JP2001049076A - Abs resin composition for blow molding and blow-molded item therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ABS resin composition for blow molding which is excellent in rigidity and surface property and has an excellent balance of moldability and impact-resistance, and a blow-molded item therefrom. SOLUTION: This resin composition is prepared by bending 5-50 pts.wt. of one or more additives selected from talc powder, mica, kaolin and whisker with 100 pts.wt. of an ABS resin the methy ethyl ketone-soluble part of which has a reduced viscosity of 0.3-1.5 dl/g (0.3% N,N-dimethylformamide solution at 30 deg.C). Preferably, the talc powder has an average particle size of not more than 5 μm.

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 rigidity and surface properties of a blow molded article, and which has an excellent balance between blow moldability and impact resistance, and a blow molded article comprising the same. Things.

[0002]

2. Description of the Related Art Conventionally, thermoplastic resins 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. I have.
In recent years, to obtain electrical and electronic parts such as air ducts and lighting fixtures, automotive parts such as air spoilers and consoles, and furniture such as desk tops, thermal and mechanical properties Excellent engineering plastics (for example, see JP-A-7-03)
No. 2454) is used.

Conventionally, the resin composition for blow molding described in JP-A-7-032454 has a flexural modulus of 250.
When the product thickness is reduced to 0MPa or less by using an air spoiler to reduce the weight, there is a problem that the amount of deformation is large in the test of applying a load to the center of the product, which is one of the product tests, and the product does not fall within the product specifications. .

In order to solve these problems, a flexural modulus of 2500 MPa or more is desired, and the use of a glass fiber reinforced ABS resin has been attempted. However, the appearance of the surface of the molded product is deteriorated, and the sanding before coating is difficult. It takes time, the impact resistance is reduced, and the situation is not always satisfactory.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ABS resin composition which is excellent in rigidity and surface properties of a blow-molded product and which has an excellent balance of blow-moldability and impact resistance, and a blow-molded product thereof. It is the purpose.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve these problems, and as a result, by adding a specific inorganic substance to an ABS resin, the rigidity is high and the flexural modulus is 2500 MPa or more. Surprisingly, conventional fillers had a large drop in impact resistance, but there was little drop in impact resistance. The drop weight strength at low temperatures of -30 ° C was 1.5 kgm or more, and They found that the moldability was good and completed the present invention. That is, the ABS resin composition for blow molding according to the present invention has a reduced viscosity of methyl ethyl ketone-soluble component of 0.3 to 1.5 dl / g.
To 100 parts by weight of an ABS resin (0.3% solution of N, N-dimethylformamide), one or two or more kinds selected from talc powder, mica, kaolin, and whiskers were added to 5 parts by weight.
５０50 parts by weight. The ABS resin blow-molded article according to the present invention is obtained by blow-molding the above-described resin composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The ABS resin in the present invention comprises:
ABS resin consisting of styrene, butadiene and acrylonitrile, heat-resistant ABS resin in which part or most of styrene of the ABS resin is replaced by α-methylstyrene or maleimide, etc., butadiene to ethylene-propylene rubber or polybutyl acrylate, etc. ABS-based resins such as substituted (heat-resistant) AES resin and (heat-resistant) AAS resin, and (heat-resistant) ABS-based resin in which butadiene is replaced with silicon rubber or silicon-acrylic composite rubber. These may be used alone or in combination of two or more. The ABS resin generally contains 5 to 55% by weight of acrylonitrile unit, preferably 10 to 40% by weight, 5 to 30% by weight of butadiene unit, preferably 10 to 25% by weight and styrene unit (α-methylstyrene or (Including a maleimide unit) 40 to 9
0% by weight, preferably 50 to 80% by weight, 0 to 30% by weight, preferably 0 to 30% by weight of a vinyl compound copolymerizable with these.
-25% by weight.

[0008] Examples of the vinyl compound copolymerizable with these compounds include methyl methacrylate, ethyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate,
(Meth) acrylates such as butyl methacrylate, glycidyl acrylate, glycidyl methacrylate,
Glycidyl α, β-unsaturated acid compounds such as glycidyl ethacrylate are exemplified.

The method for producing the above ABS resin is not particularly limited, and emulsion polymerization, suspension polymerization, solution polymerization and the like can be applied. Emulsion polymerization is easy to control the particle size of rubber particles, Is preferably used from the viewpoint of impact resistance.

[0010] As the emulsion polymerization method, a usual method can be applied. That is, the compound may be reacted in an aqueous medium in the presence of a radical initiator. At that time, the compound may be used as a mixture or, if necessary, may be used in a divided form. Furthermore, the method of adding the compound is not particularly limited, and the compound may be charged all at once or may be added sequentially.

Examples of the radical initiator include water-soluble or oil-soluble peroxides such as potassium persulfate, ammonium persulfate, cumene hydroperoxide and paramenthane hydroperoxide. Other polymerization accelerators, polymerization degree regulators, and emulsifiers may be appropriately selected from those used in known emulsion polymerization methods.

