JPH08143740A - Antibacterial thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] [Object] An object of the present invention is to obtain a resin composition capable of obtaining an extruded sheet having an excellent balance of physical properties such as antibacterial properties, chemical resistance, and impact strength development. [Structure] An antibacterial thermoplastic resin composition for an extruded sheet, which comprises a thermoplastic resin and an antibacterial zeolite, and the antibacterial zeolite is in the range of 0.1 to 5% by weight based on the total weight of the thermoplastic resin. Stuff.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition for extruded sheets which has excellent antibacterial properties, chemical resistance and impact resistance.

More specifically, by using antibacterial zeolite in a thermoplastic resin containing an acrylic rubber resin and a high nitrile resin, refrigerator parts (inner box for incorporating the interior of the refrigerator), sink, toilet Suitable for parts etc.

[0003]

2. Description of the Related Art Conventionally, as an inorganic antibacterial agent, for example, activated carbon carrying silver has been disclosed (JP-A-49-61950).
No.), and N- (fluorodichloromethylthio) -phthalimide, for example, is known as an organic antibacterial and antifungal agent.
However, the former (inorganic type) has a problem that silver ions are quickly eluted into a solution and an antibacterial effect cannot be obtained permanently. On the other hand, the latter (organic type) may not show an antibacterial action depending on the type of bacteria (lacks versatility depending on the type of bacteria), and even if it is a type with heat resistance, it is 150 to 300 ° C. In some cases, when kneaded into the resin, it decomposes or evaporates, and the effect decreases.

As a solution to the above problems of conventional antibacterial agents, so-called antibacterial zeolite in which an antibacterial component is supported on zeolite has been developed (Japanese Patent Publication No. Sho 6).
1-22977, JP-A-60-181002).

It is well known that thermoplastic resins such as ABS, PS, MMA and PC are molded into sheets, pipes, round bars and the like by an extruder and are commercially available. These are secondarily molded and used for Kanban, refrigerator inner box, file, rain doy, etc.

[0006] The ASA resin also has good chemical resistance (property that cracks are less likely to occur under environmental stress) to relatively polar solvents such as alcohols, organic halides and fatty acids. It is known. However, the conventional ASA resin is insufficient for chemicals such as CFC 141b, dioctyl phthalate, and detergent that have a great influence on the ASA resin. Further, the ASA resin has a defect that impact strength development is low. In order to obtain high impact strength manifestation, usually, a means of increasing the rubber content is adopted, but this method leads to a decrease in surface hardness and rigidity, so that the use application of the resin is significantly limited, which is not preferable. .

[0007]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As a result of intensive investigations by the present inventors in order to obtain a resin composition having an excellent physical property balance among antibacterial properties, chemical resistance, and impact strength development, zeolite (inorganic antibacterial agent) was selected. Antibacterial activity can be maintained semi-permanently by using, and the graft copolymer having an acrylic ester rubber component, by blending a graft copolymer using a conjugated diene rubber and a high acrylonitrile copolymer, It was found that a resin composition capable of obtaining an extruded sheet having an excellent balance of physical properties such as antibacterial property, chemical resistance, and impact strength development can be obtained, and the present invention has been accomplished.

[0008]

SUMMARY OF THE INVENTION The gist of the present invention consists of a thermoplastic resin and an antibacterial zeolite,
An antibacterial thermoplastic resin composition for an extruded sheet, wherein the antibacterial zeolite is in the range of 0.1 to 5% by weight based on the total weight of the thermoplastic resin.

By incorporating an antibacterial zeolite (silver compound inorganic antibacterial agent) into the thermoplastic resin sheet plate, growth of microorganisms such as mold, yeast and bacteria is suppressed and a clean atmosphere state is created on the surface of the sheet plate. The antibacterial action of silver lasts forever. The reason for this is that when the zeolite (silver-based inorganic compound) itself is stored in air, there is no decomposition, vaporization, evaporation, etc. of silver ions in the zeolite and it lasts semipermanently. Zeolite as an antibacterial agent is effective in a small amount, but is preferably contained in an amount of 0.1 to 5% by weight based on the thermoplastic resin.

The present invention will be described in more detail below. In the present invention, as the "zeolite", both natural zeolite and synthetic zeolite can be used. Zeolite is generally an aluminosilicate having a three-dimensional skeleton structure, and has a general formula of XM ₂ /nO.Al ₂ O
Displayed as ₃ · YSiO ₂ · ZH ₂ O. Here, M represents an ion-exchangeable ion and is usually a monovalent or divalent metal ion. n is the valence of the (metal) ion.
X and Y represent the respective metal oxides, silica coefficient, and Z represents the number of crystal waters.

