JPH05331345A - Antifungal thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition which can give a molding excellent in environmental stress cracking resistance and antifungal properties by mixing a polymer mixture comprising a polymer of a vinyl monomer and a polymer of an acrylic ester with a rubber-containing styrene resin and a specified antifungal agent. CONSTITUTION:The composition comprises 0.5-50wt.% polymer mixture prepared by mixing 20-90wt.% (in terms of the solid matter) emulsion of a polymer of a vinyl monomer having a glass transition temperature of 20 deg.C or above, a gel fraction of 10% or below, a solubility parameter of 9.0-11.0 (cal/cc)<2> and a weight-average molecular weight (in terms of PS) of 2X10<5>-40X10<5> with l0-80wt.% (in terms of the solid matter) emulsion of a (co)polymer of an acrylic ester monomer and having a glass transition temperature of 20 deg.C or below, a gel fraction of 70% or below and a solubility parameter of 8.4-9.8(cal/cc)<1/2> and separating the polymers from the resulting emulsion, 45-99.4wt.% rubber- containing styrene resin and 0.1-5wt.% antifungal hydroxyapatite.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition having excellent resistance to environmental stress cracking and antibacterial properties. More specifically, it relates to an antibacterial thermoplastic resin composition suitable as a molding material for kitchen appliances, bath appliances, washing machines, refrigerators and the like.

[0002]

2. Description of the Related Art Water supply products such as kitchen utensils and bath products are
Microorganisms such as mold and bacteria are prone to breed, and in particular, they have the drawback of being darkened by mold. Conventionally, in order to prevent this, an organic antibacterial agent has been kneaded into the resin, or the surface of the resin has been treated. However, the organic antibacterial agent has a drawback that durability and safety are not sufficient. In addition, chemicals such as detergents are used in kitchens and bathrooms, but the styrene resin has a problem that it is deteriorated by contact with these chemicals.

[0003]

[Problems to be Solved by the Invention]
An object of the present invention is to provide a thermoplastic resin composition having excellent chemical resistance (environmental stress crack resistance) and antibacterial property by improving the resin composition without impairing the properties of the styrene resin.

[0004]

Means for Solving the Problems As a result of earnest studies for this purpose, the present inventor has found that a resin composition obtained from a vinyl copolymer from an acrylic ester polymer and a vinyl monomer polymer. It was also found that the thermoplastic resin composition of the above purpose can be obtained by adding a specific antibacterial agent.

That is, the present invention is as follows: (A) It is a polymer of vinyl type monomer, its glass transition temperature is over 20 ° C, gel content is 10% or less, and its solubility parameter is 9.0-11.0 (cal / cc) ^1/2 . Yes, and has a polystyrene-based weight average molecular weight of 2 × 10
20 to 90% by weight (as solid content of the polymer) of a polymer emulsion of ⁵ or more and less than 40 × 10 ⁵ and (B) a homopolymer of an acrylic acid ester monomer or an acrylic acid ester monomer And another copolymerizable monomer, the glass transition temperature of which is 20 degrees Celsius or less, the gel content is 70% or less, and the solubility parameter is 8.4 to 9.8 (cal / c).
c) Component (A) polymer obtained by mixing 10 to 80% by weight (as the solid content of the polymer) of a ^1/2 polymer emulsion in the emulsion state and then separating from the emulsion 0.5 to 50% by weight of a polymer mixture with the component (B) polymer, 45-99.4% by weight of rubber-containing styrene resin and 3. An antibacterial thermoplastic resin composition comprising 0.1 to 5% by weight of antibacterial hydroxyapatite.

The present invention will be described in detail below. The vinyl-based monomer constituting the component (A) polymer of the present invention is
For example, aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene and chlorostyrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl acrylate,
Acrylic ester monomers such as ethyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octadecyl acrylate and glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, decyl methacrylate, octadecyl methacrylate and Methacrylic acid ester monomers such as hydroxyethyl methacrylate, amide monomers such as acrylamide and methacrylamide, unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid and itaconic acid, ethylene, propylene, 1-butene, Olefin monomers such as isobutylene and 2-butene, maleimide,
N-methylmaleimide, N-ethylmaleimide and N-
Maleimide monomers such as phenylmaleimide, acid anhydride monomers such as maleic anhydride, butadiene, conjugated diene monomers such as isoprene and chloroprene, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, hexyl vinyl ether, octadecyl vinyl ether, There are vinyl ether monomers such as phenyl vinyl ether and glycidyl vinyl ether, and vinyl ketone monomers such as methyl vinyl ketone and phenyl vinyl ketone.

