JPH09316263A - Thermoplastic resin composition excellent in blow moldability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in blow moldability, by adding a vinyl cyanide-based copolymer having a specific viscosity to two kinds of graft copolymers. SOLUTION: This composition comprises (A) 1-50wt.% of a diene-based rubber-containing graft copolymer having 10-100% graft ratio, (B) 10-60 pts.wt. of a (meth)acrylic acid alkyl ester-based rubber-containing graft copolymer, (C) 10-90 pts.wt. of a vinyl cyanide-based copolymer having 0.5-1.5dL/g reduced viscosity ηsp /c and (D) 0-50 pts.wt. of a vinyl-based copolymer mixture in 100 pts.wt. of the total amount of the component A to the component D. The weight- average particle diameter of the diene-based rubber-like polymer as the component A is 0.05-0.5μm and its ratio is 10-80wt.%. The component C is a polymer obtained by copolymerizing a mixture of 10-50wt.% of a vinyl cyanide-based monomer and 90-50wt.% of an aromatic vinyl-based monomer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition which has excellent blow moldability and is well balanced in weather resistance, impact resistance and thermal stability, and
The present invention relates to a blow-molded product which has an excellent balance of weather resistance and mechanical properties and has excellent productivity.

[0002]

2. Description of the Related Art Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile and aromatic vinyl monomers such as styrene and α-methylstyrene are graft-copolymerized on a rubber-like polymer represented by a diene rubber. Polymerized rubber-containing graft copolymer or so-called A prepared by blending this rubber-containing graft copolymer with a rigid vinyl copolymer such as styrene / acrylonitrile copolymer.
Since BS resin is excellent in impact resistance, mechanical strength, and moldability, it is a semi-engineering plastic that has intermediate properties between general-purpose resins and engineering plastics, and is used for automobiles, motorcycles, OA equipment,
Widely used in home appliances and household products.

In recent years, the blow molding method, which has attracted attention for molding hollow products, has been developed mainly for polyolefin resins, but it is possible to obtain a large molded product by using a relatively simple device. is there. For this reason, it has attracted attention as a technology for molding structural parts and large parts using engineering plastics other than polyolefin resin.
Regarding the S resin, a blow molding resin composition having improved coating resistance (JP-A-3-243646) and a blow molding resin composition having improved heat resistance (JP-A-4-254)
No. 31) is proposed.

However, the above-mentioned Japanese Patent Application Laid-Open No. 3-24364.
No. 6, JP-A-4-25431 and other known ABS resin compositions for blow molding have coating resistance,
Although it is excellent in terms of heat resistance, it has a problem of poor weather resistance because it uses a diene rubber polymer having a double bond that is easily decomposed by sunlight.
As means for improving such problems, plating and coating on the surface of the resin molded product, or a method of attaching a film or the like to prevent contact with direct sunlight, a method of adding a weathering agent to the resin composition, etc. are generally used. Target. The present situation is that plating, painting, and film sticking are not advantageous at all in terms of complicated process steps, cost increase, and deterioration over time. Cases where not only sufficient weather resistance is not shown simply by adding weather resistance with an additive, but also when a large parison is formed by melting with a blow molding machine, a large amount of gas caused by the additive causes a problem during production. There are many. As a method of solving these, by using AAS resin in combination with ABS resin,
Thermoplastic resin composition with improved weather resistance
0-118733) has been proposed. Here, a resin composition having excellent weather resistance is proposed by blending a copolymer obtained by graft-polymerizing a large particle diameter rubber having a weight average particle diameter of 0.5 to 5 μm and a copolymer obtained by graft-polymerizing an acrylic ester rubber. are doing. However, the weight average particle size is 0.5
When a rubber having a diameter of more than μm is used, mechanical properties are deteriorated and appearance is often deteriorated. Further, the composition not only has insufficient blow moldability, but also has a problem that the color tone of the molded product deteriorates because it is held at a high temperature for melting for a long time during parison formation.

[0005]

SUMMARY OF THE INVENTION The present invention has been achieved as a result of studying to solve the problems in the prior art described above. Therefore, the object of the present invention is to
A rubber-reinforced styrene thermoplastic resin composition represented by an ABS resin having excellent color stability, weather resistance and blow moldability, and a blow molded product having excellent weather resistance, mechanical properties, molding processability, etc. To provide.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that the diene rubber-containing graft copolymer (I) and the (meth) acrylic acid alkyl ester rubber-containing graft. By adding the vinyl cyanide-based copolymer (III) having a specific viscosity to the copolymer (II), a styrene-based thermoplastic resin composition excellent in color tone stability, weather resistance and blow molding can be obtained. It was also found that the blow-molded product obtained by blow-molding the styrene-based thermoplastic resin composition exhibits excellent color stability, weather resistance, mechanical properties and productivity, Reached

