JP2003020378A - Transparent sliding thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent sliding thermoplastic resin composition based on a rubber-reinforced styrene resin, excellent in sliding characteristics and heat resistance, with excellent molding processability. SOLUTION: The resin composition consists of a rubber reinforced styrene resin (A) comprising a graft polymer (a-1) obtained by polymerizing one or more monomers selected from aromatic vinyl monomers, vinyl cyanide monomers and (meth)acrylic ester monomers in the presence of a rubbery polymer, or a (co)polymer (a-2) obtained by polymerizing the graft polymer (a-1) with one or more monomers selected from aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylic ester monomers or the like, and a polysiloxane compound (B) containing at least a phenylated polysiloxane. The composition gives a resin molding (3 mm thick) having a total light transmittance of 75% or higher and a haze value of 10.0 or lower.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a transparent slidable thermoplastic resin composition which is excellent in slidability, heat 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.

However, not only such transparency but also slidability may be required for game machines and home appliances. Slidability is a method to prevent scratches when the products are rubbed against each other and the shavings impair the product value when the scratches are significant. As such, a method of adding a silicon type, a fluorine type, a polymer olefin type, or the like is known. However, if a large amount of these sliding agents is added to the transparent resin in order to impart satisfactory slidability, the transparency cannot be maintained. Therefore, at present, it is not possible to satisfy both the transparency and the slidability. No material available.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and is based on a rubber-reinforced styrene resin which is excellent in slidability, heat resistance, and moldability. It is intended to provide a transparent sliding thermoplastic resin composition.

[0005]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventors have found that by using a specific rubber-reinforced styrene resin and a specific compound in a specific range, sliding The present invention has been accomplished by finding that a transparent sliding thermoplastic resin composition having excellent properties, heat resistance, and molding processability can be obtained. That is, the present invention is
(1) an aromatic vinyl-based monomer in the presence of a rubber-like polymer,
Graft polymer (a-1) or (a-1) obtained by polymerizing one or more monomers selected from vinyl cyanide-based monomers and (meth) acrylic acid ester-based monomers (Co) polymer obtained by polymerizing at least one monomer selected from aromatic vinyl-based monomers, vinyl cyanide-based monomers, (meth) acrylic acid ester-based monomers, and the like. Coalescence (a-
2) a rubber-reinforced styrenic resin (A) and a polysiloxane compound (B) containing at least a phenyl group-containing polysiloxane, and a total light transmittance of a resin molded product of 75% or more, and A transparent sliding thermoplastic resin composition having a haze of 10.0 or less, (2) the weight average particle diameter of the rubber-like polymer constituting the graft polymer (a-1) is 0.05 to 2.0 μ, The intrinsic viscosity of the acetone-soluble component of the rubber-reinforced styrene resin (A) is 0.2 to 0.8d.
1 / g of the transparent sliding thermoplastic resin composition according to (1), (3) a polysiloxane compound containing at least a phenyl group-containing polysiloxane with respect to 100 parts by weight of the rubber-reinforced styrene resin (A) ( B) The transparent sliding thermoplastic resin composition according to (1) or (2), which comprises 0.1 to 10 parts by weight, and (4) the polysiloxane (B) has a viscosity (50 ° C. or lower) of 50. The transparent sliding thermoplastic resin composition according to claim 1, 2 or 3, which has a viscosity of about 2000 cs.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The transparent sliding 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.

The polysiloxane compound (B) used in the present invention must contain at least a phenyl group-containing polysiloxane. By containing this phenyl group-containing polysiloxane, it is possible to impart slidability while maintaining the transparency of the rubber-reinforced styrene resin (A), and does not contain this phenyl group-containing polysiloxane. In this case, the transparency is lowered, which is not preferable. Examples of such a phenyl group-containing polysiloxane include phenyl polysiloxane and phenylmethyl polysiloxane, and examples of other polysiloxane compounds include methyl polysiloxane, dimethyl polysiloxane, and methyl ethyl polysiloxane. One or two or more of them can be used. Further, in the present invention, it is necessary to contain at least a phenyl group-containing polysiloxane as the polysiloxane compound (B) as described above, but among all the polysiloxane compounds (B) used, the phenyl group-containing polysiloxane is preferable. It is preferable to contain 50% by weight or more of siloxane.

The polysiloxane compound (B) is preferably used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the rubber-reinforced styrene resin (A). When the polysiloxane compound (B) is less than 0.1 parts by weight, sufficient slidability cannot be obtained, and when it exceeds 10 parts by weight, transparency and heat resistance are deteriorated.