Further, the vinyl-based monomer constituting the component (A) polymer of the present invention may be a polyfunctional vinyl monomer, for example, divinylbenzene, ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, allyl (meth) acrylate, vinyl (meth) There are acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate and the like.

Next, the component (A) polymer of the present invention is required to have a glass transition temperature of more than 20 degrees Celsius. Furthermore, the preferred glass transition temperature is 30 degrees Celsius or higher.
The polymer mixture obtained by mixing the (A) component polymer and the (B) component polymer in which the glass transition temperature of the (A) component polymer is 20 ° C. or lower may be handled as powder or pellets. Since it is difficult, it is industrially disadvantageous, and when mixed with a rubber-containing styrene resin, the heat resistance is greatly reduced, which is not preferable.

The component (A) polymer of the present invention has a composition of 9.0 to 11.0.
It is necessary to have a solubility parameter in the range of (cal / cc) ^1/2 , and more preferable range is 9.5 to 1
It is 0.5 (cal / cc) ^1/2 . A thermoplastic resin composition obtained by mixing a rubber-containing styrene resin with a polymer mixture in which a component (A) polymer having a solubility parameter outside the scope of the present invention is mixed with a component (B) polymer. Is not preferable because surface defects such as flow marks appear on the molded product.

The solubility parameter as used herein means John Wiley End Sands Co., Ltd., New York City 1
Issued in 1975, edited by Brand Wrap (J. Bran Drup) and Inmargut (EH Immergut), Polymer Handbook, 2nd Edition IV337-IV359
Using the solubility parameter values described on the page, the solubility parameter δ _T of the copolymer is calculated as the solubility parameter δ _{n of} the individual vinyl monomer homopolymer constituting the copolymer composed of m kinds of vinyl monomers. And its weight fraction W _n ,
It is calculated by the following formula [I].

[0011]

For example, the solubility parameters of polybutyl acrylate and polyethyl acrylate are respectively 8.8.
Assuming (cal / cc) ^1/2 and 9.4 (cal / cc) ^1/2 , the solubility parameter of a copolymer composed of 70% by weight of polybutyl acrylate and 30% by weight of polyethyl acrylate is
It can be calculated as 9.0 (cal / cc) ^1/2 .

The component (A) polymer of the present invention has a polystyrene-based weight average molecular weight of 2 × 10 ⁵ or more and 40 × 10 5.
Must be less than ⁵ . Using a polymer mixture obtained by mixing the component (A) polymer having a weight average molecular weight of less than 2 × 10 ^{5 based on} polystyrene with the component (B),
A thermoplastic resin composition obtained by mixing with a rubber-containing styrene resin is not preferable because a surface defect phenomenon such as a flow mark appears in a molded product.

The polystyrene-based weight average molecular weight referred to in the present specification is a weight average molecular weight determined by gel permeation chromatography, assuming that the component (A) polymer is polystyrene. That is,
In the measurement of the weight average molecular weight, polystyrene having a narrow molecular weight distribution and a known molecular weight is used as a reference substance, and the relationship between the outflow peak volume of the gel permeation chromatogram and the molecular weight is obtained to prepare a calibration curve. Then
The gel permeation chromatogram of the component (A) polymer is measured, the molecular weight is determined from the outflow volume using the above calibration curve, and the weight average molecular weight is calculated according to a conventional method.

The component (A) polymer of the present invention must have a gel content of 10% or less. The gel content referred to in the present invention means that about 1.0 g of the component (A) polymer is accurately measured (S
₀ g), put in a basket made of 400 mesh stainless steel wire mesh, immerse in 100 g of methyl ethyl ketone, leave it for 24 hours at 5 degrees Celsius, pull up the basket, and air dry at room temperature ( A) Weight of polymer insoluble component S ₁ g
Is measured and the value calculated from them according to the following formula [II] is referred to.