That is, the weight average particle diameter is 0.05 to
Diene rubbery polymer (a) 10-8 having a thickness of 0.5 μm
Vinyl cyanide-based monomer (b) in the presence of 0% by weight,
Graft ratio obtained by graft-polymerizing a monomer mixture comprising an aromatic vinyl-based monomer (c) and, if necessary, other vinyl-based monomer (d) copolymerizable therewith In the presence of 1 to 50 parts by weight of a diene rubber-containing graft copolymer (I) whose content is 10 to 100% and a (meth) acrylic acid alkyl ester rubber polymer (e). By graft-polymerizing a monomer mixture comprising the polymer (b), the aromatic vinyl-based monomer (c), and optionally other vinyl-based monomer (d) copolymerizable therewith. The resulting (meth) acrylic acid alkyl ester rubber-containing graft copolymer (I
I) 10 to 60 parts by weight, vinyl cyanide-based monomer (b)
10 to 50% by weight and aromatic vinyl monomer (c) 90 to
Vinyl cyanide-based copolymers (III) 10 to 90 which are copolymers of 50% by weight of a monomer mixture and have a reduced viscosity ηsp / c of 0.5 to 1.5 dl / g.
A monomer composed of 1 part or more of a monomer selected from parts by weight, vinyl cyanide monomer (b), aromatic vinyl monomer (c), and other copolymerizable vinyl-based monomer (d). A vinyl-based copolymer mixture (I obtained by polymerizing a monomer mixture)
V) 0 to 50 parts by weight, (I) + (II) + (I
The present invention provides a thermoplastic resin composition having a total amount of II) + (IV) of 100 parts by weight and excellent in blow moldability.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The diene rubber-like polymer (a) constituting the diene rubber-containing graft copolymer (I) used in the present invention means polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, butyl acrylate-
Examples thereof include a butadiene copolymer, a methyl methacrylate-butadiene copolymer, and an ethylene-propylene-diene rubber. These diene rubbery polymers are used alone or in a mixture of two or more. Among these rubber-like polymers, polybutadiene, styrene-butadiene copolymer and acrylonitrile-butadiene copolymer are particularly preferably used.

Further, the weight average particle diameter of the diene rubbery polymer (a) needs to be 0.05 to 0.5 μm. In particular, the range of 0.1 to 0.45 μm is preferable. If the weight average particle diameter is out of the range of 0.05 to 0.5 μm, a blow molded product having a good appearance cannot be obtained, and mechanical properties are not expressed, which is not preferable. The average particle size of the rubber-like polymer here is a value measured by the sodium alginate method.

The diene-based rubber-containing graft copolymer (I), the (meth) acrylic acid alkyl ester-based rubber-containing graft copolymer (II), the vinyl cyanide-based copolymer (III), and the vinyl-based copolymer used in the present invention. The vinyl cyanide-based monomer (b) constituting the copolymer (IV) is a compound having a polymerizable double bond and a cyano group, and specific examples thereof include acrylonitrile and methacrylonitrile. , Of these vinyl cyanide-based monomers,
Acrylonitrile is particularly preferably used.

The diene rubber-containing graft copolymer (I), the (meth) acrylic acid alkyl ester rubber-containing graft copolymer (II), the vinyl cyanide-based copolymer (III), and the vinyl-based copolymer used in the present invention. The aromatic vinyl monomer (c) constituting the copolymer (IV) is an aromatic compound having a polymerizable double bond, and specific examples thereof include styrene, α-methylstyrene and p-methyl. Examples thereof include styrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene and o, p-dichlorostyrene. Of these aromatic vinyl monomers, styrene and α-methylstyrene are Particularly preferably used. Moreover, these can use 1 type (s) or 2 or more types.

The diene rubber-containing graft copolymer (I), the (meth) acrylic acid alkyl ester rubber-containing graft copolymer (II), the vinyl cyanide copolymer (III), and the vinyl copolymer. Other copolymerizable vinyl-based monomers (d) used in (IV) include methyl methacrylate, ethyl methacrylate, and n-methacrylic acid.
-Propyl, n-butyl methacrylate, methacrylic acid t
Unsaturated carboxylic acid alkyl esters such as -butyl, n-hexyl methacrylate, cyclohexyl methacrylate, chloromethyl methacrylate and 2-chloroethyl methacrylate, maleimide compounds such as N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide , Maleic anhydride, acrylic acid, unsaturated carboxylic acids such as methacrylic acid, unsaturated dicarboxylic acids such as maleic acid, unsaturated dicarboxylic acid anhydrides such as maleic anhydride, and unsaturated amide compounds such as acrylamide, Especially methacrylic acid, methyl methacrylate,
N-phenylmaleimide is particularly preferably used. When used, these monomers may be used alone or in combination of two or more.

