JP2003147152A - Transparence-durable antistatic thermoplastic resin composition having excellent impact resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparence-durable antistatic thermoplastic resin composition which is excellent in transparence, an antistatic property, and impact resistance, and has excellent molding processability. SOLUTION: The transparence-durable antistatic thermoplastic resin composition comprises a rubber reinforced styrene resin (A) composing of a graft polymer (a-1) comprising polymerizing in the presence of a rubber-like polymer at least one monomer selected from among an aromatic vinyl, a vinyl cyanide, and a (meth)acrylate, or a (co)polymer (a-2) comprising polymerizing the graft polymer (a-1) and at least one monomer selected from among the aromatic vinyl, the vinyl cyanide, and the (meth)acrylate, and at least two of polyether ester amides (B) which have different refractive indexes (the difference of the refractive indexes is >=0.01), total light transmittance when a resin molding (having a thickness of 3 mm) of the composition is formed being >=75%, and a haze thereof being <=10.0.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a transparent persistent antistatic thermoplastic resin composition which is excellent in transparency, antistatic property, impact resistance and molding processability.

[0002]

2. Description of the Related Art Manufactured under the names HIPS, ABS, etc.
The rubber-reinforced styrene resin sold is excellent in appearance, mechanical properties and molding processability, and is used in various fields such as vehicle parts and electric products. However, such a rubber-reinforced styrene resin is generally opaque, but depending on the product, transparency such as PMMA or polycarbonate resin may be required. In order to meet such a requirement, transparency can be obtained even in a rubber-reinforced styrene-based resin by adjusting the composition ratio of each component constituting the resin, as described in, for example, JP-A-4-180907. Known to get.

As a further market need, not only such transparency but also antistatic property may be required for game machines, pachinko parts, OA equipment and home appliances. However, the rubber-reinforced styrene resin has a high surface resistivity value and is easily charged, and therefore has drawbacks such as dust adhering to the product and deteriorating the appearance of the product, and electrical and electronic products causing damage due to static electricity. . Therefore, a material having an antistatic property while maintaining transparency is desired,
JP-A-8-120147 proposes a material having transparency and antistatic property, but such a method has a drawback that a material having sufficient impact characteristics cannot be obtained.

[0004]

The present invention has been made to solve the above problems, and is a rubber-reinforced styrenic resin having excellent transparency, antistatic property, impact resistance and molding processability. It is an object of the present invention to provide a transparent persistent antistatic thermoplastic resin composition based on.

[0005]

Means for Solving the Problems As a result of intensive studies in view of such problems, the present inventors have found that a specific rubber-reinforced styrenic resin and a specific polyether ester amide are mixed by two or more kinds, The present invention has been achieved by finding that a transparent continuous antistatic thermoplastic resin composition having excellent transparency, antistatic property, impact resistance and molding processability can be obtained. That is, the present invention is (1) selected from aromatic vinyl-based monomers, vinyl cyanide-based monomers and (meth) acrylic acid ester-based monomers in the presence of a rubbery polymer. Graft polymer (a-1) or (a-1) obtained by polymerizing at least one kind of monomer, and aromatic vinyl-based monomer, vinyl cyanide-based monomer and (meth)
A rubber-reinforced styrene-based resin (A) composed of a (co) polymer (a-2) obtained by polymerizing one or more monomers selected from acrylic acid-based monomers and at least a refractive index It is composed of two or more different polyether ester amides (B) having different refractive indices (0.01 or more), and has a total light transmittance of 75% or more and a haze of 1 when formed into a resin molded product.
Transparent persistent antistatic thermoplastic resin composition of 0.0 or less, (2) weight average particle diameter of rubber-like polymer constituting the graft polymer (a-1) is 0.05 to 2.0 μm, rubber (1) The transparent persistent antistatic thermoplastic resin composition according to (1), wherein the acetone-soluble component of the reinforced styrene resin (A) has an intrinsic viscosity of 0.2 to 0.8 dl / g, and (3) the rubber reinforced styrene resin. Two or more kinds of polyether ester amides (B) 3 having different refractive indexes with respect to 100 parts by weight of the resin (A)
To 30 parts by weight of the transparent persistent antistatic thermoplastic resin composition (1) or (2), and (4) the polyether ester amide (B) has a refractive index of 1.40 to 1.6.
The transparent persistent antistatic thermoplastic resin composition according to (1), (2), or (3), which is 0, is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The transparent persistent antistatic thermoplastic resin composition of the present invention will be described in detail below.

