JPH09272785A - Abs resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ABS resin compsn. which is improved in both drawdown of parison and injection molding time, is excellent in high-cycle productivity, and can be blow molded. SOLUTION: This compsn. comprises 0.2-4wt.% acrylic resin having a reduced viscosity of 0.2 or higher but lower than 0.8, 0.2-6wt.% acrylic resin having a reduced viscosity of 0.8-5, and 99.6-90wt.% ABS resin of which the acetone sol. component has a reduced viscosity of 0.2-1.0.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ABS resin composition, and more particularly to an ABS resin composition suitable for blow molding. More specifically, automobile parts such as air spoilers, glove boxes, instrument panels, door rims, bumpers, computer and television housings, workstations, desk tops, office equipment such as drawers, office supplies, refrigerators and air conditioners. Household appliances such as device panels, cases such as cameras and tools,
The present invention relates to an ABS resin composition for blow molding suitable for housing-related products such as doors and wall panels, sports / leisure products such as snow boats and surfboards, and sundries such as mannequins and plows.

[0002]

2. Description of the Related Art In recent years, automobiles, office automation equipment, office equipment,
In the fields of home appliances, furniture, cases, housing-related products, sports / leisure products, miscellaneous goods, etc., large blow-molded products with a double-wall structure have been highlighted for the purpose of weight saving, resource saving, and cost reduction. Is taking a bath. In recent years, ABS resins have also been tried as a material for the large blow molded products (for example, JP-A-3-243646 and 3-263451).
No. 4-25431, No. 4-120157, etc.). Furthermore, AB with improved drawdown of parison during blow molding with acrylic resin
S resins have also been tried (eg plastics, 1
(November 1992, p. 97, etc.). However, although this technique improves the drawdown of the parison, there is a problem that the injection time of the parison is long and the productivity is poor.

[0003]

DISCLOSURE OF THE INVENTION The present invention is an AB having an improved blowdown property of a parison having improved drawdown and improved injection time of the parison.
It is an object to provide an S resin composition.

[0004]

Means for Solving the Problems The present inventors have completed the present invention as a result of repeated studies for solving the above problems. That is, in the present invention, a) the reduced viscosity is 0.2 to 0.
0.2-4 weight of acrylic resin (I) less than 8 and b) 0.2 of acrylic resin (II) with reduced viscosity of 0.8-5
~ 6 parts by weight and c) the acetone-soluble component has a reduced viscosity of 0.2
The ABS resin composition is characterized by comprising 99.2 to 90 parts by weight of ABS resin (III) of 1.0 to 1.0.

Hereinafter, the present invention will be described in detail. The acrylic resins (I) and (II) referred to in the present invention each include at least 5 vinyl monomers represented by the formula (1).
A resin containing 0% by weight or more and 50 parts by weight or more of a (co) polymerized (co) polymer.

[0006]

Embedded image (However, in the formula, R ₁ is H or CH ₃ , R ₂ is H,
It represents any one of an alkyl group, a substituted alkyl group, an aryl group, an aralkyl group and an alkaryl group. )

Specific examples thereof include PMMA resins and acrylic resins such as methyl methacrylate / alkyl acrylate copolymers. Preferred are methyl methacrylate / alkyl acrylate copolymers, and these can be used alone or in combination. Examples of the polymerization method of the acrylic resin include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, an emulsion-suspension polymerization method, and a bulk-suspension polymerization method. Regarding the polymerization method, an emulsion polymerization method is preferable from the viewpoint of polymerization stability.

In the ABS resin composition of the present invention, an acrylic resin (I) having a reduced viscosity of 0.2 to less than 0.8
One point of the invention is to use 0.2 to 4 parts by weight of acrylic resin (II) having a reduced viscosity of 0.8 to 1.5 in the range of 0.2 to 6 parts by weight. AB alone
It is not possible to improve the drawdown of the parison of the S resin composition and improve the injection time at the same time. That is, the acrylic resin (I) alone does not improve the drawdown of the parison of the ABS resin composition. On the other hand, the acrylic resin (II) alone does not improve the injection time of the parison of the ABS resin composition.

The reduced viscosity of the acrylic resin (I) in the present invention is in the range of 0.2 to less than 0.8, preferably 0.25 to 0.5. The reduced viscosity is 0.
When it is less than 2, the drawdown of the parison of the ABS resin composition is not improved, and when it is 0.8 or more, the effect of improving the injection time of the parison becomes small. Also, acrylic resin (I)
Is in the range of 0.2 to 4 parts by weight in the ABS resin composition of the present invention, preferably in the range of 0.5 to 3 parts by weight. If it is less than 0.2 parts by weight, the drawdown of the parison of the ABS resin composition cannot be improved, and if it exceeds 4 parts by weight, the injection time of the parison is not improved.

