JP2001279049A - Abs-based resin composition for blow molding use and the resultant blow molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ABS-based resin composition excellent in blow moldability and thermal linear expansion coefficient and capable of giving blow molded products with excellent rigidity, surface disposition and impact resistance, and to provide such blow molded products. SOLUTION: This ABS-based resin composition comprises (a) a graft polymer obtained by graft polymerization of at least one compound selected from the group consisting of aromatic vinyl compounds, vinyl cyanide, α,β-unsaturated glycidyl ester compounds, (meth)acrylic esters and maleimide in the presence of a rubbery elastomer and (b) a polymer made from at least one compound selected from the group consisting of aromatic vinyl compounds, vinyl cyanide, α,β-unsaturated glycidyl ester compounds, (meth)acrylic esters and maleimide. This resin composition is such that the reduced viscosity of the MEK solubles thereof is 0.5-1.5 dl/g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ABS resin composition for blow molding, which is excellent in the surface properties, wall thickness, heat resistance, impact resistance and blow moldability of a blow molded article, and a blow molded article comprising the same.

[0002]

2. Description of the Related Art Conventionally, thermoplastic materials such as high-density polyethylene, low-density polyethylene, linear low-density polyethylene and polyvinyl chloride have been used as materials for blow molding (blow molding) for obtaining bottles and the like. ing.
In addition, recently, in order to obtain electric and electronic parts such as air ducts and lighting fixtures, automotive parts such as air spoilers and consoles, and furniture such as desk tops, they have excellent thermal and mechanical properties. In addition, a so-called engineering plastic (for example, see JP-A-4-120)
157, etc.). In the method disclosed in Japanese Patent Application Laid-Open No. 4-120157, heat resistance (heat deformation temperature) of 100 ° C. or more is obtained, but the weight of a parison such as an air spoiler is 5 kg using an accumulator type blow molding machine. / When trying to mold a large molded product with more than shots, the time to cool the molded product in the mold, the time to melt the resin for the next molding, the time to attach the mounting bracket to be inserted to the mold, etc., The molding cycle becomes longer, the viscosity difference between the resin remaining in the accumulator and the resin melted by the new screw is more likely to occur, causing hot water wrinkles (surface unevenness) on the surface of the blow molded product. Thus, problems such as so-called surface defects are likely to occur. As a means for imparting heat resistance to ABS resin, part or most of styrene is converted to α.
-Methyl styrene is generally used, but the phenomenon that the molten resin does not reach the complex shaped part or the mounting bracket part to be inserted into the blow molded product, so-called defectiveness around the meat, occurs, and the obtained blow molded product When mounting as a car exterior part or the like, a problem such as insufficient mounting strength is likely to occur.

[0003]

SUMMARY OF THE INVENTION The present invention relates to an ABS resin composition for blow molding, which is excellent in surface properties, roundness, heat resistance, impact resistance and blow moldability of a blow molded article, and a blow molded article comprising the same. The purpose is to provide.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve these problems, and as a result, the specific resin composition has excellent surface properties, blowability, and blow moldability of a blow molded product. The inventors have found that the balance between impact resistance and heat resistance is good, and have completed the present invention.

That is, the present invention provides a rubber-like elastic body,
A graft polymer (a) obtained by polymerizing at least one member selected from the group consisting of aromatic vinyl, vinyl cyanide, α, β-unsaturated glycidyl ester compound, (meth) acrylate ester and maleimide; A polymer (b) obtained by polymerizing at least one member selected from the group consisting of aromatic vinyl, vinyl cyanide, α, β-unsaturated acid glycidyl ester compound, (meth) acrylate ester and maleimide; And a rubber-like elastic body content of 5 to 40% by weight and a maleimide unit content of 0.1 to
30% by weight, α-methylstyrene content of 0.1 to 5
ABS for blow molding having 9.9% by weight, an α, β-unsaturated glycidyl ester compound content of 0.001 to 5% by weight, and a reduced viscosity of methyl ethyl ketone-soluble component of 0.5 to 1.5 dl / g. 240 ° C. based resin composition (Claim 1)
Melt value (MF ₂₄₀ ) at 1.5 to 8 g / 10
2. The ABS resin composition for blow molding according to claim 1, wherein the MF ₂₄₀ / MF ₂₂₀ is not more than 3.5 in terms of the ratio to the melt flow value (MF ₂₂₀ ) at 220 ° C. 2) and a blow-molded article (claim 3) using the ABS resin composition for blow molding according to claim 1 or 2.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The ABS resin composition for blow molding according to the present invention comprises an aromatic vinyl,
A graft polymer (a) obtained by polymerizing at least one selected from the group consisting of vinyl cyanide, an α, β-unsaturated glycidyl ester compound, a (meth) acrylate ester and a maleimide; , Vinyl cyanide, α, β-unsaturated acid glycidyl ester compound,
And (b) a polymer obtained by polymerizing at least one selected from the group consisting of (meth) acrylates and maleimides.