The rubber-reinforced styrene resin (A) used in the present invention means an aromatic vinyl monomer, a vinyl cyanide monomer and (meth) in the presence of a rubber-like polymer.
Graft polymer (a-1) obtained by polymerizing one or more kinds of monomers selected from acrylic acid ester monomers, or the graft polymer (a-1) and aromatic vinyl monomer From a (co) polymer (a-2) obtained by polymerizing one or more kinds of monomers selected from the following: a vinyl cyanide monomer, a (meth) acrylic acid ester monomer, and the like. It is a rubber-reinforced styrene resin.

The rubber-like polymer constituting the graft polymer (a-1) in the rubber-reinforced styrene resin (A) is polybutadiene, polyisoprene, butadiene-styrene copolymer, isoprene-styrene copolymer, butadiene. -Acrylonitrile copolymer, butadiene-isoprene-styrene copolymer, diene rubber such as polychloroprene, ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene (ethylidene norbornene, dicyclopentadiene, etc.) copolymer, etc. Ethylene-propylene rubber, acrylic rubber such as polybutyl acrylate, and the like, and one kind or two or more kinds can be used.

Examples of the aromatic vinyl monomer constituting the graft polymer (a-1) or (co) polymer (a-2) include styrene, α-methylstyrene and paramethylstyrene. One kind or two or more kinds can be used. Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile and the like, and one kind or two or more kinds can be used. Examples of the (meth) acrylic acid ester-based monomer include methyl methacrylate, methyl acrylate and the like, and one kind or two or more kinds can be used. In the present invention, the above-mentioned aromatic vinyl-based monomer, vinyl cyanide-based monomer and (meth) acrylic acid ester-based monomer may be optionally copolymerized with other copolymerizable monomers, for example, It is also possible to use maleimide-based monomers such as N-phenylmaleimide and N-cyclohexylmaleimide, and unsaturated carboxylic acids such as acrylic acid and methacrylic acid.

Graft polymer (a-1) used in the present invention
The weight average particle diameter of the rubber-like polymer constituting the rubber composition is 0.05 to 2.0 μ, and the intrinsic viscosity (30 ° C., dimethylformamide solvent) of the acetone-soluble component of the rubber-reinforced styrene resin (A) is 0. It is preferably in the range of 2 to 0.8 dl / g. Here, the graft polymer (a-
The weight average particle diameter of the rubber-like polymer constituting 1) is 0.0
If it is less than 5 μm, impact resistance is poor, and if it exceeds 2.0 μm, transparency is deteriorated. If the intrinsic viscosity of the acetone-soluble component of the rubber-reinforced styrene resin (A) is less than 0.2 dl / g, the impact resistance is poor, and if it exceeds 0.8 dl / g, the moldability is deteriorated.

As the polyether ester amide (B) used in the present invention, it is necessary to use at least two kinds having different refractive indexes in combination. By using two or more kinds of polyether ester amides having different refractive indexes, excellent impact resistance is imparted in addition to antistatic property while maintaining the transparency of the rubber-reinforced styrene resin (A). The material can be supplied. As such a polyether ester amide, at least one selected from the group consisting of aminocarboxylic acids having 6 or more carbon atoms, lactams having 6 or more carbon atoms, and nylon salts having 6 or more carbon atoms obtained from a diamine and a dicarboxylic acid. And a compound obtained by polycondensing a polyamide containing both terminal carboxyl groups derived from dicarboxylic acid and a polyether diol consisting of an ethylene oxide adduct of polyoxyalkylene glycol and / or bisphenol. Therefore, two or more kinds having different molecular weights, structures and / or compositions can be used. Further, in the present invention, as described above, it is necessary to use at least two kinds of polyether ester amides (B) having different refractive indexes (refractive index difference of 0.01 or more) in combination. When two or more kinds of polyether ester amides are not used in combination, or even when they are used in combination, the difference in the refractive index is less than 0.01 because the impact resistance is inferior, which is not preferable. The mixing ratio of two or more kinds of polyether ester amides having different refractive indexes is not particularly limited, but for example, 2
In the case of seeds, it is preferably in the range of 99/1 to 1/99 (weight ratio).

Regarding the proportion of the polyether ester amide (B) used, the rubber-reinforced styrene resin (A) 1
It is preferably 3 to 30 parts by weight with respect to 00 parts by weight. If the polyether ester amide (B) is less than 3 parts by weight, sufficient antistatic property cannot be obtained, and if it exceeds 30 parts by weight, transparency and heat resistance are deteriorated.

The refractive index of the polyether ester amide (B) is preferably 1.40 to 1.60 under a use environment of 30 ° C. or lower. If the refractive index of the polyether ester amide (B) is less than 1.40 or 1.60 or more, it is different from the refractive index of the rubber-reinforced styrenic resin (A), and the transparency is lowered.