Regarding the composition ratio of each component in the diene rubber-containing graft copolymer (I) used in the present invention, the diene rubber-like polymer (a) is 10 to 80% by weight.
And preferably 20 to 70% by weight. 10
If it is less than wt%, the impact resistance of the obtained thermoplastic resin composition for blow molding will be insufficient, and if it exceeds 80 wt%, the blow molding property obtained will be unsatisfactory. The vinyl cyanide-based monomer (b) is preferably 1 to 50% by weight, more preferably 5 to 40% by weight. If it is less than 1% by weight, the blow molding thermoplastic resin composition obtained has insufficient blow moldability, and if it exceeds 50% by weight, the blow molding thermoplastic resin composition obtained has insufficient impact resistance. Not preferable. The aromatic vinyl-based monomer (c) is preferably 5 to 70% by weight, more preferably 10 to 50% by weight. 5
If it is less than 10% by weight, the blow molding thermoplastic resin composition obtained has insufficient blow moldability, and if it exceeds 70% by weight, the blow molding thermoplastic resin composition obtained has insufficient impact resistance, which is preferable. Absent. , Other vinyl monomers (d)
Is preferably 0 to 50% by weight, more preferably 0 to 40% by weight. If it exceeds 50% by weight, impact resistance and blow moldability of the obtained blown thermoplastic resin composition are not preferable.

The graft ratio in the graft copolymer (I) must be 10 to 100%, and particularly 20 to 70.
% Is preferred. When the graft ratio is out of the range of 10 to 100%, the mechanical properties are significantly deteriorated. The graft ratio as used in the present invention is that acetone is added to a predetermined amount (m) of the graft copolymer and refluxed for 3 hours, this solution is centrifuged for 40 minutes, insoluble matter is filtered off, and this is kept at 60 ° C. for 5 hours. Dried under reduced pressure,
Measure the weight (n). The graft ratio was calculated by the following equation. Here, L is the rubber content of the graft copolymer. Graft ratio (%) = [(n−m × L) / (m × L)]

Regarding the composition ratio of each component in the vinyl cyanide-based copolymer (III) used in the present invention,
The vinyl cyanide-based monomer (b) must be 10 to 50% by weight, preferably 20 to 40% by weight. If it is less than 10% by weight, the blow molding thermoplastic resin composition obtained has insufficient blow moldability, and if it exceeds 50% by weight, the blow molding thermoplastic resin composition obtained has insufficient impact resistance. Not preferable. Aromatic vinyl monomer (c) must be 90 to 50% by weight, 80 to 60% by weight
Is preferred. When it is less than 50% by weight, the blow molding thermoplastic resin composition obtained has insufficient blow moldability, and when it exceeds 90% by weight, the blow molding resin composition obtained has insufficient impact resistance, which is not preferable. .

The triple sequence of the vinyl cyanide-based monomer in the vinyl cyanide-based copolymer (III) in the present invention means the segment in the copolymer represented by the formula (1). It is presumed that, when the copolymer having such a segment is exposed to a high temperature, the intramolecular cyclization reaction represented by (Formula 2) proceeds, resulting in coloration.

[0017]

Embedded image

Embedded image The proportion of the triple sequence of the vinyl cyanide monomer (d) contained in the vinyl cyanide copolymer (III) in the present invention is preferably 10% by weight or less. 10% by weight
If it exceeds, the stability of the color tone of the blow molding thermoplastic resin composition at the time of melting is deteriorated, which is not preferable. It is preferably less than 8% by weight from the viewpoint of stability of color tone when melted. The vinyl cyanide-based copolymer (III) in which the ratio of such triple sequences of the vinyl cyanide-based monomer is controlled to 10% by weight or less is a vinyl cyanide-based monomer in the residual monomer. It can be produced by controlling the ratio of components and carrying out polymerization.

Further, a vinyl cyanide-based copolymer (II
I) has a specific viscosity, that is, reduced viscosity ηsp
/ C is 0.5 to 1.5 dl / g, especially 0.7 to 1.2 d
It is an important requirement that the range is 1 / g, and if the reduced viscosity ηsp / c is less than 0.5 dl / g, it becomes difficult to obtain a good drawdown property during blow molding, and
When it exceeds 1.5 dl / g, the blow molding processability is deteriorated, which is not preferable.

The reduced viscosity ηsp / c as used in the present invention is a value calculated by the following formula after dissolving 0.2 g of a polymer in 50 ml of methyl ethyl ketone and measuring the flowing time at 30 ° C. using a viscous tube. Is. Reduced viscosity ηsp / c = [(t1 / t0) -1] / c where, t1: downflow time in the sample solution (seconds) t0: downflow time of the blank solution (seconds) c: resin concentration of the measurement sample (G / 100 ml) Reduced viscosity η of the above vinyl cyanide copolymer (III)
The method of adjusting sp / c to 0.5 to 1.5 dl / g within the range of adjustment is not particularly limited, but examples thereof include a method of adding a polymerization initiator and a chain transfer agent, and a method of adjusting the addition amount. To be

(Meth) Acrylic acid alkyl ester type rubber-containing graft copolymer (II) used in (meth)
The acrylic acid alkyl ester rubber-like polymer (e) is, for example, a straight chain or branched chain such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. A polymer obtained by copolymerizing an alkyl acrylate having an alkyl group having 1 to 20 carbon atoms, a methacrylic acid alkyl ester, or the like, or a copolymer obtained by copolymerizing two or more of these, further necessary A copolymer with another monomer copolymerizable according to, for example, α-olefins such as ethylene and propylene, aromatic vinyl, vinyl cyanide, methacrylic acid ester, methacrylic acid, acrylic acid, butadiene, etc. Can be mentioned. The (meth) acrylic acid alkyl ester-based rubbery polymer (e) is crosslinked by copolymerization with a non-crosslinked rubber or a crosslinking agent having a plurality of ethylenic double bonds in the molecule, or both. Any of the above multi-layered rubbers can be used.