The ratio of the graft copolymer (a) to the polymer (b) constituting the ABS resin composition for blow molding of the present invention is such that the rubber-like elastic material content is 5 to 40% by weight.
More preferably, the content is 7 to 35% by weight. If the rubber elastic body content is less than 5% by weight, impact resistance tends to decrease, and if it exceeds 40% by weight, heat resistance tends to decrease. The particle diameter of the rubber-like elastic body is such that a weight average particle diameter of a small particle rubber of 0.15 μm or less and a large particle rubber of 0.25 μm or more are used in combination, and the weight ratio thereof is 1/9 to 9
The range of / 1 is particularly preferable from the viewpoint of impact resistance and rigidity.

The content of the maleimide unit in the ABS resin composition for blow molding of the present invention is 0.1 to 30% by weight. The content is more preferably 0.1 to 25% by weight, most preferably 1 to 15% by weight. If the maleimide unit content is less than 0.1% by weight, the heat resistance and the roundness tend to decrease, and if it exceeds 30% by weight, the impact resistance tends to decrease.

The content of α-methylstyrene in the ABS resin composition for blow molding of the present invention is 0.1 to 59.9% by weight. The content is more preferably 1 to 58% by weight, most preferably 3 to 50% by weight. α
If the content of methylstyrene is less than 0.1% by weight, the surface properties tend to decrease, and if it exceeds 59.9% by weight, the impact resistance and the roundness tend to decrease.

The content of the α, β-unsaturated acid glycidyl ester compound in the ABS resin composition for blow molding of the present invention is 0.001 to 5% by weight. And 0.005-
Preferably it is 3% by weight, most preferably 0.01 to 2% by weight. When the content of the α, β-unsaturated glycidyl ester compound is less than 0.001% by weight, the effect of making the surface uniform is insufficient, and when it exceeds 5% by weight, the impact resistance and the roundness tend to decrease. is there.

The solvent viscosity (N, N-dimethylformamide solution, 30 ° C.) of the methyl ethyl ketone soluble portion of the ABS resin composition for blow molding of the present invention has a reduced viscosity of 0.5.
１．５1.5 dl / g. Further, 0.6 to 1.3 dl
/ G, and most preferably 0.7 to 1.1 dl / g. 0.5 dl reduced viscosity
/ G or less, blowdown during blow molding becomes severe,
There is a tendency that it becomes difficult to obtain a good molded product due to breakage of the parison, uneven thickness, impact resistance,
Thinner resistance, oil resistance, etc. decrease, and if it exceeds 1.5 dl / g, the melt viscosity at the time of blow molding becomes too high, molding becomes difficult, and the molding temperature becomes high, so that oxidation deterioration inside the molded product may occur. This tends to occur and the impact resistance tends to decrease.

The ABS resin composition for blow molding of the present invention has a melt flow value (MF ₂₄₀ ) at 240 ° C. of 1.5 to 1.5.
8 g / 10 min (10 kg load). Furthermore, 1.7-
It is preferably 7 g / 10 min, most preferably 2.0 to 7 g / 10 min, and the ratio to the 220 ° C. melt flow value (MF ₂₂₀ ), MF ₂₄₀ / MF ₂₂₀ is 3.5. It is as follows. Further, it is preferable to be 3.49 or less, and most preferably 3.48 or less.

The melt flow value at 240 ° C. is 1.5
If it is less than g / 10 minutes, the melt viscosity at the time of blow molding becomes too high and molding becomes difficult, and the molding temperature becomes high, so that oxidative deterioration inside the molded product is apt to occur and impact resistance is reduced. If the amount exceeds 8 g / 10 minutes, drawdown during blow molding becomes severe, the parison is cut off, or the thickness becomes uneven, so that it is difficult to obtain a good molded product. Further, the MF240 / MF220
Exceeds 3.5, hot water wrinkles tend to be easily formed on the surface of the molded product.