The reduced viscosity of the acrylic resin (II) in the present invention is in the range of 0.8 to 5, preferably 1
The range is from 3 to 3, more preferably from 1 to 2. If the reduced viscosity is less than 0.8, the drawdown of the parison of the ABS resin composition has a small improvement effect, and
If it exceeds, the ejection time of the parison will be remarkably long.
The acrylic resin (II) is in the range of 0.2 to 6 parts by weight in the ABS resin composition of the present invention, and preferably,
It is in the range of 1 to 5 parts by weight. A less than 0.2 parts by weight
The drawdown of the parison of the BS resin composition cannot be improved, and if it exceeds 6 parts by weight, the injection time of the parison becomes long.

The term "ABS resin" as used in the present invention means that an aromatic vinyl compound, a vinyl cyanide compound, and other copolymers can be copolymerized in the presence of a conjugated diene rubber having a rubber particle diameter of 0.05 to 2 μm. A graft copolymer obtained by polymerizing a vinyl compound, or a compound selected from the group consisting of the graft copolymer and the above-mentioned aromatic vinyl compound, vinyl cyanide compound and other copolymerizable vinyl compound. Mixture with a copolymer obtained by copolymerizing one or more compounds (hereinafter, the ABS resin defined above is referred to as resin A)
Is a resin containing 50% by weight or more.

The amount of the conjugated diene rubber in the resin A is preferably 5-40% by weight, more preferably 10-25.
The amount of the component which is graft-copolymerized with the rubber is preferably 10 to 150% by weight, more preferably 20 to 60% by weight, based on the amount of the rubber. The content of the resin A other than the graft copolymer is preferably 0 to 85% by weight,
More preferably 30 to 85% by weight, particularly preferably 50.
~ 80% by weight. The amount of vinyl cyanide compound in the components other than the conjugated diene rubber in Resin A is preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and the amount of aromatic vinyl compound is preferably 20-90
%, More preferably 30 to 80% by weight.

As the conjugated diene rubber, polybutadiene, styrene-butadiene copolymer, polyisoprene,
Examples thereof include acrylonitrile / butadiene copolymer. These are used alone or in combination, and polybutadiene is preferable. As the aromatic vinyl compound, styrene, α-methylstyrene, vinyltoluene,
Examples thereof include t-butyl styrene and chlorostyrene.
These are used alone or in combination, and styrene and α-methylstyrene are preferred. Examples of the vinyl cyanide compound include (meth) acrylonitrile. These are used alone or in combination.

Other copolymerizable vinyl compounds include:
N-phenylmaleimide, N-methylmaleimide, N-
N-phenyl substituted maleimides such as cyclohexylmaleimide, ester compounds such as methyl (meth) acrylate, organosilane compounds such as γ-methacryloxypropyltrimethoxysilane, maleic anhydride, copolymerizable carboxylic acids such as (meth) acrylic acid. Acid etc. are mentioned. These are used alone or in combination, and N-phenylmaleimide and γ-methacryloxypropyltrimethoxysilane are preferable.

Examples of the graft copolymer and the method for producing the copolymer include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, an emulsion-suspension polymerization method, and a bulk-suspension polymerization method. To be The emulsion polymerization method is preferred.

The reduced viscosity of the acetone-soluble component of the ABS resin used in the present invention needs to be in the range of 0.2 to 1.0, preferably 0.4 to 0.8. . When the reduced viscosity of the acetone-soluble component is less than 0.2, the drawdown of the parison of the ABS resin composition of the present invention is large,
If it exceeds 1.0, the load of the blow molding machine is too large to perform blow molding. Further, the ABS resin is the AB of the present invention.
It is in the range of 99.6 to 90 parts by weight, and preferably in the range of 98.5 to 93 parts by weight, in the S resin composition. 90
If it is less than 1 part by weight, the injection time of the parison of the ABS resin composition will not be improved, and if it exceeds 99.6 parts by weight, the drawdown of the parison of the ABS resin composition will not be improved.

The ABS resin used in the present invention includes:
A thermoplastic resin (B) other than the above-mentioned resin A, a (thermoplastic) elastomer (C), a compatibilizer (grafted special polymer) (D), an inorganic filler (E), etc., alone or in combination, 50 It can be included in the range of less than wt%.

As (B), a polycarbonate resin,
Examples thereof include polyolefin resins, polyphenylene ether resins, polyamide resins, polyester resins, (rubber-modified) styrene resins, AES resins, AAS resins, MBS resins and the like. Examples of (C) include styrene-based thermoplastic elastomers, acrylic-based elastomers, olefin-based (thermoplastic) elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and urethane-based thermoplastic elastomers.