As described above, the present invention comprises a specific rubber-reinforced styrenic resin (A) and at least two kinds of polyether ester amides (B) having different refractive indexes to form a resin molded product (thickness of 3 mm). Total light transmittance of 75
% And a haze of 10.0 or less. In order to set the total light transmittance of the resin molded product to 75% or more and the haze to 10.0 or less, the types of the rubber-like polymer and the monomer in (A) and their use ratios,
Weight average particle diameter of graft polymer (a-1), graft ratio, intrinsic viscosity of acetone-soluble component of (A), and polyether ester amide used in combination with these specific rubber-reinforced styrene resin (A) It can be set according to the type of (B) and its usage rate.

The mixing method of the respective components in the present invention is not particularly limited, and they can be mixed using an extruder, a Banbury mixer, a roll, a kneader and the like.

In addition, the transparent persistent antistatic thermoplastic resin composition of the present invention includes known additives such as antioxidants [2,6-di-t-butyl-4-methylphenol, 2
-(1-Methylcyclohexyl) -4,6-dimethylphenol, 2,2-methylenebis- (4-ethyl-6-
t-methylphenol), 4,4'-thiobis- (6-
t-butyl-3-methylphenol), dilaurylthiodipropionate, tris (di-nonylphenyl) phosphite, and the like. ], An ultraviolet absorber [pt-
Butylphenyl salicylate, 2,2'-dihydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzotriazole and the like are exemplified. ], Lubricants [paraffin wax, stearic acid, hydrogenated oil, stearamide, methylene bis stearamide, ethylene bis stearamide, n-butyl stearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride, etc. are exemplified. It ], A colorant [eg titanium oxide, carbon black], a filler [eg calcium carbonate, clay, silica, glass fiber, glass sphere, carbon fiber, etc.]. ] Etc. can be added as needed.

Further, in the present invention, other thermoplastic resins such as polycarbonate, polyamide, polybutylene terephthalate, polyphenylene oxide, polyoxymethylene, and chlorinated polyethylene are mixed in a range that maintains transparency, if necessary. be able to.

In order to describe the present invention more specifically, examples and comparative examples will be described below. However, the present invention is not limited to these.

[Examples] -Rubber-reinforced styrene resin (A) -Graft polymer (a-1-1): Polybutadiene latex (weight average particle diameter 0.30) in a reactor substituted with nitrogen.
μ, gel content 85%) 50 parts (solid content), water 150
Parts, ethylenediaminetetraacetic acid disodium salt 0.1 parts,
After adding 0.001 part of ferric sulfate and 0.3 part of sodium formaldehyde sulfoxylate and heating to 60 ° C., 3 parts of acrylonitrile, 12 parts of styrene, 35 parts of methyl methacrylate and cumene hydroperoxide were added.
A mixture of 2 parts was continuously added over 3 hours, and the mixture was further polymerized at 60 ° C. for 2 hours. Then, after salting out, dehydration and drying, a graft polymer (a-1-1) was obtained. The graft ratio and the intrinsic viscosity of the acetone-soluble component of the obtained graft polymer were 52% and 0.50 dl / g, respectively.

Graft polymer (a-1-2): 20 parts of polybutadiene latex (weight average particle size 0.50 μ, gel content 90%), 5 parts of acrylonitrile, 19 parts of styrene, 56 parts of methyl methacrylate, and sodium. Except for changing to 0.4 parts of formaldehyde sulfoxylate and 0.3 parts of cumene hydroperoxide (a
In the same manner as in (1-1), the graft polymer (a-1-
2) was obtained. The graft ratio and the intrinsic viscosity of the acetone-soluble component of the obtained graft polymer were 60% and 0.45 dl / g, respectively.

Graft polymer (a-1-3): 50 parts (solid content) of polybutadiene latex (weight average particle diameter 0.35 μ, gel content 90%) in a reactor substituted with nitrogen.
150 parts of water, 0.1 part of ethylenediaminetetraacetic acid disodium salt, 0.001 part of ferric sulfate, 0.3 part of sodium formaldehyde sulfoxylate were added, and after heating to 60 ° C., 15 parts of acrylonitrile, 35 parts of styrene and A mixture of 0.2 parts of cumene hydroperoxide was continuously added over 3 hours, and the mixture was further polymerized at 60 ° C. for 2 hours. Then, after salting out, dehydration and drying, a graft polymer (a-1-1) was obtained. The graft ratio of the obtained graft polymer and the intrinsic viscosity of the acetone-soluble component were 55% and 0.52 dl / g, respectively.

Copolymer (a-2-1): A reactor purged with nitrogen was charged with 130 parts of pure water and 0.3 part of potassium persulfate, and then heated to 65 ° C. with stirring. Then, 30 parts of an emulsifier aqueous solution containing 10 parts of acrylonitrile, 30 parts of styrene, 60 parts of methyl methacrylate and 0.35 part of t-dodecyl mercaptan and 2 parts of disproportionated potassium rosinate were used for 4 hours. Then, the polymerization system was heated to 70 ° C. and aged for 2 hours to complete the polymerization. After salting out, dehydration and drying, a copolymer C-1 having an intrinsic viscosity of 0.50 was obtained.