The polysiloxane compound (B) has a viscosity of 50 to 200 in a use environment of 50 ° C. or lower.
It is preferably 0 cs. When the polysiloxane compound (B) is less than 50 cs, it causes mold contamination in injection molding and roll contamination in sheet processing, which is not preferable. Further, if it exceeds 2000 cs, the handling is difficult and the productivity is lowered.

As described above, the present invention comprises a specific rubber-reinforced styrenic resin (A) and a specific polysiloxane compound (B), and has a total light transmittance of 75% when formed into a resin molded product (thickness of 3 mm). Above, and haze is 10.
The resin composition is 0 or less. In order to make the total light transmittance of the resin molded product 75% or more and the haze 10.0 or less, the type and the use ratio of the rubber-like polymer and the monomer in (A), the graft polymer (a -1) weight average particle diameter, graft ratio, intrinsic viscosity of the acetone-soluble component of (A), and these specific rubber-reinforced styrene resin (A)
Specific polysiloxane compound (B) used in combination with
It can be set according to the type and the usage ratio.

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 the transparent sliding thermoplastic resin composition of the present invention, 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 are exemplified. ], An ultraviolet absorber [pt-butylphenyl salicylate, 2,2'-dihydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-4'-
Examples include n-octoxyphenyl) benzotriazole and the like. ], 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 copolymer (a-1-1) was obtained. The graft ratio and the intrinsic viscosity of the acetone-soluble component of the obtained graft copolymer 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 copolymer (a-1-
2) was obtained. The graft ratio of the obtained graft copolymer and the intrinsic viscosity of the acetone-soluble component were 60% and 0.45 dl / g, respectively.

Graft polymer (a-1-3): 50 parts of polybutadiene latex (weight average particle size 035 μ, gel content 90%) (solid content), 150 parts of water, ethylenediaminetetraacetic acid diacetate in a reactor substituted with nitrogen. Sodium salt 0.
1 part, 0.001 part of ferric sulfate and 0.3 part of sodium formaldehyde sulfoxylate were added and after heating to 60 ° C., a mixture of 15 parts of acrylonitrile, 35 parts of styrene and 0.2 part of cumene hydroperoxide was added. It was continuously added over 3 hours and further polymerized at 60 ° C. for 2 hours. Then, after salting out, dehydration and drying, a graft copolymer (a-1-1) was obtained. The graft ratio and the intrinsic viscosity of the acetone-soluble component of the obtained graft copolymer 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.

-Polysiloxane compound (B) -B-1: Phenylmethylpolysiloxane (Toray Dow Corning SH550 viscosity: 125 cs) B-2: Phenylmethylpolysiloxane (Toray Dow Corning SH710 viscosity: 500 cs) B-3 : Dimethylpolysiloxane (Toray Dow Corning SH200 viscosity: 100cs)

[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, using the Yamashiro Seiki 3.5 ounce injection molding machine for the obtained pellets, each test piece was prepared at a cylinder setting temperature of 200 ° C., and the following respective 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.

Sliding property : According to JIS K-7218 (method B), a sliding test was conducted under the following measurement conditions, and the weight difference before and after the test was measured. Unit: mg.

[0031]

[Table 1]

[0032]

As described above, the transparent slidable thermoplastic resin composition of the present invention is excellent in slidability, heat resistance, and molding processability. It can be suitably used in the fields of home appliances, office automation equipment, game machines, etc., which require mobility.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 55/02 C08L 55/02 83/04 83/04 F term (reference) 4J002 BN06W BN061 BN12W BN121 BN14W BN141 BN15W BN151 BN16W BN161 CP032 CP033 FD010 FD050 FD070 FD090 FD170 GC00 GQ00 4J026 AA12 AA13 AA17 AA45 AA49 AA68 AA69 AA71 AA72 AC01 AC02 AC09 AC10 AC11 AC12 AC36 BA05 BA06 BA25 BA27 BA31 BA38 BB04 BB01

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. Contains at least a phenyl group-containing polysiloxane and a rubber-reinforced styrene resin (A) made of a (co) polymer (a-2) obtained by polymerizing one or more kinds of monomers selected from monomers and the like. Of a polysiloxane compound (B), which has a total light transmittance of 75 when formed into a resin molded product (3 mm thick)
% Or more and haze is 10.0 or less, a transparent sliding thermoplastic resin composition. 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 sliding thermoplastic resin composition according to claim 1. 3. A polysiloxane compound (B) containing at least phenyl group-containing polysiloxane in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber-reinforced styrene resin (A). 2. The transparent slidable thermoplastic resin composition as described in 2. 4. The viscosity (50) of the polysiloxane compound (B).
1 or 2, which is 50 to 2000 cs.
Or the transparent slidable thermoplastic resin composition described in 3 above.