As (D), ethylene / ethyl acrylate / maleic anhydride copolymer is added to acrylonitrile /
A compatibilizing agent such as a special polymer obtained by grafting a vinyl polymer onto a polyolefin such as a polymer obtained by grafting a styrene copolymer can be used. Examples of (E) include talc, calcium silicate, calcium carbonate, zinc oxide whiskers, and magnesium oxysulfate whiskers.

The ABS resin in the present invention requires 50% by weight or more of the resin A alone or in combination, preferably 70% by weight or more, more preferably 85% by weight or more. ), (D) and (E) alone or in combination with each other, can be kneaded and prepared by a known method such as an extruder, roll, Banbury mixer, kneader or the like.
When kneading, phenol-based, phosphorus-based,
Known antioxidants such as sulfur-based antioxidants, benzotriazole-based ultraviolet absorbers, light stabilizers, heavy metal deactivators, flame retardants, coloring agents such as pigments, lubricants, plasticizers, glass fibers, carbon fibers, etc. Additives can be added. The additives may be added in a step other than the kneading step, for example, a polymerization step.

The ABS resin composition of the present invention can be produced by a known method such as an extruder, roll, Banbury mixer or kneader. More specifically, it is preferable that the resin is produced by an extruder at a resin temperature in the range of 250 to 300 ° C.

Melt flow rate of the ABS resin composition of the present invention (according to JIS K-7210, 220 ° C., 10
Kg load) needs to be in the range of 0.5 to 3.5 g / 10 minutes. It is preferably 0.7 to 3.0 g / 10 minutes. If it is less than 0.5 g / 10 minutes, the load on the blow molding machine will be impaired, and if it exceeds 3.5 g / 10 minutes, the drawdown of the parison will be severe.

Blow molding is carried out by a known extrusion blow molding machine and molding conditions (for example, Plastic Age, September 1994, p. 125). However,
Due to the impact strength of the molded product, the resin temperature of the parison is 200-2.
It is preferable to control the temperature at 40 ° C. and the mold temperature in the range of 10 to 120 ° C. for molding. The ABS resin composition of the present invention is suitably used not only for blow molding but also for thermoforming such as sheet molding, calender molding, pressure molding and vacuum molding.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the present invention will be described in more detail with reference to examples. First, the following materials were used as the acrylic resin and the ABS resin. <Acrylic resin (I-1)> Methyl methacrylate 8
An acrylic resin having 0% by weight and 20% by weight of butyl acrylate, and a reduced viscosity of 0.38.

<Acrylic resin (II-1)> An acrylic resin comprising 80% by weight of methyl methacrylate and 20% by weight of butyl acrylate and having a reduced viscosity of 1.38. <Acrylic resin (II-2)> 80% by weight of methyl methacrylate and 20% by weight of butyl acrylate,
An acrylic resin with a reduced viscosity of 0.89.

<ABS resin (III-1)> Styrene content 47% by weight, acrylonitrile content 18% by weight, N-phenylmaleimide content 15% by weight, polybutadiene rubber content 20% by weight, and acetone soluble ABS resin with a reduced viscosity of 0.46 minutes. <ABS-based resin (III-2)> A styrene content of 47% by weight, an acrylonitrile content of 18% by weight, an N-phenylmaleimide content of 15% by weight, and a polybutadiene rubber content of 20% by weight. ABS resin with a viscosity of 0.13.

The methods for measuring the viscosity and melt flow rate, the method for granulating ABS resin, the method for measuring resin temperature, and the method for evaluating blow moldability were carried out by the following methods. <Method of measuring viscosity of acrylic resin (I) (II)> JI
According to S Z8803, a solution of 0.1 g of acrylic resin (exact balance) dissolved in 100 cc of chloroform was subjected to reduced viscosity (η at 25 ° C. using an Ostwald viscometer.
_SP / C) was measured.

<Method for measuring viscosity of acetone-soluble component of ABS resin> A solution of about 1 g of ABS resin dissolved in about 20 cc of acetone is centrifuged (rotation speed: 20000 rpm).
After decanting, the supernatant solution is decanted. The solution obtained by decantation was used as an explosion-proof dryer (130
(° C) to obtain an acetone-soluble matter. JIS Z8
According to 803, 0.25 g of the acetone-soluble matter (exact balance)
Was dissolved in 50 cc of methyl ethyl ketone, and the reduced viscosity (η _SP / C) at 30 ° C. was measured using a Canon Fenske viscometer.