The proportion of each component in the (meth) acrylic acid alkyl ester-based rubber-containing graft copolymer (II) is 10 to 80% by weight for the (meth) acrylic acid alkyl ester-based rubbery polymer (e). Preferably 20 to 7
0% by weight is more preferred. If it is less than 10% by weight, the impact resistance of the obtained blow molding thermoplastic resin composition is insufficient, and if it exceeds 80% by weight, the impact resistance of the blow molding thermoplastic resin composition obtained is insufficient. Is not preferable. The vinyl cyanide compound (b) is preferably 1 to 50% by weight, more preferably 5 to 40% by weight. If it is less than 1% by weight, the blow molding thermoplastic resin composition obtained has insufficient blow moldability, and if it exceeds 50% by weight, the blow molding thermoplastic resin composition obtained has insufficient impact resistance, which is not preferable. . The aromatic vinyl compound (c) is preferably 5 to 70% by weight, more preferably 10 to 60% by weight. If it is less than 5% by weight, the blow molding thermoplastic resin composition obtained has insufficient blow moldability, and if it exceeds 70% by weight, the blow molding thermoplastic resin composition obtained has insufficient impact resistance. Is not preferable. Further, the other copolymerizable vinyl monomer (d) is preferably 0 to 50% by weight, more preferably 0 to 40% by weight. If it exceeds 50% by weight, the impact resistance and blow moldability of the blow molding thermoplastic resin composition obtained are not preferable.

Rubber-containing graft copolymer (I) and vinyl cyanide copolymer (III) used in the present invention
Can be produced by a known polymerization method such as emulsion polymerization, suspension polymerization, bulk polymerization and solution polymerization, and the polymerization method itself is not limited.

The method for polymerizing the vinyl cyanide-based copolymer (III) in the present invention is to add an aromatic vinyl-based monomer during the polymerization as appropriate to the vinyl-cyanide-based monomer in the residual monomer. Aqueous suspension polymerization is preferred from the viewpoints of controlling the content, reducing oligomers, and inhibiting coloring stability during melting by auxiliary materials such as emulsifiers and solvents.

Examples of the suspension stabilizer used in the above polymerization include inorganic suspension stabilizers such as clay, barium sulfate and magnesium hydroxide, polyvinyl alcohol, carboxymethyl cellulose, polyacrylamide, methyl methacrylate / acrylamide copolymer and the like. And the like. Among them, the organic suspension stabilizer is preferable, and among them, the organic suspension stabilizer is preferable from the viewpoint of thermal coloring stability at the time of melting, and a methyl methacrylate / acrylamide copolymer is more preferable.

The total amount of water used as a dispersion medium for 100 parts by weight of the total amount of monomers used in the above-mentioned polymerization is such that good dispersibility of the monomers in water is maintained and a large amount of vinyl cyanide monomer is dissolved in water. From the viewpoint of preventing migration, it is preferably selected from the range of 80 to 350 parts by weight, more preferably 100 to 200 parts by weight.

Examples of the polymerization initiator used in the above polymerization include azonitriles such as 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (2,4,4-trimethylvaleronitrile). Compound and t-butylperoxide, t-butylperoxyneodecanate, t-butylperoxyneosexanoate, t-
Examples thereof include organic peroxides such as butyl peroxypivalate, and these can be used alone or in combination of two or more. Among them, azonitrile compounds are particularly preferable in that the polymerization rate can be easily controlled.

Examples of the chain transfer agent used here include alkyl mercaptans such as n-octyl mercaptan, t-dodecyl mercaptan and n-dodecyl mercaptan. These chain transfer agents can 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.

In order to obtain the vinyl cyanide-based copolymer (III) in the present invention, the polymerization system from the start to the end of the polymerization is controlled in order to control the ratio of the triple sequence of the vinyl cyanide monomer. The content of the vinyl cyanide-based monomer component in the residual monomer is 95% by weight or less, more preferably 80% by weight or less.
It is preferable to control the content of the vinyl cyanide-based monomer to 70% by weight or more and 95% by weight or less in the residual monomer from the start of the polymerization to the time when the polymerization rate of 10% has elapsed, by controlling the content to be not more than 70% by weight. The ratio of the vinyl cyanide-based monomer in the residual monomer is determined by the amount of the polymerization initiator, the addition of the polymerization inhibitor, the removal of the vinyl cyanide-based monomer from the polymerization system by stripping or the vinyl cyanide-based monomer. It can be controlled by appropriately combining it with the timing of addition of the monomer other than the monomer into the polymerization system during the polymerization and the adjustment of the addition amount.