The rubber-like elastic material of the graft copolymer (a) of the present invention has a glass transition temperature of 0 ° C. or less and a weight average particle size of 0.05 to 1.0 μm. It is preferable in terms of rigidity. Although the gel content is not particularly limited,
0-95%, especially 30-95% is preferred.

Examples of the rubber-like elastic material include diene rubbers such as polybutadiene, butadiene-styrene copolymer (SBR), butadiene-acrylonitrile copolymer (NBR), and butadiene-acrylate copolymer.
Styrene-propylene copolymer (EPR), ethylene-
Olefin rubbers such as propylene-non-conjugated diene copolymer (EPDM), polybutyl acrylate, poly 2-
Acrylic rubbers such as ethylhexyl acrylate, silicone rubbers and the like can be mentioned, and one or more kinds can be used. Among them, diene rubber is preferred from the viewpoint of impact resistance. Further, in order to improve the balance between rigidity and impact resistance, it is preferable to form a multilayer structure or control the particle size distribution. In the multilayer structure, the components of the rubber-like elastic body are not uniform but form a non-uniform layer. The particle size distribution refers to a combination of large particles and small particles. For that purpose, it is possible to enlarge the small particle rubber with an acidic substance or an acid latex.

The monomer to be polymerized into the rubber-like elastic material may be 30 to 89.9% by weight of aromatic vinyl, and
0 to 79.5% by weight, vinyl cyanide 10 to 40% by weight, further 20 to 40% by weight, α, β-unsaturated glycidyl ester compound 0.1 to 30% by weight, further 0.5 to 20% % By weight, (meth) acrylic acid ester 0
70% by weight, further 0-30% by weight, maleimide 0
30% by weight, more preferably 0 to 25% by weight. When the amount of the aromatic vinyl is less than 30% by weight, blow moldability is reduced,
If it exceeds 90% by weight, the thinner resistance tends to decrease and the impact resistance tends to decrease. When the content of the vinyl cyanide is less than 5% by weight, thinner resistance and impact resistance are reduced,
If it exceeds 40% by weight, the thermal stability tends to decrease.
The α, β-unsaturated acid glycidyl ester compound is contained in an amount of 0.1%.
If the amount is less than 1% by weight, the effect of uniformizing the surface properties is insufficient, and if it exceeds 30% by weight, the impact resistance tends to decrease. If the amount of the (meth) acrylate exceeds 70% by weight, impact resistance and thinner resistance tend to be reduced.
If the amount of the maleimide exceeds 30% by weight, the impact resistance tends to decrease.

Specific examples of the aromatic vinyl include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, bromostyrene, vinylnaphthalene and the like.
Specific examples of the vinyl cyanide include acrylonitrile and methacrylonitrile. Specific examples of the α, β-unsaturated glycidyl ester compound include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Examples of the acrylate include methyl methacrylate, ethyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Specific examples of the maleimide include maleimide, N-phenylmaleimide, and N-phenylmaleimide.
-Methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide and the like.

The ratio between the rubber-like elastic material and the graft monomer is not particularly limited, but the graft ratio (%) of the graft copolymer: {graft branch (weight) / rubber-like elastic material (weight)} × 10
0 is preferably from 10 to 100%, more preferably from 20 to 70%. If the graft ratio is less than 10%, the impact resistance is reduced, and 1
If it exceeds 00%, blow moldability tends to decrease.

The polymer (b) of the present invention comprises an aromatic vinyl 3
0 to 90% by weight, more preferably 50 to 80% by weight, 5 to 40% by weight of vinyl cyanide, further 20 to 30% by weight,
α, β-unsaturated glycidyl ester compound 0-30% by weight, further 0-20% by weight, (meth) acrylate 0-30% by weight, further 0-20% by weight, maleimide 0.1-50% % By weight, and more preferably 0.1 to 30% by weight.