(S ₁ / S ₀ ) × 100 (%) ... [II]

A thermoplastic resin composition obtained by mixing a rubber-containing styrene resin with a polymer mixture prepared by mixing a component (A) polymer having a gel content of more than 10% with a component (B) polymer. The molded article is not preferable because the gloss of the molded article is inferior.

Regarding the method for producing the component (A) polymer of the present invention, known techniques such as emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization can be arbitrarily applied, and production by emulsion polymerization is industrially most advantageous. Is. That is, in the present invention, the component (A) polymer and the component (B) polymer are mixed in an emulsion state, and the emulsion polymerization facilitates industrially production of a high molecular weight polymer. This is because it can be manufactured.

In producing the component (A) polymer of the present invention, the vinyl type monomer is selected such that the glass transition temperature, gel content, solubility parameter and weight average molecular weight of the obtained component (A) polymer are selected. Is optional as long as it satisfies the requirements of the present invention.

A chain transfer agent can be used for the purpose of controlling the molecular weight of the component (A) polymer. In particular,
In the case of copolymerizing a polyfunctional vinyl monomer, a chain transfer agent may be used together to prepare a component (A) polymer having a branched structure and a low gel content. ..

The chain transfer agent which can be used in the present invention includes, for example, octyl mercaptan, decyl mercaptan, dodecyl mercaptan, sulfur compounds such as ethyl thioglycolate and butyl thioglycolate, halogen compounds such as carbon tetrachloride, limonene and terpinolene. Examples include hydrocarbons, nitro compounds such as trinitrophenol and trinitrobenzene, and benzoquinone.

Next, the component (B) polymer of the present invention is a homopolymer of an acrylic acid ester monomer or a copolymer of an acrylic acid ester monomer and another copolymerizable monomer. Specific examples of the acrylic acid ester monomer are the same as the specific examples of the acrylic acid ester monomer described above as an example of the vinyl-based monomer constituting the component (A) polymer of the present invention. In addition, specific examples of the copolymerizable monomer that constitutes the component (B) polymer include acrylic monomers among the monomers described as examples of the vinyl-based monomer that constitutes the component (A) polymer. It is the same as the specific example except for the acid ester monomer.

In the component (B) polymer of the present invention, a polyfunctional vinyl monomer or a chain transfer agent can be used in the polymerization. Specific examples of the polyfunctional vinyl monomer and the chain transfer agent are as follows. The same as the specific examples described for the component (A) polymer.

The component (B) polymer of the present invention must have a glass transition temperature of 20 ° C. or lower. Further, the preferred glass transition temperature is 10 degrees Celsius or less. (B)
A thermoplastic resin obtained by mixing a component-containing polymer having a glass transition temperature higher than 20 ° C. with a rubber-containing styrene resin using a polymer mixture prepared by mixing a component (B) polymer with a component (A) polymer. The resin composition is not preferable because the environmental stress crack resistance is poor.

The component (B) polymer of the present invention must have a gel content of 70% or less. The gel content was measured by replacing the solvent with 100 g of methyl ethyl ketone,
The procedure for measuring the component (A) polymer is the same as that for the component (A) except that 100 g of toluene is used, and it can be calculated according to the above formula [II]. A thermoplastic resin composition obtained by mixing a rubber-containing styrene resin with a polymer mixture obtained by mixing a component (B) polymer having a gel content of more than 70% with a component (A) polymer is Environmental stress crack resistance is poor, which is not preferable.

The component (B) polymer of the present invention is 8.4 to 9.8.
It is necessary to have a solubility parameter in the range of (cal / cc) ^1/2 . Further, the preferable numerical range is 8.6.
It is ~ 9.6 (cal / cc) ^1/2 . The method for determining the solubility parameter is the same as the measurement operation of the component (A) polymer,
It can be calculated according to the above formula [I].

The solubility parameter of the component (B) polymer is less than 8.4 (cal / cc) ^1/2 or 9.8 (cal / cc)
A thermoplastic resin composition obtained by mixing a rubber-containing styrene resin with a polymer mixture obtained by mixing more than ^1/2 of the component (B) polymer with the component (A) polymer has The cracking property is poor, which is not preferable.

As the method for producing the component (B) polymer of the present invention, known techniques such as emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization can be arbitrarily applied. Similarly, the production by emulsion polymerization is industrially most advantageous.