The method for producing the (meth) acrylic acid alkyl ester-based rubber-containing graft copolymer (II) includes known emulsion polymerization, suspension polymerization, bulk polymerization, emulsion suspension polymerization, bulk suspension polymerization, etc. Can be used,
There is no particular limitation. A method of polymerizing by emulsion polymerization or bulk polymerization is preferably used.

Diene rubber-containing graft copolymer (I), (meth) acrylic acid alkyl ester rubber-containing graft copolymer (II), vinyl cyanide copolymer (III), vinyl copolymer ( The compounding ratio of (IV) is (I) / (II) / (III) / (IV) 1-50 parts by weight / 10-60 parts by weight / 10-90 parts by weight / 0-50
It is necessary to add 10 parts by weight, and the total amount of these is 10
It should be 0 parts by weight. When the amount of the diene rubber-containing graft copolymer (I) is less than 1 part by weight, the impact resistance is lowered, and when it exceeds 60 parts by weight, the impact resistance is remarkably lowered, which is not preferable. Further, a (meth) acrylic acid alkyl ester-based rubber-containing graft copolymer (I
When the amount of I) is less than 10 parts by weight, weather resistance is not exhibited, while 6
If the amount exceeds 0 parts by weight, the rigidity, impact resistance and fluidity are deteriorated, and further delamination occurs, which is not preferable. Here, the addition amount of the diene rubber-containing graft copolymer (I) and the (meth) acrylic acid alkyl ester rubber-containing graft copolymer (II) is the same as that of the diene rubber-like polymer (a) and (meth). The content of the alkyl acrylate rubber polymer (e) in the thermoplastic resin composition is 50.
It is important not to exceed the weight percent, and
It is important that the content of the diene rubbery polymer (a) does not exceed the content of the (meth) acrylic acid alkyl ester rubbery polymer (e). If the rubber content of both exceeds 50% by weight, impact strength and fluidity are significantly deteriorated, which is not preferable. Further, when the content of the diene rubbery polymer (a) exceeds the content of the (meth) acrylic acid alkyl ester rubbery polymer (e), the physical properties after the weathering test are significantly deteriorated, which is not preferable.

The vinyl cyanide-based copolymer (III) is 1
If it is less than 0 parts by weight, sufficient drawdown cannot be obtained.
If it exceeds the weight part, the uneven thickness is deteriorated, which is not preferable. When the vinyl copolymer (IV) exceeds 50 parts by weight, sufficient impact resistance cannot be obtained, which is not preferable.

Further, as the light resistance stabilizer used in the thermoplastic resin composition of the present invention, 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- (3-t-
Butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole,
Benzotriazo such as 2- (3,5-di-t-amyl-2-hydroxyphenyl) -5-benzotriazol
It is possible to use a hindered amine-based ultraviolet absorber such as a ru-based ultraviolet absorber or bis (2,2,6,6, -tetramethyl-4-piperidinyl) sebacate.

The thermoplastic resin composition of the present invention contains
Polyvinyl chloride, polyolefins such as polyethylene and polypropylene, polyamides such as nylon 6 and nylon 66, polyethylene terephthalate, polybutylene terephthalate, polyesters such as polycyclohexane dimethyl terephthalate, polycarbonates and various elastomers, etc. within a range that does not impair the original purpose. By blending another thermoplastic resin, the performance as a molding resin can be improved.

Further, if necessary, a reinforcing agent or a filler such as glass fiber, metal fiber, metal flake, carbon fiber,
2,6-di-butyl-4-methylphenol, 4,4 '
-Phenolic antioxidants such as butylidene-bis (3-methyl-6-t-butylphenol), tris (mixed, mono and dinonylphenyl) phosphites,
Phosphite type antioxidants such as diphenyl isodecyl phosphite, sulfur type antioxidants such as dilauryl thiodipropineate and dimyristyl thiodipropineate diasterial thiodipropineate, hydroxylalkylamines, sulfonic acid By appropriately mixing an antistatic agent such as a salt, a lubricant such as ethylenebisstearylamide, a metal soap, etc., more desirable physical properties and characteristics can be adjusted.

The method for producing the thermoplastic resin composition of the present invention is not particularly limited, and examples thereof include a rubber-containing graft copolymer (I), a (meth) acrylic acid alkyl ester-based rubber-containing graft copolymer (II), A Banbury mixer, a roll, and a single-screw or multi-screw extruder are used to obtain a mixture of a vinyl cyanide-based copolymer (III) and a vinyl-based copolymer (IV) or a mixture of the mixture and other additives. It is possible to employ a method of melt kneading using

The thus-obtained thermoplastic resin composition of the present invention has excellent balance in color tone stability, blow moldability and weather resistance, and therefore is mainly blow molded by blow molding, especially large blow molded products. However, a known method can be applied as the blow molding method without limitation.