When the content of the aromatic vinyl is less than 30% by weight, blow moldability is deteriorated.
When the vinyl cyanide content is less than 5% by weight, the impact resistance and the thinner resistance tend to decrease, and when it exceeds 40% by weight, the thermal stability tends to decrease, If the amount of the α, β-unsaturated glycidyl ester compound exceeds 30% by weight, the impact resistance tends to decrease. If the amount of the (meth) acrylate exceeds 30% by weight, the impact resistance tends to decrease. When the amount of the maleimide is less than 0.1% by weight, heat resistance and lapping property tend to decrease, and when it exceeds 50% by weight, impact resistance and blow moldability tend to decrease.

Specific examples of the monomer used for the polymer (b) include the same monomers as those exemplified for the graft polymerization of the graft copolymer (a).
From the viewpoints of rigidity, blow moldability, heat deformation resistance, etc., styrene is preferred as aromatic vinyl, acrylonitrile as vinyl cyanide, methyl methacrylate as (meth) acrylate, and phenylmaleimide as maleimide.

The method for producing the ABS resin composition for blow molding is not particularly limited, and may be a known emulsion polymerization method, emulsion-suspension polymerization method, emulsion-bulk polymerization method, bulk polymerization method, solution polymerization method, or the like. Can be performed. For example, it is produced by reacting the vinyl monomer in the presence of a rubber-like elastic material to obtain a graft copolymer (a). Further, the polymer (b) is produced by copolymerizing the vinyl monomer. It is also possible to react the vinyl monomer in the presence of a rubber-like elastic material to produce the graft copolymer (a) and the polymer (b) in the same reactor. Further, the obtained graft copolymer (a) and polymer (b) may be mixed in a latex state and salted out to obtain a powder, or they may be separately salted out to obtain a powder and mixed. .

The ABS resin composition for blow molding includes, in addition to the ABS resin composition, a heat-resistant ABS resin composition in which part or most of styrene is replaced with α-methylstyrene and / or maleimide, butadiene. Was replaced with ethylene-propylene rubber (heat resistant) AES
Resin compositions, (heat-resistant) AAS resin compositions replaced with polyacrylic esters, and ASS resin compositions replaced with silicone-based rubber (heat-resistant).
These compositions may be used alone or in combination of two or more.

The ABS resin composition for blow molding of the present invention contains a lubricant, an antioxidant, talc, an alkali metal hydroxide or carbonate, or an alkaline earth metal as long as the effects of the present invention are not impaired. Hydroxides, carbonates or oxides, and, if necessary, one or more of pigments, plasticizers, ultraviolet absorbers, light stabilizers and the like. Further, in order to further improve drawdown resistance and the like, Teflon (registered trademark), a high molecular weight AS resin (weight average molecular weight of 500,000 to 3,000,000 in polystyrene), a high molecular weight PMMA (weight average molecular weight of
(Million, 000 to 3,000,000) can also be added.

Further, the ABS resin composition for blow molding of the present invention comprises one or more of styrene resin, polycarbonate, polyamide, polybutylene terephthalate and the like.
It may be used in combination with more than one kind. As styrene resins, general-purpose (GP) polystyrene, impact resistance (HI)
PS) Polystyrene and AS resin which is a copolymer of styrene and acrylonitrile. The ABS resin composition for blow molding of the present invention produced in this way is molded by a method such as ordinary blow molding, for example, accumulator type blow molding, direct blow molding, etc., to produce the blow molded article of the present invention. Is done. In this blow molding step, it is preferable to blow-mold the obtained resin composition with a parison or sheet at 200 ° C. or higher from the viewpoints of blow-up properties and surface properties. In order to obtain a better effect, an inert gas such as nitrogen, carbon dioxide, helium, argon, or neon may be used instead of air when the parison and the sheet are inflated.

[0026]

EXAMPLES Examples and comparative examples are shown below, but the present invention is not limited thereto. In addition, "parts" shown below all means "parts by weight".

The relationship between the abbreviations in the embodiment and their contents is as follows. R-1: weight average particle size 0.10 μm, gel content 90
% Polybutadiene using an acid group-containing latex to enlarge the polybutadiene having a weight average particle diameter of 0.40 μm R-2: a weight average particle diameter of 0.25 μm, and a gel content of 90%
% Polybutadiene R-3: weight average particle diameter 0.10 μm, gel content 90
% Polybutadiene R-4: weight average particle diameter 0.06 μm, gel content 92
% Butadiene-styrene copolymer (butadiene 65% by weight, styrene 35% by weight) αMSt: α-methylstyrene St: styrene AN: acrylonitrile PMI: N-phenylmaleimide GMA: glycidyl methacrylate CHP: cumene hydroperoxide tDM: t -Dodecylmercaptan PN: sodium palmitate ABS: sodium dodecylbenzenesulfonate.