In producing the component (B) polymer, the acrylic ester monomer or the copolymerizable monomer is selected by the glass transition temperature of the obtained component (B) polymer,
It is optional as long as the gel content and the solubility parameter satisfy the requirements of the present invention.

In the present invention, 20 to 90% by weight of the component (A) polymer and 10 to 80% by weight of the component (B) are mixed to obtain a polymer mixture, which contains the component (B) polymer. The thermoplastic resin composition obtained by mixing a polymer mixture having a ratio of less than 10% with a rubber-containing styrenic resin is inferior in environmental stress crack resistance, and when it exceeds 80% by weight from the thermoplastic resin composition. The resulting molded article is not preferable because a surface defect phenomenon such as a flow mark appears.

In the present invention, the emulsion of the component (A) polymer and the emulsion of the component (B) polymer are mixed in an emulsion state. When the component (A) polymer or the component (B) polymer is produced by emulsion polymerization, the emulsion polymerization liquid obtained by emulsion polymerization can be used as it is, but it is produced by another polymerization method. In some cases, a step of emulsifying the obtained polymer is necessary.

For the emulsification method of the polymer obtained by another polymerization method, any known technique can be applied. For example, (A)
A method of mixing and stirring a polymer solution with an emulsifier and water to form an emulsion and then removing the solvent, (B) a method of mixing and stirring fine powder obtained by pulverizing a polymer with an emulsifier and water to form an emulsion , (C) The polymer may be pulverized in the presence of an emulsifier and water to give an emulsion, but not limited thereto.

There are no particular restrictions on the type of emulsifier used for emulsion polymerization of the (A) component polymer or (B) component polymer or for the emulsification of the polymer. Anionic surfactants, cationic surfactants and amphoteric interfaces are used. The active agent and the nonionic surfactant can be arbitrarily selected, but the anionic surfactant can be most advantageously used.

The component (A) polymer emulsion and the component (B) polymer emulsion are mixed by using, for example, a fixed container type mixing device, a rotary container type mixing device, a pipeline mixer and a static mixer. Can be mixed.

The method of separating the polymer mixture from the mixture of the component (A) polymer emulsion and the (B) component polymer emulsion is as follows:
For example, a method of adding an acid such as hydrochloric acid, sulfuric acid and phosphoric acid, an electrolyte such as sodium chloride, calcium chloride, aluminum chloride and magnesium sulfate, and a precipitation agent such as a water-soluble polymer such as polyvinyl alcohol or polyethylene glycol to the emulsion. , A method of freezing the emulsion to destroy the emulsion and a method of spraying the emulsion into a high temperature gas.

The polymer mixture separated from the mixed liquid of the component (A) polymer emulsion and the component (B) polymer emulsion can be further fed to a melt kneader to be melt-kneaded. Examples of melt-kneading devices that can be used include Banbury mixers, co-kneaders, single-screw or twin-screw extruders, and mixing rolls.

As the monomer constituting the rubber component of the rubber-containing styrene resin in the present invention, conjugated diene monomers such as butadiene, isoprene, chloroprene and cyclopentadiene, 2,5-norbornadiene, 1,4
Homopolymerization of non-conjugated diene monomers such as cyclohexadiene and 4-ethylidene norbornene, or aromatic vinyl monomers such as conjugated dienes or non-conjugated dienes and styrene, α-methylstyrene and vinyltoluene, acrylonitrile and methacryl Vinyl cyanide monomer such as ronitrile, methyl acrylate, ethyl acrylate,
Acrylic ester monomers such as butyl acrylate, hexyl acrylate, cyclohexyl acrylate and octadecyl acrylate, methyl methacrylate,
Use copolymers of methacrylic acid ester monomers such as ethyl methacrylate, butyl methacrylate, hexyl methacrylate and hydroxyethyl methacrylate, and olefin monomers such as ethylene, propylene, 1-butene, isobutylene and 2-butene. You can

As the rubber component, a copolymer obtained by copolymerizing a polyfunctional vinyl monomer as a crosslinking monomer can also be used. Examples of the polyfunctional vinyl monomer include divinylbenzene and ethylene glycol diethylene. (Meth) acrylate, 1,
3-butylene glycol di (meth) acrylate, 1,
4-butylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, allyl (meth) acrylate, vinyl (meth) acrylate, diethylene glycol di (meth) acrylate and triethylene glycol di ( (Meth) acrylate and the like.

