin composition is deteriorated, which is not preferable. . Among these, those having a range of 20 to 50% by weight of the vinyl cyanide-based monomer (b) and 80 to 55% by weight of the aromatic vinyl-based monomer (c) are particularly preferable.

The reduced viscosity (ηsp / c) of the vinyl cyanide-based copolymer (II) in the present invention is determined in order to further improve the blow molding processability of the obtained thermoplastic resin composition for blow molding. It is necessary to be 0.5 to 1.5 dl / g. 1.50 dl / g even if less than 0.5 dl / g
It is not preferable that the ratio exceeds the value, because the blow moldability of the obtained thermoplastic resin composition for blow molding is extremely poor. Above all, reduced viscosity (ηsp / c) 0.70 to 1.30 dl /
g is particularly preferred.

The vinyl-based copolymer (III) in the present invention comprises vinyl cyanide-based monomer (b) in an amount of 5 to 30% by weight, aromatic vinyl-based monomer (c) in an amount of 75 to 45% by weight, and Other vinyl-based monomer (e) 0 copolymerizable with
It is necessary to set the content to 60% by weight. If the amount of the vinyl cyanide monomer (b) is less than 5% by weight, the resulting thermoplastic resin composition for blow molding has insufficient impact resistance, and if it exceeds 30% by weight, the thermoplastic resin for blow molding obtained. It is not preferable because the blow molding processability of the composition deteriorates. Further, when the aromatic vinyl monomer (c) is less than 45% by weight, the blow molding thermoplastic resin composition obtained has poor blow molding processability, and when it exceeds 75% by weight, the blow molding thermoplastic resin obtained. It is not preferable because the impact resistance of the resin composition is not sufficient. Further, if necessary, other copolymerizable vinyl-based monomer (e) may be used as a constituent component, but if it exceeds 60% by weight, impact resistance of the blow molding thermoplastic resin composition obtained. Since it is difficult to maintain the content of the other copolymerizable vinyl monomer (e), 0 to 60% by weight is required. In particular, vinyl cyanide-based monomer (b)
10-25% by weight, aromatic vinyl monomer (c) 70-
It is preferably 50% by weight and 0 to 50% by weight of another vinyl-based monomer (e) copolymerizable therewith.

Further, the reduced viscosity (ηsp / c) of the vinyl copolymer (III) in the present invention is set to 0 in order to further improve the blow molding processability of the obtained blow molding thermoplastic resin composition. 2-0.8 dl / g is preferable.
Even if it is less than 0.2 dl / g or exceeds 0.80 dl / g,
The blow molding processability of the obtained thermoplastic resin composition for blow molding is extremely poor, which is not preferable. Among them, the reduced viscosity (ηsp / c) of 0.30 to 1.70 dl / g is particularly preferable.

In the blow molding thermoplastic resin composition of the present invention, the rubber-containing graft copolymer (I), the vinyl cyanide copolymer (II) and the vinyl copolymer (I) are used.
The compounding ratio of II) is the rubber-containing graft copolymer (I).
10 to 50 parts by weight, vinyl cyanide-based copolymer (II)
10 to 80 parts by weight, vinyl copolymer (III) 0 to 5
0 parts by weight, and the total must be 100 parts by weight. If the amount of the rubber-containing graft copolymer (I) is less than 10 parts by weight, the obtained thermoplastic resin composition for blow molding has insufficient impact strength, and if it exceeds 50 parts by weight, blow molding processability is poor, which is not preferable. If the amount of the vinyl cyanide-based copolymer (II) is less than 10 parts by weight, the obtained thermoplastic resin composition for blow molding has insufficient impact strength, and if it exceeds 80 parts by weight, the blow molding processability is inferior. . If the amount of the vinyl copolymer (III) exceeds 50 parts by weight, the blow molding thermoplastic resin composition obtained is inferior in impact resistance, which is not preferable.

Specific examples of large hollow resin parts for automobiles and two wheels of the present invention include bumpers, air spoilers, radiator grilles, scooter housings, and the like. Specific examples of large hollow resin parts for houses include partitions and desk top plates. , A furniture, a bathtub side cover, and the like, and large-sized hollow resin parts for electric equipment include doors of electric refrigerators, office equipment, and the like, and the thermoplastic resin composition for blow molding of the present invention is suitable.