The antibacterial metal ion in the antibacterial zeolite used in the present invention is at least one kind of metal ion selected from the group consisting of silver ion, copper ion and zinc ion.

The content of silver ions in zeolite is 0.1
It is suitable to be -15%, preferably 0.1-5% from the viewpoint of exhibiting excellent antibacterial activity. Further, the content of copper ions in the zeolite is preferably 0.1 to 8%, and the content of zinc ions is preferably 0.1 to 8%.

The antibacterial zeolite used in the present invention is characterized by excellent heat resistance (550 ° C.), is extremely thermally stable, and no composition change is observed at 220 to 250 ° C. The crystal structure is stable even when the temperature is raised to around 500 ° C.

Therefore, even if the thermoplastic resin containing the antibacterial zeolite is molded under normal sheet extrusion conditions, the resin does not discolor.

The thermoplastic resin used in the present invention will be described in detail below.

The acrylic acid alkyl ester rubbery copolymer (a) used for the graft copolymer (A) is composed of 15 to 99.9% by weight of alkyl acrylate and a conjugated diene and / or alkyl acrylate. It is obtained by emulsion-copolymerizing 0.1 to 85% by weight of a copolymerizable monomer.

The term "acrylic acid alkyl ester" as used herein refers to an acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms or an aromatic acrylic acid ester having a benzene ring such as a phenyl group or a benzyl group, and is preferable. Examples thereof include n-butyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, and the like, and one kind or two or more kinds can be used. If the amount used is 30% by weight or less, an acrylic ester compound having a functional group such as glycidyl acrylate, 2-hydroxyethyl acrylate, tetrahydrofurfuryl acrylate, dimethylaminoethyl acrylate is used in combination with the above. It is also possible to do so.

Examples of the conjugated diene include 1,3-butadiene, isoprene, chloroprene and the like.

The monomers copolymerizable with the alkyl acrylate ester include allyl acrylate, allyl methacrylate, divinylbenzene, ethylene glycol dimethacrylate, butylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, and triaryl isocyanurate. Polyfunctional monomers such as methylolpropane triacrylate and pentaerythritol tetraacrylate, unsaturated cyan compounds such as acrylonitrile, aromatic vinyl compounds such as styrene, alkyl methacrylates such as methyl methacrylate, and unsaturated compounds such as methacrylic acid. A monofunctional monomer such as a carboxylic acid compound can be used, and one kind or two or more kinds can be used. When the amount of conjugated diene used is small, one or more polyfunctional monomers are usually used.

The proportion of the alkyl acrylate in the rubber acrylic copolymer (a) is 15 to 99.9% by weight, which is 35 to 35 in terms of performance balance between impact strength development and chemical resistance. It is more preferably 85% by weight. If the blending amount is less than 15% by weight, the chemical resistance of the resin composition becomes poor, which is not preferable.
If the amount exceeds 9.9% by weight, the crosslinked structure of the rubber-like polymer is insufficient, and the impact strength development and appearance of the resin composition are impaired, which is not preferable. From the viewpoint of impact strength development, the gel content of the rubbery copolymer (a) needs to be 70% by weight or more.

The average particle diameter of the rubbery copolymer (a) is
The range of 0.03 to 0.2 μm is preferable. The rubbery copolymer (a) is an acid group-containing copolymer latex (i).
Alternatively, if necessary, by adding a metal salt of oxyacid (ii) to the acid group-containing copolymer latex (i),
0.15-0.5 μm, preferably 0.2-0.4 μm
Is enlarged to the size of. By using the enlargement operation, a rubber having a large particle size can be stably obtained in a short time.

The acid group-containing copolymer latex (i) is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid, sorbic acid and p-styrenesulfonic acid. 3 to 40% by weight of one or more unsaturated acids, the number of carbon atoms of the alkyl group is 1 to 12
It can be obtained by emulsion polymerization of 97 to 35% by weight of at least one kind of the acrylic acid alkyl ester and 0 to 40% by weight of another monomer copolymerizable therewith. Of these, a copolymer of methacrylic acid and butyl acrylate is a good example.