Examples 1 to 6 and Comparative Examples 1 to 6 Production of Graft Copolymer (a) (1) Production of Graft Copolymer (a-1) In a polymerization vessel equipped with a stirrer, 280 parts of water and acid groups were added. Weight average particle diameter 0.40μ enlarged using Latec (S) containing
m, 60 parts of polybutadiene latex (R-1) (in terms of solid content), 0.3 part of sodium formaldehyde sulfoxylate, 0.0025 part of ferrous sulfate, and 0.01 part of disodium ethylenediaminetetraacetate were charged and deoxygenated. Then, after heating to 60 ° C. while stirring in a nitrogen stream, A
A monomer mixture composed of 10 parts of N, 30 parts of St, and 0.3 parts of CHP was continuously dropped at 60 ° C. for 5 hours. After completion of the dropwise addition, the polymerization temperature was set to 65 ° C., and stirring was continued for 1 hour.
The polymerization was terminated. The resulting latex was salted out with calcium chloride, and washed, filtered and dried to obtain a powdery graft copolymer (a-1). Table 1 shows the results.

Production of Acid Group-Containing Latex (S) An acid group-containing latex (S) necessary for enlarging the rubber polymer (r) to the rubber polymer (R) was produced as follows.

In a polymerization vessel equipped with a stirrer, 200 parts of water, 0.6 parts of sodium dioctylsulfosuccinate, 0.5 parts of sodium formaldehyde sulfoxylate, 0.0025 parts of ferrous sulfate, and 0.01% of disodium ethylenediaminetetraacetate After the mixture was deoxygenated and heated to 70 ° C. while stirring in a nitrogen stream, butyl methacrylate 25 was added.
Part, butyl acrylate 5 parts, tDM 0.1 part, CH
0.15 parts of the monomer mixture was continuously dropped at a polymerization temperature of 70 ° C. over 2 hours, and then 50 parts of butyl methacrylate, 4 parts of butyl acrylate, and 1 part of methacrylic acid were added.
A monomer mixture of 6 parts, 0.5 parts of tDM, and 0.15 parts of CHP was continuously dropped over 4 hours. After dropping, 1
Stirring was continued for another hour to complete the polymerization. Polymerization conversion rate is 97
%Met. The enlargement from the rubber polymer (r) to the rubber polymer (R) is caused by a weight average particle diameter of 0.10 μm and a gel fraction of 90.
% Polybutadiene latex (100 parts)
%, And the mixture was heated to 60 ° C., and 3.2 parts of an acid group-containing latex (S) was added.
At 1 ° C. for 1 hour to enlarge, and a weight average particle size of 0.4
A polybutadiene latex of 0 μm was obtained. Graft copolymer (a-2), (a-3), (a-4) In the same manner as the graft copolymer (a-1), a rubber polymer and a monomer mixture shown in Table 1 were used. Then, graft copolymers (a-2), (a-3) and (a-4) were produced. Table 1 shows the results.

[0031]

[Table 1] (2) Production of Polymer (b) Polymer (b-1) A polymerization vessel equipped with a stirrer was charged with 250 parts of water and 1.0 part of PN, and after deoxygenation, stirred at 70 ° C. in a nitrogen stream.
Until heated. Further, 0.4 part of sodium formaldehyde sulfoxylate, 0.0025 part of ferrous sulfate and 0.01 part of disodium ethylenediaminetetraacetate are charged, and then αMSt 60 parts, AN 30 parts, St 10 parts, tD
A monomer mixture consisting of 0.25 parts of M and 0.2 parts of CHP was dropped at a polymerization temperature of 70 ° C. continuously over 7 hours.
After completion of the dropwise addition, the polymerization temperature was set to 75 ° C., and stirring was continued for 1 hour to terminate the polymerization. The obtained latex was salted out with calcium chloride, and washed, filtered and dried to obtain a powdery polymer (b-1). Table 2 shows the results.

Polymers (b-2), (b-3) and (b-
4) In the same manner as for the polymer (b-1), using the monomer mixture shown in Table 2, the polymers (b-2), (b-3) and (b-
4) was manufactured. Table 2 shows the results.