The rubber component used in the rubber-containing styrenic resin of the present invention is required to have a graft active site. Specifically, it has a carbon-carbon double bond in the rubber molecule. Is preferred. As a method for polymerizing the above-mentioned monomer, a known technique such as emulsion polymerization or solution polymerization can be used. Further, the rubber component may be a mixture of two or more rubber components.

In the present invention, it is essential that the monomer constituting the resin component of the rubber-containing styrenic resin contains a styrene monomer and a nitrile monomer, such as styrene, α-methylstyrene, Aromatic vinyl monomers such as vinyltoluene, t-butylstyrene and chlorostyrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octadecyl acrylate. And acrylic acid ester monomers such as glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, decyl meta. Methacrylic acid ester monomers such as relate, octadecyl methacrylate and hydroxyethyl methacrylate, amide monomers such as acrylamide and methacrylamide, unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid and itaconic acid, ethylene, propylene , 1-butene, isobutylene and 2-
Olefin monomers such as butene, maleimides such as maleimide, N-methylmaleimide, N-ethylmaleimide and N-phenylmaleimide, acid anhydride monomers such as maleic anhydride, butadiene, isoprene and chloroprene Conjugated diene monomers, vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, hexyl vinyl ether, octadecyl vinyl ether, phenyl vinyl ether and glycidyl vinyl ether, and vinyl ketone monomers such as methyl vinyl ketone and phenyl vinyl ketone. These can be used alone or as a copolymer.

The rubber-containing styrene resin in the present invention is, for example, ABS (acrylonitrile-butadiene-).
Styrene) resin, heat resistant ABS (acrylonitrile-butadiene-styrene-α-methylstyrene) resin, AA
Examples thereof include S (acrylonitrile-acrylic acid ester-styrene) resin, AES ((acrylonitrile-EPDM-styrene) resin, and MBAS (methyl methacrylate-butadiene-acrylonitrile-styrene) resin.

The content of the rubber component contained in the rubber-containing styrene resin of the present invention is 2 to 70% by weight, preferably 5 to 70% by weight.
60% by weight. When the content of the rubber component is less than 2% by weight, impact resistance of the thermoplastic resin composition obtained by mixing with the polymer mixture is low, and when it exceeds 70% by weight, rigidity or heat resistance is reduced.

Further, the resin component of the rubber-containing styrene resin of the present invention comprises 40 to 90% by weight of styrene monomer, 5 to 50% by weight of nitrile monomer and 0 to 40 other copolymerizable monomer. It is preferably composed by weight. If the styrene-based monomer is less than 40% by weight, the fluidity is low, and if it exceeds 90% by weight, the impact resistance is lowered. If the amount of the nitrile monomer is less than 5% by weight, the impact resistance is low, and if it exceeds 50% by weight, the fluidity is lowered.

The antibacterial hydroxyapatite used in the present invention is one in which a metal having a bactericidal action is adsorbed and immobilized on hydroxyapatite in an ionic state.
As the antibacterial metal, silver, copper and zinc are preferable. Further, hydroxyapatite is hydroxyapatite represented by the following formula [III]. M ₁₀ (XO ₄ ) ₆ (OH) ₂ ... [III] (In the formula, M is an alkali metal such as Ca, Ba, or Mg;
Are P, Si, and C. )

The content of the antibacterial hydroxyapatite of the present invention is 0.1 to 5% by weight based on the whole thermoplastic resin composition. The content of antibacterial hydroxyapatite
If it is less than 0.1% by weight, the bactericidal property is not sufficient,
If it exceeds, impact resistance and fluidity are deteriorated, which is not preferable.

The antibacterial thermoplastic resin composition of the present invention contains the polymer mixture in the range of 0.5 to 50% by weight, the rubber-containing styrene resin in the range of 45 to 99.4% by weight, and the antibacterial agent in the range of 0.1 to 5% by weight. Therefore, it is excellent in moldability and is also excellent in environmental stress crack resistance (chemical resistance), mechanical strength and antibacterial property.