Metal salt of oxyacid used in the present invention (ii)
Is an alkali metal salt or alkaline earth metal salt of oxyacid mainly containing an element selected from the group of elements belonging to the second and third periods of Groups IIIA to VIA in the periodic table of elements. ,
One or more oxyacid salts selected from salts of zinc, nickel and aluminum, specifically, salts of sulfuric acid, nitric acid, phosphoric acid with potassium, sodium, magnesium, calcium, zinc and aluminum, Preferred examples include potassium sulfate, sodium sulfate, and sodium phosphate. The metal salt of oxyacid (ii) is added in the form of an aqueous solution.

The amount of the above-mentioned thickening agent added is 100 parts by weight (as a solid content) of the alkyl acrylate rubber copolymer (a) (as a solid content), and the acid group-containing copolymer latex (i) of 0. 5 to 8 parts by weight (as solid content), and 0.5 to 5 parts by weight (as solid content) of the acid group-containing copolymer latex (i) when the metal salt of oxygen acid (ii) is used in combination.
And 0.05 to 2 parts by weight (as solid content) of an aqueous solution of a metal salt of oxyacid (ii).

The enlarged rubber-like copolymer (a ') latex thus obtained is subsequently subjected to graft polymerization. Graft polymerization is carried out by using the enlarged rubber-like copolymer (a ')
It is carried out by graft-polymerizing 20 to 80 parts by weight of at least one monomer selected from unsaturated cyan compounds, aromatic vinyl compounds and unsaturated ester compounds in the presence of 20 to 80 parts by weight of latex. If the amount of the monomer used in the graft polymerization is less than 20 parts by weight, coarse particles may be generated in the coagulation step after the graft polymerization or the appearance of the resin composition may be deteriorated, which is not preferable. Further, when it is used in an amount of more than 80 parts by weight, a large amount of emulsifier is required in order to stably carry out the graft polymerization, and this causes coloring of the resin composition during thermal processing, which is not preferable.

Examples of unsaturated cyan compounds used in the graft polymerization include acrylonitrile, methacrylonitrile, ethacrylonitrile, maleonitrile and fumaronitrile. As the aromatic vinyl compound, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene,
p-ethylstyrene, p-tert-butylstyrene,
Halogenated styrene and the like are exemplified. Further, examples of the unsaturated ester compound include acrylic acid ester compounds such as methyl acrylate, ethyl acrylate, and butyl acrylate, and methacrylic acid such as methyl methacrylate, benzyl methacrylate, glycidyl methacrylate, and 2-hydroxyethyl methacrylate. Ester compounds are exemplified, and one or more of these are used in combination.

As the graft polymerization method, a known emulsion polymerization method can be adopted. It is possible to carry out a method in which the monomers are collectively charged and then polymerized, a method in which a part is charged first and the rest is dropped, and a method in which the entire amount is dropped and optionally polymerized, in one step or in two or more steps. It is also possible to change the kind and composition ratio of the monomer in each stage. The obtained graft copolymer latex is coagulated by a known method and is obtained as a graft copolymer (A) through steps such as dehydration, washing and drying.

The composite rubbery polymer (b ') latex used for the graft copolymer (B) is a conjugated diene rubbery polymer (b-1) latex or a polyorganosiloxane rubbery polymer (b). -2) seed polymerizing 20 to 95% by weight of a monomer mixture consisting of an alkyl acrylate ester and a monomer copolymerizable therewith in the presence of 5 to 80% by weight (as solid content) of a latex. Is obtained by

The conjugated diene rubbery polymer (b-1) used here is a copolymer comprising 50% by weight or more of a conjugated diene and 50% by weight or less of a monomer copolymerizable therewith. is there. Examples of the conjugated diene include 1,3-butadiene, isoprene and chloroprene, and examples of the copolymerizable monomer include unsaturated cyan compounds such as acrylonitrile and aromatic vinyl compounds such as styrene. Preferable examples of the conjugated diene rubbery polymer include polybutadiene, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber and the like. They are,
Obtained by emulsion polymerization.

The conjugated diene rubbery polymer (b-1) latex is preferably large particles having an average particle diameter of 0.2 to 0.8 μm. The rubber of such a large particle is 0.03
By stably adding a thickening agent similar to the acid group-containing copolymer latex (i) used in the graft copolymer (A) to the base rubber latex having a particle diameter of 0.15 μm, the stability and efficiency can be improved. can get. In order to obtain a large particle of enlarged rubber as shown here, the pH of the base rubber latex should be
Is 9 or more and it is necessary to use an acid group-containing copolymer latex having a high unsaturated acid content. In the bloat operation, it is rare that all the base rubbers become bloated rubbers, and usually a certain amount of unbloated base rubber remains. Therefore, the enlarged rubber has a two-dispersion particle size distribution. The preferred average particle size range of the conjugated diene rubber is 0.2 to 0.8 μm.
However, when focusing only on the large particle size side in the expanded rubber excluding the unexpanded base rubber, the average particle size is
0.4 to 1.0 μm is a preferable range.