In the present invention, if necessary, 2,6-di-t-butyl-4-methylphenol, 4,
Phenolic antioxidants such as 4'-butylidene-bis (3-methyl-6-t-butylphenol); phosphorus-based oxidations such as tris (mixed, mono- and dinonylphenyl) phosphites and diphenyl isodecyl phosphite Antioxidants, sulfur-based antioxidants such as dilauryl thiodipropionate, dimyristyl thiodipropionate diasterial thiodipropionate, 2-hydroxy-4
-Octoxybenzophenone, 2- (2-hydroxy-
UV absorbers such as 5-methylphenyl) benzotriazole, bis (2,2,6,6, -tetramethyl-4-
Light stabilizers such as piperidinyl), antistatic agents such as hydroxylalkylamine and sulfonate, lubricants such as ethylenebisstearylamide and metal soap, glass fibers,
Inorganic filler such as carbon fiber, tetrabromobisphenol A, decabromodiphenyl oxide, TBA
It is also possible to add a flame retardant such as an epoxy oligomer, a TBA polycarbonate oligomer, antimony trioxide, a coloring agent, and the like.

Since the thermoplastic resin composition for blow molding of the present invention has an excellent balance of impact resistance and blow molding processability and excellent luster, it is a large hollow resin part for automobiles and motorcycles, and a large hollow resin for homes. Suitable for parts and large hollow resin parts for electrical equipment.

An example of a method for producing the blow molding thermoplastic resin composition of the present invention will be described below. The method for producing the rubber-containing graft copolymer (I) in the present invention is not particularly limited, and may be an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method,
It can be produced by a conventionally known polymerization method using a solution polymerization method or a combination thereof. The method for polymerizing the vinyl cyanide-based copolymer (II) in the present invention includes:
From the viewpoint of high reduced viscosity, conventionally known suspension polymerization is preferable.

The polymerization initiator used for suspension polymerization is 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2 '.
-Azobis (2,4,4-trimethylvaleronitrile)
And organic peroxides such as t-butylperoxide, t-butylperoxyneodecanate, t-butylperoxyneoxexanoate, t-butylperoxypivalate, and the like. Two or more kinds can be used in combination, and among them, an azonitrile compound is particularly preferable because the control of the polymerization rate is easy. Examples of the chain transfer agent used herein include alkyl mercaptans such as n-octyl mercaptan, t-dodecyl mercaptan, and n-dodecyl mercaptan. These chain transfer agents are 1
They may be used alone or in combination of two or more. The method of use may be any of batch addition, divisional addition, and continuous addition.

The vinyl-based copolymer (II
The production method of I) is not particularly limited, and it can be produced by an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method, or a conventionally known polymerization method using a combination thereof.

Regarding the thermoplastic resin composition for blow molding of the present invention, a rubber-containing graft copolymer (I), a vinyl cyanide copolymer (II) and a vinyl copolymer (II)
The compounding / melt-extruding of I) is not particularly limited, and a generally known method can be adopted. Rubber-containing graft copolymer (I), vinyl cyanide-based copolymer (II)
When blending the vinyl copolymer (III) and the vinyl copolymer (III), for example, a ribbon blender, a V-type blender, a Henschel mixer, or the like can be used. And single screw extruder, 2
A kneading process using an extruder such as a shaft extruder, a Banbury mixer, a mixing roll, a pressure kneader or the like can be adopted.

[0029]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but these examples do not limit the present invention. Parts and% in Reference Examples, Examples and Comparative Examples represent parts by weight and% by weight, respectively. In addition, the obtained rubber-containing graft copolymer (I),
Each physical property value of the vinyl cyanide-based copolymer (II), the vinyl-based copolymer (III) and the blow molding thermoplastic resin composition was determined by the following test methods.

Weight average particle size and particle size distribution: sodium alginate method

Graft ratio: Acetone was added to a predetermined amount (M) of the rubber-containing graft copolymer, and the mixture was refluxed for 3 hours. After centrifuging the solution for 40 minutes, the insoluble matter was filtered. After drying under reduced pressure for a time, the weight (N) was measured. The graft ratio was determined by the following equation. Here, L in the formula is the rubber content (%) in the rubber-containing graft copolymer. Graft rate (%) = 100 × (N−M × L / 100) /
(M × L / 100) Reduced viscosity (ηsp / c): Measured using a Ubbelohde viscometer from a methyl ethyl ketone solution having a measurement temperature of 30 ° C. and a sample concentration of 0.4 g / dl.