In the present invention, the polymer mixture, the rubber-containing styrene resin and the antibacterial hydroxyapatite are mixed to prepare a thermoplastic resin composition. The mixing method is, for example,
The desired thermoplastic resin composition can be produced by mixing the polymer mixture in the form of powder or pellets and the rubber-containing styrene resin with the antibacterial hydroxyapatite. Examples of the mixing device include a Henschel mixer, a V-type blender, and a tumbler. Further, another mixing method is a melt-kneading method, and specific examples of the melt-kneading device include a Banbury mixer, a cokneader, a single-screw or twin-screw extruder, and a mixing roll.

[0048]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The parts and% described in Examples and Comparative Examples are
All by weight.

Examples 1 to 6 Comparative Examples 1 to 6 [Production of (A) Component Polymer A-1 to A-3] 150 parts of pure water and 2 parts of potassium stearate were charged into an autoclave and stirred. While heating to 50 degrees Celsius. 0.005 parts of ferrous sulfate heptahydrate, ethylenediamine 4
An aqueous solution prepared by dissolving 0.01 parts of tetrasodium acetate dihydrate and 0.3 parts of sodium formaldehyde sulfoxylate dihydrate in 10 parts of pure water was injected. Then, 100 parts of the monomer mixture having the composition shown in Table 1 was continuously added over 4 hours. At the same time, an aqueous solution prepared by dissolving 0.05 part of potassium persulfate in 25 parts of pure water was continuously added over 6 hours. After the addition of the monomer mixture was completed, 0.1 part of diisopropylbenzene hydroperoxide was added, the temperature of the system was raised to 70 ° C., and the mixture was further stirred for 2 hours to complete the polymerization.

[0050]

[Table 1]

[Production of Component (B) Polymer--B-1 to
B-4] 120 parts of pure water and 2 parts of sodium dodecylbenzenesulfonate were charged into an autoclave and heated to 65 degrees Celsius while stirring. Here, ferrous sulfate heptahydrate 0.
005 parts, ethylenediaminetetraacetic acid tetrasodium salt dihydrate
An aqueous solution prepared by dissolving 0.01 part and 0.3 part of sodium formaldehyde sulfoxylate dihydrate in 10 parts of pure water was injected. Next, a monomer mixture having the composition shown in Table 2
20% of 100 parts was poured into an autoclave, and an aqueous solution prepared by dissolving 0.05 parts of potassium persulfate in 20 parts of pure water was continuously added over 6 hours. After addition to the potassium persulfate aqueous solution,
The contents of the autoclave were cooled to complete the polymerization.

[0052]

[Table 2]

[Production of Polymer Mixture] 50 parts of the component (A) polymer emulsion (as the solid content of the polymer) and 50 parts of the (B) polymer emulsion (as the solid content of the polymer) are emulsified. Mix in a liquid state, and further polyethylene glycol-polypropylene glycol block copolymer (80% ethylene oxide polymerization ratio in the total molecule, polypropylene glycol molecular weight 1750, manufactured by Asahi Denka Co., Ltd., trade name Pluronic F-68) 0.7 Parts of 10% aqueous solution were added. next,
An aqueous solution prepared by dissolving 5 parts of calcium chloride / dihydrate in 400 parts of pure water was heated to 80 to 95 ° C., and the mixed emulsion was poured into the mixture while stirring to precipitate a polymer mixture.
The obtained slurry was filtered, washed with water, and dried in an atmosphere of 70 ° C to obtain a polymer mixture.

Each physical property value was determined by the following methods. (1) Glass transition temperature (A) component polymer or (B) component polymer Emulsion liquid was dropped into methanol to obtain a solid, which was then dried, and a 910 differential scanning calorimeter and 990 thermal analysis using a Dupont measuring instrument were performed. It measured using the meter.

(2) Gel content (A) component polymer or (B) component polymer Emulsion liquid was dropped into methanol to obtain a solid, which was dried to about 1.0 g.
Was precisely weighed, measured by the method described above, and calculated by the formula [II]. However, the solvent used was different between the component (A) polymer and the component (B) polymer, methyl ethyl ketone was used for the component (A) polymer, and toluene was used for the component (B) polymer.