On the other hand, polyorganosiloxane (b-2)
Is a component composed of an organosiloxane and, if necessary, a crosslinking agent and / or a graft crossing agent. Examples of the organosiloxane include various cyclic compounds having a 3-membered ring or more, and a 3- to 6-membered ring is preferably used. For example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
Examples thereof include trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and these may be used alone or in combination of two or more.

As the crosslinking agent, a trifunctional or tetrafunctional silane type crosslinking agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane,
Tetrabutoxysilane or the like is used. Particularly, a tetrafunctional crosslinking agent is preferable, and tetraethoxysilane is particularly preferable. The amount of the crosslinking agent used is 0 to 30% by weight in the polyorganosiloxane (b-2).

[0033] As the graft-linking agent, the following formula ^{_{CH 2 = C (R 2)}} -COO- (CH 2) p -SiR 1 n O (3-n) / 2 - (I) CH 2 = CH-SiR 1 _{n O (3-n) /} 2 - (II) HS- (CH 2) p -SiR 1 n O (3-n) / 2 - (III) ( the formulas R ¹ is a methyl group, an ethyl group, a propyl Group or phenyl group, R ² is a hydrogen atom or a methyl group, n is 0,
1 or 2, and p represents a number of 1 to 6. A compound capable of forming the unit represented by the formula (1) is used. The (meth) acryloyloxysiloxane capable of forming the unit of the formula (I) has a high grafting efficiency and thus can form an effective graft chain, which is advantageous in terms of impact resistance expression. Methacryloyloxysiloxane is particularly preferable as a unit capable of forming the unit of formula (I). Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-
Examples thereof include methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, and δ-methacryloyloxybutyldiethoxymethylsilane. The amount of the graft crossing agent used is 0 to 10% by weight in the polyorganosiloxane (b-2).
Is.

The average particle size of the polyorganosiloxane (b-2) latex is preferably in the range of 0.08 to 0.6 μm. When the average particle size is less than 0.08 μm, the impact resistance of the molded product obtained from the resin composition deteriorates, and when the average particle size exceeds 0.6 μm, the impact resistance of the molded product obtained from the resin composition. Is deteriorated, and the appearance of the molded surface is deteriorated, which is not preferable.

The polyorganosiloxane (b-2) latex can be produced by the method described in, for example, US Pat. Nos. 2,891,920 and 3,294,725. It is preferable to prepare a mixture solution of a graft crossing agent, if necessary, by a method of shear mixing with water using a homogenizer or the like in the presence of a sulfonic acid emulsifier such as alkylbenzene sulfonic acid or alkyl sulfonic acid. Alkylbenzene sulfonic acid is suitable because it acts as an emulsifier of the organosiloxane and at the same time serves as a polymerization initiator. At this time, alkylbenzene sulfonic acid metal salt,
It is preferable to use a metal salt of alkyl sulfonic acid in combination, because it is effective in maintaining the polymer stably during the graft polymerization.

The polyorganosiloxane rubber-like polymer (b-2) latex is neutralized by the addition of an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide or sodium carbonate, and then the following alkyl acrylate is mainly added. It is used for seed polymerization of the monomer as a component.

The composite rubbery polymer (b ') latex is
In the presence of 5 to 80% by weight (as a solid content) of the conjugated diene rubbery polymer (b-1) latex or the polyorganosiloxane (b-2) latex, an acrylic acid alkyl ester and a monomer copolymerizable therewith can be used. It is obtained by seed polymerization of 20 to 95% by weight of a monomer mixture containing a monomer.

Examples of the alkyl acrylate include the same ones as those used in the graft copolymer (A). Examples of the monomer copolymerizable with the acrylic acid alkyl ester include monofunctional monomers such as acrylonitrile, styrene, n-hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate, and crosslinking agents and grafts shown below. Examples include polyfunctional monomers such as crossing agents. Of these, it is preferable to use a cross-linking agent and a graft crossing agent in combination in terms of impact strength development.