The blow-molded product thus obtained has excellent productivity represented by mechanical properties such as weather resistance and impact resistance, and blow moldability.
It is useful as a large molded product that can be used outdoors without painting, such as for wheels, electric equipment, office automation equipment, and household products.

[0038]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples described below, Izod impact strength and weather resistance were measured according to the following test methods by molding a test piece from the obtained thermoplastic resin composition by injection molding.

Izod impact strength: ASTM D256
(23 ° C with 12.7mm notch)

Yellowing Degree (YI Value): JIS K710
Injection molded square plate (120 x 100 x 3m)
m) is a colorimetric color difference meter (ND-10 manufactured by Nippon Denshoku Industries Co., Ltd.)
Type 0) tristimulus values X, Y,
Z is measured, and Y. I. Values were calculated. Y. I. = 100 * (1.28X-1.06Z) * Y

Weather resistance: Injection molded 3.
A 2 mm notched Izod impact strength test piece was irradiated with WEATHER-OMETER manufactured by Suga Test Instruments Co., Ltd. under the following conditions, and the retention rate of the impact strength before and after irradiation was calculated according to the following formula. Temperature condition: 63 ± 2 ° C. Irradiation time: 300 hours Retention rate (%) = Impact strength after irradiation / Impact strength before irradiation ×
100

The ratio of the triple sequence of the vinyl cyanide-based monomer in the vinyl cyanide-based copolymer (III) is ¹³
Utilizing the fact that the α-carbon signal shift of the vinyl cyanide-based monomer appearing in C-NMR slightly differs depending on the difference of the adjacent monomer species, the ratio of the triple sequence was quantified from the signal integral value. The measurement conditions are as follows. Apparatus: JEOL JNM-GSX400 Model observation frequency: 100.5 MHz solvent: DMSO-d ₆ Concentration: 445 mg / 2.5 mL chemical shift reference: Me ₄ Si Temperature: 110 ° C. Observation width: 20000 Hz Data point: 32K flip angle: 90 ° (21μs) pulsedelaytime: 5.0s Accumulation number: 7400 or 8400 Decoupling: gated decoupling (without NOE)

The blow moldability and uneven thickness were evaluated by the following methods. Blow moldability: Judgment was made according to the following criteria from the parison length when a 30 cm parison was held for 30 seconds at a molding temperature of 240 ° C. ⊚: No drawdown ○: 5 cm or less drawdown Δ: 5 to 10 cm drawdown x: 10 cm or more drawdown

Unevenness: A 1,000 ml square bottle was blow-molded, and the wall thickness distribution was visually observed and judged according to the following criteria. ○: Less uneven thickness ×: Greater uneven thickness

[Reference Example 1] (Production of rubber-containing graft copolymer (I-1)) In a reactor purged with nitrogen, 120 parts by weight of pure water, 0.5 part by weight of glucose, and 0.5 part by weight of sodium pyrophosphate. Parts, 0.005 parts by weight of ferrous sulfate and 50 parts by weight of polybutadiene latex (rubber particle size 0.4 μm) (solid content conversion)
Was charged, and the time when the temperature in the reactor reached 65 ° C. with stirring as a polymerization initiation time, a mixture of 35 parts by weight of styrene, 15 parts by weight of acrylonitrile and 0.3 part by weight of t-dodecyl mercaptan was used for 5 hours. Was continuously dropped. At the same time, an aqueous solution containing 0.25 parts by weight of cumene hydroperoxide, 2.5 parts by weight of potassium oleate and 25 parts by weight of pure water was continuously added dropwise over 7 hours to complete the reaction.

The obtained rubber-containing graft copolymer latex was coagulated with sulfuric acid, neutralized with caustic soda, and then washed,
By filtering and drying, shown in Table 1 in powder form,
A rubber-containing graft copolymer (I) was obtained.

Reference Example 2 (Production of Rubber-Containing Graft Copolymer (I-2)) In the conditions of Reference Example 1, 45 parts by weight of polybutadiene latex (rubber particle diameter 0.25 μm) (solid content conversion), The procedure was changed to 8 parts by weight of acrylonitrile, 28 parts by weight of styrene, and 19 parts by weight of methyl methacrylate to obtain a rubber-containing graft copolymer (I-2) shown in Table 1.

Reference Example 3 (Production of Rubber-Containing Graft Copolymer (I-3)) In the conditions of Reference Example 1, 45 parts by weight of polybutadiene latex (rubber particle size: 0.25 μm) (solid content conversion), The procedure was changed to 11 parts by weight of acrylonitrile, 28 parts by weight of styrene, and 16 parts by weight of N-phenylmaleimide to obtain a rubber-containing graft copolymer (I-3) shown in Table 1.

Reference Example 4 (Meth) acrylic acid alkyl ester rubber-containing graft copolymer (II) Ethyl acrylate was emulsion-polymerized to complete the reaction. Subsequently, 50 parts by weight of a monomer mixture consisting of 60% by weight of styrene and 40% by weight of acrylonitrile was emulsion-polymerized in the presence of 50 parts by weight of this latex (calculated as solid content). The polymer latex obtained was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to prepare a powdery polymer composition.