(3) Solubility Parameter The solubility parameter value [unit is (cal / cc) ^1/2 ] of each polymer used for calculating the solubility parameter in each example is as follows. Butyl polyacrylate; 8.8 polymethylmethacrylate; 9.5 polyacrylonitrile; 12.5 polystyrene; 9.1

(4) Weight average molecular weight Two GMH-6 type columns manufactured by Toyo Soda Kogyo Co., Ltd. HLC-802A type gel permeation chromatography were serially measured. A refractometer was used as the detector, and tetrahydrofuran was used as the solvent. As the sample, a solid obtained by precipitating the component (A) polymer emulsion with methanol was used.

[Production of Thermoplastic Resin Composition] Polybutadiene 50%, Acrylonitrile 13% and Styrene 37
% ABS resin powder, 30% acrylonitrile and 70% styrene AS resin beads (polystyrene-based weight average molecular weight 1.1 × 10 ⁵ ), polymer mixture powder ((A) component polymer (A-species)) B) Component polymer (B-
(Species) in the ratio shown in Table 3) and antibacterial hydroxyapatato (manufactured by Sangi Co., Ltd., trade name Apacider A) are mixed in a Henschel mixer, and a central machine VC-40 (single shaft with vent) is mixed. It was supplied to an extruder to obtain pellets. Next, a physical property measurement sample was prepared using the pellets, and physical properties were measured. The results are shown in Tables 3 and 4.

[0059]

[Table 3]

[0060]

[Table 4]

The physical properties of the examples and comparative examples were determined by the following methods. (1) Tensile strength ASTM D-638 (2) Izod impact strength ASTM D-256 (3) Vicat softening point JIS K-6870 (4) Melt flow rate JIS K-6874

(5) Chemical resistance ASTM D-638 type I dumbbells were flexed by 50 mm, fixed on a jig, coated with acetic acid, and the time required for breaking when left at 23 ° C was measured. It is represented by. In addition,> 300 in Table 3 shows that it does not break even after 300 minutes.

(6) Antibacterial property The antibacterial property was measured according to JIS Z-2911. A 50 mm × 50 mm × 2 mm sample was placed on the medium in a petri dish, and a mold spore suspension (about 1 g) was sprayed on the medium, and the mixture was allowed to stand in a 27 ° C. atmosphere for 14 days to observe the growth state of mycelia. The bacteria used are Asp
ergillus niger FERM S-1, Penicillium citrinum Thom
FER-M S-5, Rhizopus stolonifer Lind FERM S-7, Clad
osporium cladosporioides de Vrieg FERM S-8, Chaeto
mium globosum kunzeex Fries FERM S-11 was used.
The antibacterial property was evaluated according to the following criteria. A: No hyphal growth was observed in the sample. B: Mycelia developed in the sample at 1/3 or less of the sample. C: Mycelia developed in the sample at 1/3 or more of the sample.

[0064]

As described above, since the antibacterial thermoplastic resin composition of the present invention is excellent in moldability, mechanical strength, environmental stress crack resistance and antibacterial property, it can be used for kitchen appliances, bathroom appliances,
It is useful as a molding material used in places with high humidity such as washing machines and refrigerators.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C08L 55/02 LMB 7142-4J LME 7142-4J 57/00 LMH 7242-4J

Claims (1)

[Claims] 1. (A) It is a polymer of vinyl type monomer, its glass transition temperature is over 20 degrees Celsius, gel content is 10% or less, and its solubility parameter is 9.0-11.0.
20 to 90% by weight of a polymer emulsion having a (cal / cc) ^1/2 and a polystyrene-based weight average molecular weight of 2 × 10 ⁵ or more and less than 40 × 10 ⁵ (as solid content of polymer) )When,
(B) A homopolymer of an acrylic acid ester monomer or a copolymer of an acrylic acid ester monomer and another copolymerizable monomer, having a glass transition temperature of 20 ° C. or lower and containing a gel. The ratio is 70% or less, and the solubility parameter is
Polymer emulsion of 8.4 to 9.8 (cal / cc) ^1/2 10 to 80
0.5 to 50% by weight of a polymer mixture of the component (A) component polymer and the component (B) polymer, which is obtained by mixing the polymer with the weight% (as the solid content of the polymer) in the emulsion state and then separating from the emulsion. %, 2. 45-99.4% by weight of rubber-containing styrene resin and 3. An antibacterial thermoplastic resin composition comprising 0.1 to 5% by weight of antibacterial hydroxyapatite.