Examples of the cross-linking agent include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate and 1,4-butylene glycol dimethacrylate, and examples of the graft crossing agent include allyl methacrylate. , Triallyl cyanurate, triallyl isocyanurate and the like. These crosslinking agents and graft crossing agents may be used alone or in combination of two or more.

The total amount of the cross-linking agent and the graft crossing agent used is 0.1 to 10% by weight in the monomer mixture containing alkyl acrylate as a main component, and the monofunctional monomer is 0 to 0% by weight. It is preferably 30% by weight. In addition, the composite rubber-like polymer (b ') needs to have a gel content of 70% by weight or more from the viewpoint of impact strength development.

The method of seed polymerization of a monomer mixture containing an alkyl acrylate as a main component in the presence of a conjugated diene rubbery polymer (b-1) latex or a polyorganosiloxane (b-2) latex is as follows. A method of dropping a monomer mixture while polymerizing at any time, a method of preliminarily impregnating a base rubber-like polymer with a monomer mixture and then polymerizing by adding an initiator or the like, a polymerization after impregnating a monomer mixture A method of continuously performing the operation for several times while changing the composition of the monomer mixture in each stage can be mentioned. Of these, the method of preliminarily impregnating the base rubber-like polymer with the monomer mixture and then polymerizing is preferred. In addition, during seed polymerization, an emulsifier may be newly added for the purpose of improving polymerization stability, but the amount thereof is preferably as small as possible.

The obtained composite rubbery polymer (b ') latex is subsequently subjected to graft polymerization. Graft polymerization is carried out by using a composite rubber-like polymer (b ') latex 20-8.
It is carried out by graft-polymerizing 20 to 80 parts by weight of one or more kinds of monomers selected from unsaturated cyan compounds, aromatic vinyl compounds and unsaturated ester compounds in the presence of 0 parts by weight (as solid content). .

The kind and amount of the monomer used in the graft polymerization and the method of the graft polymerization are the same as those in the graft copolymer (A). The latex obtained is coagulated,
The graft copolymer (B) is obtained through steps such as dehydration, washing and drying.

The latex of the conjugated diene rubbery copolymer (c) used for the graft copolymer (II) is 70 to 100% by weight of the conjugated diene and 0 to 3 monomers copolymerizable therewith.
It is obtained by emulsion polymerization with 0% by weight.

The conjugated diene used here is 1,3.
-Butadiene, isoprene and chloroprene are preferred examples, and it is preferable to use 70% by weight or more from the viewpoint of developing impact strength.

As the monomer copolymerizable with the conjugated diene, unsaturated cyan compounds such as acrylonitrile, aromatic vinyl compounds such as styrene, methacrylic acid alkyl esters such as methyl methacrylate, and unsaturated compounds such as methacrylic acid. A monomer such as a carboxylic acid compound can be used, and one kind or two or more kinds can be used.

The average particle size of the latex of the conjugated diene rubbery copolymer (c) is preferably 0.03 to 0.2 μm. The latex of the conjugated diene-based rubbery copolymer (c) is the acid group-containing copolymer latex (i) of the type and amount described in the description of the graft copolymer (A) or, if necessary, a metal salt of oxygen acid. Addition of (ii) up to 0.15-0.5 μm, preferably 0.2-0.
Enlarged to 4 μm. By this bloat operation,
It is possible to stably obtain an enlarged rubber-like copolymer (c ′) latex having a large particle size suitable for impact strength development in a short time.

The enlarged rubber-like copolymer (c ') latex is subsequently subjected to graft polymerization. Graft polymerization is carried out by expanding rubber-like copolymer (c ') latex 20 to 8
It is carried out by graft-polymerizing 20 to 80 parts by weight of one or more kinds of monomers selected from unsaturated cyan compounds, aromatic vinyl compounds and unsaturated ester compounds in the presence of 0 parts by weight (as solid content). .

Preferred examples of the monomer used in the graft polymerization include those described in the description of the graft copolymer (A). As for the graft polymerization method, a known emulsion polymerization method can be adopted as in the case of the graft copolymer (A). The obtained graft copolymer latex is coagulated by a known method, and is subjected to steps such as dehydration, washing and drying to obtain a graft copolymer (II).

The copolymer used in the present invention is 35 to 6
It is obtained by polymerizing a monomer mixture consisting of 5 wt% of an unsaturated cyan compound and 65 to 35 wt% of an aromatic vinyl compound.