[Reference Example 5] (Vinyl-based copolymer (III
-1) Production) In a stainless steel autoclave with a capacity of 20 liters,
A solution prepared by dissolving 0.05 parts by weight of a methyl methacrylate / acryeuamide copolymer (described in Japanese Patent Publication No. 45-24151) in 165 parts by weight of ion-exchanged water was added, and 400 rpm was added.
The system was stirred and the inside of the system was replaced with nitrogen gas. Next, 42 parts by weight of acrylonitrile, 4 parts of styrene, 0.46 parts by weight of t-dodecylmercaptan, 2,2'-azobis (2,4
-Dimethylvaleronitrile) (0.39 parts) and 2,2'-azobisisobutylnitrile (0.05 parts) were added to the reaction system with stirring, and the temperature was raised to 58 ° C to initiate polymerization. After 15 minutes had passed from the start of the polymerization, 54 parts of styrene from the feed pump provided at the top of the autoclave
Added over 0 minutes. During this period, the reaction temperature was raised to 65 ° C. After the addition of styrene to the reaction system was completed, the temperature was raised to 100 ° C. over 50 minutes. After that, according to the normal method,
After cooling the reaction system, separating the polymer, washing, and drying,
Bead-shaped vinyl copolymer (III-1) shown in Table 2
I got

Reference Example 6 (Vinyl-based copolymer (III
-2) Production) Among the conditions of Reference Example 5, polymerization was carried out in the same manner as in Reference Example 5 except that t-dodecyl mercaptan was changed to 0.6 part, and the vinyl-based copolymerization shown in Table 2 was performed. Combined (III-
2) was obtained.

[Reference Example 7] (Vinyl-based copolymer (III
Production of -3)) In the conditions of Reference Example 5, t-dodecyl mercaptan was set to 0.
Polymerization was carried out in the same manner as in Reference Example 5 except that the vinyl copolymer (II-3) shown in Table 2 was obtained.

[Reference Example 8] (Vinyl-based copolymer (III
-4) Production) Of the conditions of Reference Example 5, the addition amounts of acrylonitrile and styrene of the monomer mixed solution were 40 and 60 parts by weight, respectively, and the additional addition of styrene was 0 part. Polymerization was performed by the method to obtain a vinyl-based copolymer (II-4) shown in Table 2.

[Reference Example 9] (Vinyl-based copolymer (IV-
Production of 1)) In a stainless steel autoclave having a capacity of 20 L, a methyl methacrylate / acrylamide copolymer (Japanese Patent Publication No.
No. 24151 publication) 0.05 part of ion-exchanged water 16
The solution dissolved in 5 parts was stirred at 400 rpm, and the inside of the system was replaced with nitrogen gas. Next, 75 parts by weight of styrene, 25 parts by weight of acrylonitrile, 0.4 part of t-dodecyl mercaptan.
A mixed solution of 6 parts and 0.15 part of 2,2′-azobisisobutylnitrile was added while stirring the reaction system,
The temperature was raised to 60 ° C. and polymerization was performed for 110 minutes. After this, 100
The temperature was raised to 50 ° C. over 50 minutes to complete the polymerization. afterwards,
Cooling the reaction system, separating the polymer, washing and drying,
A bead-shaped vinyl copolymer (IV-1) shown in Table 3 was obtained.

[Reference Example 10] (Vinyl-based copolymer (IV
-2) Production) 40 parts by weight of styrene, 20 parts by weight of acrylonitrile and 40 parts by weight of N-phenylmaleimide were suspension-polymerized in the same manner as in Reference Example 9 to give a bead-like compound of Table 3.
The described vinyl copolymer (IV-2) was produced.

[0056]

[Table 1]

[Table 2]

[Table 3] [Examples 1 to 4, Comparative Examples 1 to 5] Reference Examples 1 to 10 above
The rubber-containing graft copolymer (I-1 to 3) obtained in Step 1, the (meth) acrylic acid alkyl ester-based rubber-containing graft copolymer (II), the vinyl cyanide-based copolymer (III-
1-4) and vinyl-based copolymers (IV-1, 2)
Were mixed in a ratio shown in Table 4 by a Henschel mixer, and then melt-mixed and pelletized by an extruder. After drying each obtained pellet, a test piece is molded by injection molding to evaluate Izod impact strength, color stability and weather resistance, and blow molding is performed to evaluate blow moldability and uneven thickness. did. Table 4 shows the results.