The ABS resin set of the present invention has a reduced viscosity of methyl ethyl ketone soluble component of 0.3 to 1.5 dl / g.
(N, N-dimethylformamide 0.3% solution, 30
C). More preferably 0.4 to 1.3.
dl / g, and more preferably 0.5 to 1.1 dl / g.
g. If it is less than 0.3 dl / g, impact resistance, thinner resistance and oil resistance will be reduced, and if it exceeds 1.5 dl / g, blow moldability will be reduced.

As a means for adjusting the reduced viscosity, known methods such as a polymerization temperature, a polymerization degree adjusting agent, and a polymerization accelerator are applied. However, the polymerization adjusting agent can easily control the reduced viscosity, and the polymerization stability can be improved. Is preferably used.

The talc (talc) is a mineral containing hydrous magnesium silicate (4SiO ₂ · 3MgO · H ₂ O), which is composed of about 60% by weight of SiO _{2 and} about 30% by weight of MgO. Then, this talc powder is used. The use amount of the talc powder is preferably 5 to 50 parts by weight, more preferably 5 to 50 parts by weight based on 100 parts by weight of the ABS resin.
It is 40 parts by weight, more preferably 5 to 30 parts by weight. If the amount is less than 5 parts by weight, the flexural modulus does not become 2500 MPa or more. If the amount exceeds 50 parts by weight, the effect of improving the bending elasticity is saturated or the impact strength is reduced, which is not preferable. The average particle size of the talc powder is preferably 5 μm or less, more preferably 4 μm or less. If it exceeds 5 μm, the impact strength tends to decrease. The talc powder is
Those having different average particle sizes may be used in combination. The talc powder may be surface-treated with a silane coupling agent or the like.

The above mica (mica), kaolin (white clay)
Is a mineral composed of aluminosilicate and phyllosilicate containing an alkali metal.

The whiskers include aragonite-based calcium carbonate whiskers, aluminum borate whiskers, magnesium oxide whiskers, magnesium hydroxide whiskers, 6
And potassium titanate whiskers.

The blending of the components and blends of the resin composition, the granulation (pelleting), and the blow molding may be performed by a method known per se. For example, the ABS resin and talc may be mixed with a Henschel mixer, melt-extruded into pellets using a single-screw or multi-screw extruder, and blow-molded.

The ABS resin composition may further contain a lubricant, an antioxidant, a hydroxide or carbonate of an alkali metal, and, if necessary, a pigment, as long as the effects of the present invention are not impaired.
One or more plasticizers, ultraviolet absorbers, light stabilizers and the like may be mixed.

The resin composition may be used alone or in combination of two or more of styrene resin, polycarbonate, polyamide, polybutylene terephthalate and the like.

As the styrene resin, general-purpose (G
P) polystyrene, high impact polystyrene (HIP
S) and AS resin which is a copolymer of styrene and acrylonitrile.

As the blow molding method, besides ordinary blow molding, sheet parison method, cold parison method,
There are various methods such as a bottle pack method, an injection blow molding method, and a stretch blow molding method, and any method can be adopted. In this blow molding step, the obtained resin composition is heated to 200 ° C. in terms of blow-up properties, surface properties, and the like.
It is preferable to blow-mold the above parison or sheet. Furthermore, to obtain a higher effect, when inflating the parison and the sheet, instead of air, nitrogen,
An inert gas such as carbon dioxide, helium, argon, or neon may be used.

The ABS resin composition of the present invention is particularly suitable for blow molding as described above, but can provide excellent molded products in extrusion molding as in the case of blow molding.

[0023]