[0033]

[Table 2] Examples 1 to 6 and Comparative Examples 1 to 6 Graft copolymers (a-1) to (a-4) and polymer (b)
-1) to (b-4) were mixed at a ratio shown in Table 3 with 100 parts of a resin mixture, and a phosphorus-based stabilizer (ADK STAB P
0.4 parts of EP-36, manufactured by Asahi Denka Kogyo Co., Ltd., 0.4 parts of phenolic stabilizer (ADK STAB AO-30, manufactured by Asahi Denka Kogyo Co., Ltd.), 0.7 part of ethylenebisstearylamide as a lubricant (Nippon Yushi Co., Ltd.), polyethylene wax (Neo Wax ACL, Yasuhara Yushi Kogyo Co., Ltd.)
0.5 parts, calcium hydroxide as a hydroxide of an alkaline earth metal (Super Microstar, manufactured by Maruo Calcium Co., Ltd.) 0.5 parts, and talc (Microace L-1 (average particle size: 1. 8 μm), 0.5 part of Nippon Talc), mixed with a Henschel mixer, and mixed with a vented single screw extruder (HV-40-28, manufactured by Tabata Machine Industry Co., Ltd.).
Extruded at a set temperature of 0 ° C. and pelletized. The obtained pellets were evaluated by the following method. Tables 3 and 4 show the results.
Shown in

[0034]

[Table 3]

[0035]

[Table 4] The evaluation methods in this example and comparative examples are summarized below. (A) Blow molding The ABS resin in the form of pellets obtained as described above is blow molded using a DA-50 blow molding machine (accumulator capacity: 0.5 l) manufactured by Placo Co., Ltd. I got The molding conditions are as follows: parison temperature is about 240 ° C,
Injection speed (index) is 150, screw rotation speed is 60r
pm, blow pressure was 6 kg / cm ² G (air), cooling time was 100 seconds, and mold temperature was 60 ° C.

(1) Surface appearance (1-a) Defective concave portion (dent) (W) 60 × (L) 400 × (H) 30 (mm), box-shaped blow-molded product having an average thickness of 3.5 mm Draw a rectangle of 40 × 80 (mm) on the surface of the molded product using a, and visually count the uneven concave defective portions (hecks) (size is 0.02 mm or more) in the rectangle, and The average of the numbers was determined. Evaluation was made according to the following criteria. ：: The average number of dents is less than one. Δ: The average number of dents is 1 to 5. X: The average number of dents is 5 or more.

(1-b) Defects in hot water wrinkles (uneven surface) When a cylindrical blow molded product having an outer diameter of 70 mm, a length of 400 mm, and an average thickness of 3.2 mm is formed, the cooling time is reduced from 100 seconds to 2 seconds.
When the time was changed to 00 seconds, the presence or absence of hot water wrinkles on the molded product surface was visually observed. Evaluation was made according to the following criteria. ：: No hot water wrinkles were generated. X: Hot water wrinkles occurred.

(2) Roundness A (B) 100 × (L) 310 × (H) 40 (mm) box-type blow-molded product having an average thickness of 3.5 mm, and M6 insert bolts were incorporated at both ends. The state of the blow molding around the bolt head was visually observed and evaluated according to the following criteria.

：: Good (A sectional explanatory view including the insert bolt of the blow molded product (the insert bolt is not a sectional explanatory view)), as shown in FIG. The resin composition 2 is almost rotated and there is no gap) ×: defective (cross-sectional explanatory view including the insert bolt of the blow-molded product (insert bolt is not a cross-sectional explanatory view)). The ABS resin composition 2 is not sufficiently turned around P2 around the stepped portion 1 of FIG.

(3) Drawdown Property A parison having a length of about 500 mm (weight of 500 g of parison) was left to stand after being injected, and the time required for the parison to separate from the die and drop was measured and evaluated. ：: The time required for the parison to fall after the parison injection exceeds 60 seconds. Δ: Time from parison injection to parison fall is 20 to
60 seconds. ×: Time from parison injection to parison fall is less than 20 seconds.

(4) Drop Weight Strength Using a cylindrical blow-molded product having an outer diameter of 70 mm, a length of 400 mm, and an average thickness of 3.2 mm, the drop weight strength at −30 ° C. (weight of weight × half-break height (weight) J) was measured.