[0057]

[Table 4] As is clear from the results of Table 4, the thermoplastic resin compositions (Examples 1 to 4) of the present invention have a good balance of mechanical strength represented by impact resistance, color stability, weather resistance and blow moldability. It is excellent. On the other hand, in Comparative Examples 1 and 2 in which a vinyl-based copolymer having a viscosity outside the specified viscosity was used, blow moldability was poor, and in Comparative Example 3, which had many triple sequences, color tone stability was poor. Further, in Comparative Example 4 in which the amount of the rubber-containing graft copolymer is small, the impact resistance was poor,
In Comparative Example 5 in which the (meth) acrylic acid alkyl ester rubber-containing graft copolymer (II) is not added, the weather resistance is not sufficient.

[0058]

EFFECTS OF THE INVENTION The hot resin composition according to the present invention has excellent blow moldability, and has an excellent balance of weather resistance, impact resistance and thermal stability, and a good balance of weather resistance and mechanical properties. In addition to being excellent, it is possible to obtain a blow molded product with excellent productivity.

Claims (9)

[Claims] 1. The weight average particle diameter is 0.05 to 0.5 μm.
In the presence of 10 to 80% by weight of the diene rubbery polymer (a), the vinyl cyanide monomer (b), the aromatic vinyl monomer (c) and, if necessary, further A diene rubber-containing graft copolymer (I) obtained by graft-polymerizing a monomer mixture comprising other vinyl-based monomer (d) copolymerizable with these, and having a graft ratio of 10 to 100%. 1 to 50 parts by weight, in the presence of the (meth) acrylic acid alkyl ester rubber polymer (e), a vinyl cyanide monomer (b), an aromatic vinyl monomer (c), and Further, if necessary, a (meth) acrylic acid alkyl ester-based rubber-containing graft copolymer (II) obtained by graft-polymerizing a monomer mixture containing another vinyl-based monomer (d) copolymerizable with these (II) ) 10 to 60 parts by weight, vinyl cyanide Is a polymer obtained by copolymerizing a monomer mixture of 10 to 50% by weight of a vinyl monomer (b) and 90 to 50% by weight of an aromatic vinyl monomer (c), and has a reduced viscosity ηsp.
Vinyl cyanide-based copolymer (III) having an / c of 0.5 to 1.5 dl / g, 10 to 90 parts by weight, vinyl cyanide monomer (b), aromatic vinyl monomer (c) And a vinyl-based copolymer mixture (IV) obtained by polymerizing a monomer mixture of at least one monomer selected from other copolymerizable vinyl-based monomers (d)
0 to 50 parts by weight, and the total amount of (I) + (II) + (III) + (IV) is 1
A thermoplastic resin composition having an excellent blow moldability of 100 parts by weight. 2. The heat having excellent blow moldability according to claim 1, wherein the particle diameter of the (meth) acrylic acid alkyl ester rubber-like polymer (e) is 0.1 to 2.0 μm. Plastic resin composition. 3. The ratio of the triple sequence of the vinyl cyanide-based monomer (d) of the vinyl cyanide-based copolymer (III) is 10% by weight or less.
A thermoplastic resin composition having excellent blow moldability according to 1. 4. The content ratio of the diene rubber-like polymer (a) and the (meth) acrylic acid acrylic ester rubber-like polymer (e) in the thermoplastic resin composition having excellent blow moldability is both. Is less than 50% by weight, and the content of the diene rubber (a) does not exceed the content of the (meth) acrylic acid acrylic ester rubber polymer (e). The thermoplastic resin composition according to item 3, which is excellent in blow moldability. 5. The alkyl group of the (meth) acrylic acid alkyl ester in the (meth) acrylic acid alkyl ester-based rubbery polymer (e) has 1 to 20 carbon atoms. The thermoplastic resin composition according to 4, which has excellent blow moldability. 6. The thermoplastic resin composition according to claim 1, and 1 or 2 kinds of light resistance stabilizers such as a benzotriazole type ultraviolet absorber and a hindered amine type ultraviolet absorber.
A thermoplastic resin composition excellent in blow moldability, characterized in that one or more kinds thereof are added. 7. The diene rubber-containing graft copolymer (I) comprises 10 to 80% by weight of the diene rubber polymer (a) and vinyl cyanide monomer (b). 1 to 50% by weight, the aromatic vinyl-based monomer (c) is 5 to 70% by weight, and the other vinyl-based monomer (d) is 0 to 50% by weight. From 6
A thermoplastic resin composition having excellent blow moldability according to 1. 8. The composition ratio of each component in the (meth) acrylic acid alkyl ester rubber-containing graft copolymer (II) is 10 to 80% by weight of the (meth) acrylic acid ester rubbery polymer (e), and cyan. 1 to 50% by weight of the vinyl compound (b), 5 to 70% by weight of the aromatic vinyl compound (c), and 0 to 50% by weight of the other copolymerizable vinyl monomer (d). The thermoplastic resin composition having excellent blow moldability according to any one of claims 1 to 7. 9. The composition ratio of each component in the vinyl cyanide-based copolymer (III) is such that the vinyl cyanide-based monomer (b) is 20 to 40% by weight, and the aromatic vinyl-based monomer (c). It is 80-60 weight%, The thermoplastic resin composition excellent in blow moldability of Claim 1 to 8 characterized by the above-mentioned.