Copolymer (a-2-2): The same operation as in (a-2-1) is carried out except that 30 parts of acrylonitrile and 70 parts of styrene are used as monomers, and an intrinsic viscosity of 0.
A copolymer of 5 was obtained.

-Polyether ester amide (B) -B-1: Perestat NC6321 (manufactured by Sanyo Kasei Co., Ltd. Refractive index: 1.516) B-2: Perestat NC7530 (manufactured by Sanyo Chemical Co., Ltd. Refractive index: 1. 536) BI: polyethylene oxide (manufactured by Sumitomo Seika Co., Ltd.
Carbon number: 8-10) B-II: Sodium dodecylbenzene sulfonate

[Examples 1 to 4 and Comparative Examples 1 to 6] The above components were mixed at the compounding ratio shown in Table 1 to obtain 40 mm.
Melt kneading was carried out at 200 ° C. using a twin-screw extruder to obtain pellets. Also, the obtained pellets are IS-
90B injection molding machine, cylinder set temperature 200 ℃
Each test piece was prepared in and the following evaluations were performed. The evaluation results are shown in Table 1. Regarding the intrinsic viscosity of the rubber-reinforced styrenic resin used in the examples and comparative examples, apart from the above-mentioned mixing, the graft polymer and the copolymer were mixed in an extruder at the ratios shown in Table 1. After that, the acetone-soluble component was extracted and the intrinsic viscosity was measured.

Total light transmittance : Using a test piece having a thickness of 3 mm, a reflection / transmittance meter HR-1 manufactured by Murakami Color Research Laboratory Co., Ltd.
It was measured at 00.

Haze : Murakami Color Research Laboratory Co., Ltd. reflection / transmittance meter HR using the same test piece as the total light transmittance measurement.
It was measured at -100.

Impact resistance : Notched Izod impact strength was measured according to ASTM D-256. Unit: MPa.

Molding processability : Melt flow rate was measured according to ASTM D-1238. 220 ° C x 10k
g, unit: g / 10 min.

Antistatic property : Using an injection-molded square test piece having a thickness of 3 mm, the condition was adjusted at 23 ° C. and a humidity of 50% RH for 1 month, and the surface specific resistance value before and after the water washing treatment was calculated by Toago Denshi Kogyo ( It was measured by Ultramegahm Meter SN8210 manufactured by Co., Ltd. Unit: Ω

[0031]

[Table 1]

[0032]

As described above, the transparent persistent antistatic thermoplastic resin composition of the present invention is excellent in transparency, antistatic property, impact property and molding processability, and requires transparency. Appliances and OA that are required to have antistatic properties
It can be suitably used in the field of equipment, game machines and the like.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J002 BN06W BN061 BN12W BN121                       BN14W BN141 BN15W BN151                       BN16W BN161 CL08X CL08Y                       CL082 CL083 FD010 FD050                       FD070 FD090 FD10X FD10Y                       FD102 FD103 FD170

Claims (4)

[Claims] 1. In the presence of a rubbery polymer, at least one monomer selected from aromatic vinyl-based monomers, vinyl cyanide-based monomers and (meth) acrylic acid ester-based monomers. A graft polymer (a-1) obtained by polymerizing a monomer, or the graft polymer (a-1) and an aromatic vinyl-based monomer, a vinyl cyanide-based monomer and a (meth) acrylic acid ester-based monomer. At least a different refractive index (refractive index difference) from the rubber-reinforced styrenic resin (A) made of a (co) polymer (a-2) obtained by polymerizing one or more kinds of monomers selected from the monomers. Of at least 0.01) and two or more kinds of polyether ester amides (B). The resin molded product (thickness: 3 mm) has a total light transmittance of 75% or more and a haze of 10.
A transparent persistent antistatic thermoplastic resin composition having a value of 0 or less. 2. The rubber-like polymer constituting the graft polymer (a-1) has a weight average particle diameter of 0.05 to 2.0 .mu.m and an intrinsic viscosity of an acetone-soluble component of the rubber-reinforced styrene resin (A). Is 0.2 to 0.8 dl / g. The transparent persistent antistatic thermoplastic resin composition according to claim 1. 3. A rubber-reinforced styrene resin (A) (100 parts by weight) and at least two kinds of polyether ester amides (B) having different refractive indexes (3 to 30 parts by weight). The transparent persistent antistatic thermoplastic resin composition described. 4. The transparent, persistent antistatic thermoplastic resin composition according to claim 1, 2, or 3, wherein the polyether ester amide (B) has a refractive index of 1.40 to 1.60.