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". (A) Production of ABS resin 1) ABS resin 1: i) Graft copolymer A In a polymerization vessel equipped with a stirrer, 280 parts of water and a polybutadiene latex 60 having a weight average particle diameter of 0.3 μm and a gel fraction of 90% are placed. Parts (in terms of solid content), 0.3 parts of sodium formaldehyde sulfoxylate, ferrous sulfate 0.0025
Parts, disodium ethylenediaminetetraacetate 0.01 part, and after deoxygenation, heated to 60 ° C. while stirring in a nitrogen stream, acrylonitrile 10 parts, styrene 30 parts
, A monomer mixture consisting of 0.3 parts of cumene hydroperoxide was continuously dropped at 60 ° C over 5 hours.
After completion of the dropwise addition, the polymerization temperature was set to 65 ° C., and stirring was continued for 1 hour, and then the polymerization was terminated. The polymerization conversion was 98% and the graft ratio was 40%. ii) Copolymer B 250 parts of water and 1.0 part of sodium palmitate were charged into a polymerization vessel equipped with a stirrer, and after deoxygenation, heated to 70 ° C. while stirring in a nitrogen stream. Further, after 0.4 part of sodium formaldehyde sulfoxylate, 0.0025 part of ferrous sulfate and 0.01 part of disodium ethylenediaminetetraacetate were charged, 60 parts of α-methylstyrene, 30 parts of acrylonitrile, 10 parts of styrene, and t- A monomer mixture consisting of 0.25 parts of dodecyl mercaptan and 0.2 parts of cumene hydroperoxide 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 polymerization conversion was 98%. iii) 30 parts of the above graft copolymer A and copolymer B70
Were mixed in the form of latex. The resulting mixture was salted out with calcium chloride, washed, filtered, and dried to obtain an ABS resin powder. 2) ABS resin 2: a copolymer B of the ABS resin 1
30 parts of acrylonitrile and 7 parts of styrene
Except that it was changed to 0 parts, A
A BS resin powder was obtained. The polymerization conversion of the copolymer A was 99%. 3) ABS resin 3: a copolymer B of the ABS resin 1
Of monomer mixture and sodium palmitate in 23 parts of N-phenylmaleimide, 20 parts of acrylonitrile, 57 parts of styrene, sodium dodecylbenzenesulfonate.
Except that it was changed to 0 parts, A
A BS resin powder was obtained. The polymerization conversion of the copolymer A was 97%. 4) ABS resin 4: Polybutadiene latex of graft copolymer A of ABS resin 1 is ethylene-propylene rubber latex having a weight average particle size of 0.5 μm and a gel fraction of 60% by weight (Mitsui Chemicals, Inc. EPT EN
ABS resin powder was obtained in the same manner as ABS resin 1 except that the resin composition was changed to B type). Graft copolymer A
Was 97%, and the graft ratio was 38%. (B) Talc powder The talc powder used in the examples and comparative examples is listed below. a: Micro Ace L-1 manufactured by Nippon Talc (average particle size:
1.8 μm) b: Micro Ace K-1 manufactured by Nippon Talc (average particle size:
3.2 μm) c: Simgon made by Nippon Talc (average particle size:
6.0 μm) For the measurement of the average particle size of the talc powder, a centrifugal sedimentation type particle size distribution analyzer: Model SA-CP2-20 manufactured by Shimadzu Corporation was used. (C) Glass fiber In this comparative example, the glass fiber was CS-3 manufactured by Nitto Boseki Co., Ltd.
PE-331 was used. (D) ABS resin for blow molding Examples 1 to 6 and Comparative examples 1 to 5 Table 1 shows the ABS resins 1 to 4 and the talc powders a to c.
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.), 0.5 part of ethylenebisstearylamide as a lubricant (Nippon Yushi Co., Ltd.), polyethylene wax (Neo Wax ACL, Yasuhara Yushi Kogyo Co., Ltd.)
0.5 parts) and 1.0 part of calcium hydroxide (Super Microstar, manufactured by Maruo Calcium Co., Ltd.) as an alkali metal hydroxide, mixed with a Henschel mixer, and vented single screw extruder ( HV-40-28, manufactured by Tabata Machine Industry Co., Ltd.) at a set temperature of 270 ° C., pelletized, and ABS of Examples 1 to 6 and Comparative Examples 1 to 5.
A system resin was obtained.

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 was blow molded using a DA-50 blow molding machine manufactured by Placo Co., Ltd. to obtain a molded body. The molding conditions were as follows: a parison temperature of about 240 ° C., an injection speed (index) of 150, a screw rotation speed of 60 rpm, a blow pressure of 6 kg / cm ² G (air), a cooling time of 100 seconds, and a mold temperature of 60 ° C. there were. (1) Surface appearance (W) 60 mm × (L) 400 mm × (H) 30 mm, using a box-shaped blow molded body with an average thickness of 3.5 mm, draw a rectangle of 40 × 80 mm on the surface of the molded body, inside the rectangle (Size: 0.02 to 0.2 mm) were visually counted, and the average value of the number of dents at five rectangular points 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 one or more and less than three. X: The average number of dents is 3 or more. (2) Drawdown Property The parison was allowed to stand after being injected with a length of about 500 mm (weight of parison: 500 g), 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. (3) Drop weight strength A cylindrical blow molded article having an outer diameter of 70 mm, a length of 400 mm, and an average thickness of 3.2 mm was used, and the drop weight strength at −30 ° C .: weight of the weight × half of the breaking height (kg · m) ) 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) Heat deformation temperature: HDT The blow molded product obtained was cut out to produce a test piece, and the load was measured at 4.6 kg / cm ² load according to ASTM D-648. (D) Flexural strength and flexural modulus The blow-molded product thus obtained was cut out to produce a test piece, which was measured at 23 ° C. in accordance with ASTM D-790.

The results obtained are shown in Table 1 together with the formulation.

[0026]

[Table 1]

[0027]

As is clear from the results shown in Table 1, the ABS resin for blow molding of the present invention to which a predetermined amount of talc powder is added has excellent drawdown resistance during blow molding.
Blow molded product with uniform and excellent surface properties, flexural modulus 25
A blow-molded product having a drop weight strength of not less than 00 MPa and a strength of not less than 1.5 kgm can be obtained.

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Claims (3)

[Claims] 1. A talc based on 100 parts by weight of an ABS resin having a reduced viscosity of methyl ethyl ketone-soluble component of 0.3 to 1.5 dl / g (0.3% N, N-dimethylformamide solution at 30 ° C.). An ABS-based resin composition for blow molding, comprising 5 to 50 parts by weight of one or more selected from powder, mica, kaolin, and whisker. 2. The resin composition according to claim 1, wherein the talc powder has an average particle size of 5 μm or less. 3. A blow-molded article using the resin composition according to claim 1.