1/2 inch, notched Izod impact strength: The injection molded article of the thermoplastic resin composition for blow molding was in accordance with ASTM D256.

Gloss: The gloss of the obtained blow-molded product was measured for reflectance at an incident angle of 60 ° by using a digital variable angle gloss meter UGV-5D manufactured by Suga Test Instruments Co., Ltd.

Blow Molding Workability: A sample whose 1.5 m parison did not draw down for 30 seconds or more was judged as ⊚, and a sample which did not draw down for 15 seconds or more was judged as ◯. Also,
A sample having a severe drawdown or a sample in which melt fracture was caused and a parison having a uniform thickness was not obtained was determined as x.

Examples and comparative examples will be shown below. Reference Example 1: Production of Rubber-Containing Graft Copolymer (I) A 120 parts of pure water and 0.5 glucose in a reactor substituted with nitrogen.
Part, sodium pyrophosphate 0.5 part, ferrous sulfate 0.0
The weight average particle diameter of 05 parts and rubber is 0.22 μm, and the ratio of 70% to 130% of the weight average particle diameter is 95% by weight.
50 parts of polybutadiene latex (solid content conversion)
Was charged, and the temperature in the reactor was raised to 65 ° C. while stirring. When the internal temperature reached 65 ° C, polymerization was started, and a mixture of 35 parts of styrene, 15 parts of acrylonitrile and 0.3 part of t-dodecyl mercaptan was continuously added dropwise over 5 hours. At the same time, an aqueous solution containing 0.25 parts of cumene hydroperoxide, 2.5 parts of potassium oleate and 25 parts of pure water was continuously added dropwise over 7 hours.
The reaction was completed. The obtained rubber-containing graft copolymer latex is coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to obtain rubber-containing graft copolymer (I) A.
I got Table 1 shows the graft ratio of this rubber-containing graft copolymer (I) A and ηsp / c of the resin component.

Reference Example 2: Production of Rubber-Containing Graft Copolymer (I) B The polybutadiene latex of Reference Example 1 was prepared by adding a rubber having a weight average particle diameter of 0.18 μm and 70% to 130% of the weight average particle diameter.
% Polybutadiene latex having a ratio of 90% by weight (solid content conversion), 29 parts of styrene, and 11 parts of acrylonitrile, except that the same procedure as in Reference Example 1 was carried out, and the rubber-containing graft copolymer shown in Table 1 was used. Combined (I) B was obtained.

Reference Example 3: Production of Rubber-Containing Graft Copolymer (I) C The polybutadiene latex of Reference Example 1 was prepared from the rubber having a weight average particle diameter of 0.30 μm and 70% to 130% of the weight average particle diameter.
%, The rubber-containing graft copolymer (I) C shown in Table 1 was obtained in the same manner as in Reference Example 1, except that the content of polybutadiene latex was 95% by weight (in terms of solid content). .

Reference Example 4: Production of Rubber-Containing Graft Copolymer (I) D The polybutadiene latex of Reference Example 1 was prepared from the rubber having a weight average particle diameter of 0.20 μm and 70% to 130% of the weight average particle diameter.
%, The rubber-containing graft copolymer (I) D shown in Table 1 was obtained in the same manner as in Reference Example 1 except that the content of polybutadiene latex was 65% by weight (solid content). .

Reference Example 5: Vinyl cyanide type copolymer (I
I) Production of a A methyl methacrylate / acrylamide copolymer (Japanese Patent Publication No. 45-2415) was placed in a stainless steel autoclave having a capacity of 20 L and equipped with a baffle and a Faudra type stirring blade.
A solution of 0.05 part in 165 parts of ion-exchanged water was stirred at 400 rpm, and the inside of the system was replaced with nitrogen gas. Next, acrylonitrile 28 parts, styrene 72
Part, t-dodecyl mercaptan 0.05 part, 2,2'-
A mixed solution of 0.40 parts of azobisisobutyronitrile was added while stirring the reaction system, and the temperature was raised to 60 ° C. to initiate polymerization. After raising the reaction temperature to 65 ° C over 15 minutes, the temperature was raised to 100 ° C over 50 minutes. Thereafter, the reaction system was cooled, the polymer was separated, washed, and dried according to a usual method to obtain a vinyl cyanide-based copolymer (II) a shown in Table 2.