<Method for measuring melt flow rate of ABS resin composition> According to JIS K-7210, predrying (about 90 ° C., 3 hours) was performed, and then the measurement was performed under the following conditions. Measuring instrument: Melt Indexer (Toyo Seiki Seisakusho Co., Ltd.) Type C501DI Temperature: 220 ° C, load: 10 kg

<Production Method of ABS Resin Composition> An acrylic resin and an ABS resin were pre-blended with a tumbler, and then an ABS resin composition of each sample was produced under the following extruder and extrusion conditions. Extruder: TEN5040, screw design diameter 50 mm, L / D 40 screw rotation speed 180 rpm, manufactured by Tabata Machine Industry Co., Ltd. Set temperature (cylinder to die): 250 to 270 ° C Vacuum vent: Approximately 600 mmHg suction

<Blow moldability> AB obtained by the above production
Pre-dry the S resin composition (about 90 ° C., 3 hours), and use a blow molding machine with an accumulator for 2.0 k
A parison with a length of 650 mm was injected. The force to eject the parison is constant, and the die gap has a parison length of 6
It was adjusted to be 50 ± 10 mm. At this time, the time required for injection was measured and used as the injection time. The time required for the initially ejected parison (about 650 mm) to extend 100 mm by free fall was taken as the drawdown time.

Molding machine: manufactured by Placo Co., Ltd. DA65 (screw diameter 65 mm) (screw design: full flight) Accumulator capacity 3.0 L Die: diverge type (diameter 210 mm) Molding temperature: cylinder, accumulator, die set temperature 220 to 230 ° C. (resin temperature of about 225 ° C.) Drawdown: A range of about 5 to 30 seconds is preferable for molding. Injection time: The higher the cycle time, the better the high cycle property, but considering the measuring time, it is preferably about 20 seconds or less.

[0033]

【Example】

Example 1 1 part by weight of the acrylic resin (I-1), 5 parts by weight of the acrylic resin (II-1) and the ABS resin (III-
1)) 94 parts by weight were pre-blended with a tumbler and granulated with the above-mentioned extruder to obtain an ABS resin composition. The ABS
The blow molding property of the resin composition was evaluated by the blow molding machine described above. Table 1 shows the results. Clearly, the drawdown of the parison is excellent, and the injection time is fast and the high cycle property is excellent.

Example 2 3 parts by weight of the acrylic resin (I-1), 3 parts by weight of the acrylic resin (II-1) and the ABS resin (III-
1) The procedure of Example 1 was repeated except that the amount was 94 parts by weight. The blow moldability of the ABS resin composition was evaluated by the blow molding machine described above. Table 1 shows the results. clearly,
Excellent drawdown of parison, quick injection time and high cycle performance.

Comparative Example 1 5 parts by weight of the acrylic resin (I-1), 1 part by weight of the acrylic resin (II-1) and the ABS resin (III-
1) The procedure of Example 1 was repeated except that the amount was 94 parts by weight. Table 1 shows the results. Obviously, it's inferior to the parison drawdown. Comparative Example 2 6 parts by weight of the above acrylic resin (II-1) and ABS
The same procedure as in Example 1 was performed except that 94 parts by weight of the resin (III-1) was used. Table 1 shows the results. Obviously, the parison has a long firing time.

Comparative Example 3 6 parts by weight of the above acrylic resin (II-2) and ABS
The same procedure as in Example 1 was performed except that 94 parts by weight of the resin (III-1) was used. Table 1 shows the results. Obviously, the injection time is long. Comparative Example 4 6 parts by weight of the above acrylic resin (II-1) and ABS
Example 1 was carried out in the same manner as in Example 1 except that 94 parts by weight of the system resin (III-2) was used. Table 1 shows the results. Obviously, it's inferior to the parison drawdown.

[0037]

[Table 1]

[0038]

INDUSTRIAL APPLICABILITY The ABS resin composition of the present invention is extremely useful industrially because it can satisfy the drawdown of the parison and the improvement of the injection time at the same time in blow molding and the productivity is improved. .

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Claims (4)

[Claims] 1. A) 0.2 to 4 parts by weight of an acrylic resin (I) having a reduced viscosity of 0.2 to less than 0.8 and b) an acrylic resin (II) 0 having a reduced viscosity of 0.8 to 5. 2 to 6 parts by weight and the reduced viscosity of the c) acetone-soluble component are 0.2 to 1.0.
ABS resin composition (III) of 99.6 to 90 parts by weight. 2. A melt flow rate of 0.5 to 3.5 g /
AB according to claim 1, characterized in that it is in the range of 10 minutes.
S resin composition. 3. The ABS resin composition according to claim 1, which is for blow molding. 4. The ABS resin composition according to claim 1, which is for an air spoiler for automobiles.