(B) Reduced viscosity The obtained pellet was added to methyl ethyl ketone at 23 ° C. for 12 hours.
After dissolving for hours, the mixture was centrifuged, and the soluble matter was precipitated with methanol. The precipitate was dried with a vacuum drier to obtain a sample. The obtained sample was made into a 0.3% solution of N, N-dimethylformamide, and was measured at 30 ° C. with a Ube-Rohde viscometer.
Was measured.

(C) Melt flow value The obtained pellets were measured at 220 ° C., 10 kg load and 240 ° C., 10 kg load according to ASTM D-1238. (D) Heat deformation temperature: HDT A test piece was prepared by cutting out the obtained blow molded product, and was measured at a load of 0.45 MPa in accordance with ASTM D-648.

(E) Flexural strength and flexural modulus The blow-molded product obtained was cut out to prepare a test piece, which was measured at 23 ° C. in accordance with ASTM D-790.

[0045]

As is clear from the results shown in Table 1, according to the ABS resin for blow molding of the present invention, the heat deformation temperature is 10%.
At 0 ° C. or higher, a blow-molded article having excellent drawdown resistance and roundness during blow molding, excellent surface appearance of the blow-molded article, and excellent impact resistance can be obtained.

[Brief description of the drawings]

FIG. 1 is an explanatory cross-sectional view showing a state in a case where the roundness is good in the evaluation of the roundness of an example and a comparative example.

FIG. 2 is a cross-sectional explanatory view showing a state in which the meat-measuring property is poor in the meat-measuring property of a comparative example.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Insert bolt 2 ABS resin composition 3 Step P1 ABS resin composition 2 has turned substantially, and around the step part 3 of the insert bolt 1 with no gap P2 ABS resin composition 2 has turned sufficiently. Around the step of insert bolt 1 with no gap

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 220/42 C08F 220/42 222/40 222/40 291/02 291/02 C08J 5/00 CER C08J 5 / 00 CER C08L 55/02 C08L 55/02 // (C08L 51/04 (C08L 51/04 25:08 25:08 33:18 33:18 33:14 33:14 33:06 33:06 35:00 ) 35:00) B29K 55:02 B29K 55:02 F term (reference) 4F071 AA07 AA10X AA22X AA33X AA34X AA36X AA76 AA81 AA88 AF23 AF45 AF53 AH05 BA01 BB05 BC04 4F208 AA13K AH17 AM04 LA01 4GB01BG04 BN062 BN122 BN142 BN232 CD191 GG01 4J026 AA12 AA13 AA16 AA45 AA67 AA68 AB44 BA05 BA06 BA27 BA30 BA33 BA37 DB02 DB03 DB04 DB05 FA03 GA09 4J100 AB02P AB03P AB04P AB08P AB09P AL03S AL04S AL10T AM03AM0348

Claims (3)

[Claims] 1. An aromatic vinyl, in the presence of a rubber-like elastic body,
A graft polymer (a) obtained by polymerizing at least one selected from the group consisting of vinyl cyanide, an α, β-unsaturated glycidyl ester compound, a (meth) acrylate ester and a maleimide; , Vinyl cyanide, α, β-unsaturated acid glycidyl ester compound,
A resin composition comprising a polymer (b) obtained by polymerizing at least one selected from the group consisting of (meth) acrylates and maleimides, and (i) a rubber-like elasticity in the resin composition. Body content of 5 to 40% by weight, (ii)
The maleimide unit content in the resin composition is from 0.1 to 30.
(Iii) α-methylstyrene content in the resin composition is 0.1 to 59.9% by weight, and (iv) α, β-unsaturated glycidyl ester compound content in the resin composition. Is 0.001 to 5% by weight, and (v) the reduced viscosity of the methyl ethyl ketone soluble component of the resin composition is 0.5 to 1.5.
An ABS resin composition for blow molding having excellent heat resistance, wherein the composition is dl / g. 2. Melt flow value at 240 ° C. (MF ₂₄₀ )
Is 1.5 to 8 g / 10 min (10 kg load), and 220
Ratio to the melt flow value (MF ₂₂₀ ) in ° C., MF ₂₄₀ / MF
_2. A for blow molding according to claim 1, wherein ₂₂₀ is 3.5 or less.
BS resin composition. 3. An AB for blow molding according to claim 1 or 2.
A molded article obtained by molding the S-based resin composition.