Reference Example 6: Vinyl cyanide type copolymer (I
I) Production of b Polymerization was carried out in the same manner as in Reference Example 5, except that the conditions of Reference Example 5 were changed to 24 parts of acrylonitrile, 71 parts of styrene, 5 parts of methyl methacrylate, and 0.1 part of t-dodecyl mercaptan. The vinyl cyanide copolymer (I shown in Table 2)
I) b was obtained.

Reference Example 7: Vinyl cyanide type copolymer (I
I) Production of c Polymerization was carried out in the same manner as in Reference Example 5, except that the conditions of Reference Example 5 were changed to 1.5 parts of t-dodecyl mercaptan. Polymer (I
I) c was obtained.

Reference Example 8: Vinyl cyanide type copolymer (I
I) Production of d Of the conditions of Reference Example 5, t-dodecyl mercaptan was changed to 0
The polymerization was carried out in the same manner as in Reference Example 5 except that the amount of the vinyl cyanide copolymer (II) d shown in Table 2 was changed.
I got

Reference Example 9: Vinyl Cyanide Copolymer (I
I) Production of e Among the conditions of Reference Example 5, acrylonitrile was 10 parts and styrene was 90 parts, and polymerization was carried out in the same manner as in Reference Example 5, and the vinyl cyanide copolymer (II) shown in Table 2 was obtained. e
I got

Reference Example 10: Vinyl Copolymer (III)
B. Production of a: Among the conditions of Reference Example 5, acrylonitrile 28 parts, styrene 72 parts, and t-dodecyl mercaptan 0.5 parts were used,
After that, polymerization was carried out in the same manner as in Reference Example 5 to obtain vinyl copolymer (III) b shown in Table 3.

Reference Example 11: Vinyl Copolymer (III)
(B) Production of acrylonitrile (35 parts), styrene (35 parts), N-phenylmaleimide (30 parts) and t-dodecylmercaptan (0.5 parts) in the conditions of Reference Example 5, and then polymerization was carried out in the same manner as in Reference Example 5, Vinyl-based copolymers (I
II) was obtained. Reference Example 12: Vinyl Copolymer (II
I) Production of Ha Under the conditions of Reference Example 5, 28 parts of acrylonitrile, 72 parts of styrene and 1.4 parts of t-dodecyl mercaptan were used.
Then, polymerization was carried out in the same manner as in Reference Example 5 to obtain vinyl copolymer (III) C shown in Table 3.

Examples: 1-4: Preparation of thermoplastic resin composition for blow molding Rubber-containing graft copolymers (I) A-B prepared in Reference Examples 1-2 and Reference Examples 5-6. 40 mmφ after kneading the produced vinyl cyanide-based copolymers (II) a to b and the vinyl-based copolymer (III) a produced in Reference Example 10 in a Henschel mixer at a mixing ratio shown in Table 4. An extrusion blow molding thermoplastic resin composition was obtained with an extruder. A test piece was prepared from the obtained thermoplastic resin composition for blow molding by injection molding, and the Izod impact strength was measured. The measured value is shown in Table 4. Also, blow molding,
The results of the blow molding processability and the glossiness of the molded product are also shown in Table 4. The Izod impact strength in Table 4 is 20 kg.
If it is less than cm / cm, the effect of the present invention is not obtained and the glossiness is 9
5% or more is the high gloss grade of the present invention.

Comparative Examples: 1 to 9: Production of Blow Molding Thermoplastic Resin Compositions Rubber-containing graft copolymers (I) A to D produced in Reference Examples 1 to 4 and Reference Examples 5 to 9 The produced vinyl cyanide-based copolymers (II) a to e and Reference Examples 10 to 12
After kneading the vinyl-based copolymers (III) (a) to (c) produced in (4) with a Henschel mixer at a mixing ratio shown in Table 4, 4
The thermoplastic resin composition for blow molding was obtained by extrusion with a 0 mmφ extruder. A test piece was prepared from the obtained thermoplastic resin composition for blow molding by injection molding, and the Izod impact strength was measured. The measured value is shown in Table 4. In addition, blow molding was performed, and the results of the blow molding processability and the glossiness of the molded product are also shown in Table 4.

From Examples 1 to 4, it is understood that the blow molding thermoplastic resin composition according to the claims of the present invention has an excellent balance of impact resistance and blow molding processability, and excellent gloss. However, in Comparative Examples 1 and 2, the compounding ratios of the rubber-containing graft copolymer (I), the vinyl cyanide-based copolymer (II) and the vinyl-based copolymer (III) are out of the range specified by the present invention. Therefore, Comparative Example 1 has low impact strength, and Comparative Example 2 has poor gloss. In Comparative Examples 3 to 9, since the rubber-containing graft copolymer (I), the vinyl cyanide copolymer (II) and the vinyl polymer (III) are out of the range defined by the present invention, Comparative Examples 7 has low impact strength,
Blow molding processability was inferior in Comparative Examples 6 and 9, and Comparative Examples 3 and 4
Is inferior in glossiness, and Comparative Examples 5 and 8 are inferior in impact strength and blow molding processability. As described above, the blow molding thermoplastic resin composition of the present invention has an excellent balance of impact resistance, gloss, and blow molding processability from the examples and comparative examples. This is a rubber-containing graft copolymer having a specific composition and a vinyl cyanide-based copolymer and a vinyl-based copolymer having a specific composition and a reduced viscosity using a rubbery polymer having a specific particle size and a particle size distribution. It is first realized by combining polymers in a specific ratio.

[0049]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[0050]

The thermoplastic resin composition for blow molding of the present invention comprises a rubber-containing polymer having a specific particle size and a specific particle size distribution and a rubber-containing graft copolymer having a specific composition and a specific composition and It is characterized by combining a vinyl cyanide-based copolymer having a reduced viscosity and a vinyl-based copolymer in a specific ratio, and has an excellent balance of impact resistance, gloss and blow molding processability. The thermoplastic resin composition for blow molding of the present invention can be used for blow molding by utilizing these characteristics. However, large hollow resin parts for automobiles and motorcycles, large hollow resin parts for houses, and electric equipment Suitable as a resin material for large hollow resin parts. It is intended to provide a thermoplastic resin composition for blow molding, which has an excellent balance of impact resistance, gloss and blow moldability required as a resin material for large hollow resin parts for electric equipment.

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Claims (5)

[Claims] 1. A weight average particle diameter of 0.15 to 0.25 μm
And vinyl cyanide in the presence of 20 to 80 parts by weight of the rubbery polymer (a) having a particle size distribution in which 80% by weight or more of all particles fall between 70% and 130% of the weight average particle size. A monomer mixture 80 comprising 5 to 50% by weight of a monomer (b), 10 to 90% by weight of an aromatic vinyl monomer (c) and 0 to 80% by weight of an unsaturated carboxylic acid alkyl ester (d). To 50 parts by weight of a rubber-containing graft copolymer (I), 15 to 55% by weight of a vinyl cyanide monomer (b) and an aromatic vinyl monomer (c). 10 to 80 parts by weight of a vinyl cyanide-based copolymer (II) having a reduced viscosity of 0.5 to 1.5 dl / g, and a vinyl cyanide-based monomer (b) 5 ~ 30% by weight,
75 to 45% by weight of an aromatic vinyl monomer (c) and another vinyl monomer (e) copolymerizable therewith with 0 to 60%
Vinyl copolymer (III) consisting of 0 to 50 parts by weight of rubber-containing graft copolymer (I), vinyl cyanide copolymer (II) and vinyl copolymer (III) A thermoplastic resin composition for blow molding, wherein the total is 100 parts by weight. 2. The thermoplastic resin composition for blow molding according to claim 1, wherein the vinyl cyanide-based copolymer (II) has a reduced viscosity of 0.7 to 1.3 dl / g. 3. The vinyl cyanide-based copolymer (II)
Is 20 to 45% by weight of vinyl cyanide-based monomer component (b) and 80 to 55% by weight of aromatic vinyl-based monomer component (c). Thermoplastic resin composition for molding. 4. The thermoplastic resin composition for blow molding according to claim 1, wherein the vinyl copolymer (III) has a reduced viscosity of 0.2 to 0.8 dl / g. 5. A thermoplastic resin for blow molding according to claim 1, which is suitable for large hollow resin parts for automobiles, two wheels, large hollow resin parts for housing, and large hollow resin parts for household electric appliances. Resin composition.