Here, examples of the unsaturated cyan compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, maleonitrile, fumaronitrile and the like, of which acrylonitrile is a preferable example.
Aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-ethylstyrene, p-tert-butylstyrene, 2,4.
-Dimethyl styrene, halogenated styrene, etc. are exemplified, and among these, styrene and α-methyl styrene are preferable.

The unsaturated cyan compound used in the copolymer (III) is required to be 35 to 65% by weight in the monomer mixture, and more preferably 40 to 60% by weight. The amount of unsaturated cyanide compound is 3 in the monomer mixture.
If it is less than 5% by weight, the chemical resistance of the resulting molded article will be insufficient, and if it exceeds 65% by weight, the fluidity at the time of molding will be inferior and yellowing will tend to occur during polymerization.

The thermoplastic resin composition of the present invention comprises one or more graft copolymers (I) and graft copolymers (I) selected from the group of graft copolymers (A) and graft copolymers (B). II) and the copolymer (III).

The blending ratio of the graft copolymer (I), the graft copolymer (II) and the copolymer (III) is such that the proportion of the rubber-like polymer in the thermoplastic resin composition (D) is within a preferable range. Is decided to become. That is, of the enlarged rubber-like copolymer (a '), the composite rubber-like polymer (b') and the enlarged rubber-like copolymer (c ') in 100% by weight of the thermoplastic resin composition (D). 15-30% by weight of total
And the proportion of the alkyl acrylate ester units forming the rubbery polymer is the thermoplastic resin composition (D) 10
It is blended so as to be 5 to 25% by weight with respect to 0% by weight.

When the total amount of the rubber-like polymer is less than 15% by weight, impact strength is poorly developed, which is not preferable, and when it exceeds 30% by weight, the surface hardness and rigidity are lowered and the use thereof is limited. Therefore, it is not preferable.
Further, if the acrylic acid alkyl ester unit forming the rubber-like polymer is less than 5% by weight, the chemical resistance is poor, which is not preferable, and if it exceeds 25% by weight, it is difficult to obtain excellent impact strength expression. Is not preferable.

To mix the antibacterial zeolite and the thermoplastic resin, they are usually mixed with a V-type blender, a Henschel mixer or the like. At this time, various stabilizers, lubricants, plasticizers, release agents are added as necessary. , Dyes, pigments, inorganic fillers,
Metal fine particles, antistatic agents, etc. can be added.
These mixtures are kneaded by a screw extruder, resin is extruded from a die and cooled by a roll to form a sheet. Further, these mixtures can be molded into a pipe, a round bar, a square mold or the like by using a deformed mold.

[0057]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In addition, "part" in the following Examples and Comparative Examples represents parts by weight. The average particle size of the rubber-like polymer latex was measured from an image photographed with a transmission electron microscope after fixing it with osmium tetroxide or the like.

First, a method for synthesizing a thermoplastic resin will be described. The antibacterial zeolite was added during blending (compounding).

Synthesis of alkyl acrylate rubber copolymer (a-1) n-butyl acrylate 40 parts 1,3-butadiene 60 parts diisopropylbenzene hydroperoxide 0.2 parts tert-dodecyl mercaptan 0.4 parts Potassium oleate 1 part Sodium N-lauroyl sarcosinate 1 part Rongalit 0.5 part Distilled water 195 parts For the substances other than 1,3-butadiene in the above composition, the oxygen contained therein is replaced with nitrogen. , So that the reaction was virtually not hindered. After that, add all substances to 5
A 0 liter autoclave was charged and the temperature was raised to 55 ° C with vigorous stirring. Add the following mixture to this,
Polymerization was carried out at 55 ° C. for 8 hours. As a result, an acrylic acid alkyl ester rubbery copolymer (a-1) latex having a monomer conversion rate of 99% and a particle size of 0.07 μm was obtained.

Ethylenediaminetetraacetic acid disodium salt 0.012 parts Ferrous sulfate heptahydrate 0.004 parts Distilled water 5 parts Synthesis of alkyl acrylate rubber copolymer (a-2) n -Butyl acrylate 79.4 parts 1,3-Butadiene 20 parts Allyl methacrylate 0.6 parts Diisopropylbenzene hydroperoxide 0.15 parts Potassium oleate 1 part Sodium N-lauroyl sarcosinate 1 part Rongalit 0.5 parts Distilled water 195 Parts and ethylenediaminetetraacetic acid disodium dihydrate 0.009 parts ferrous sulfate heptahydrate 0.003 parts distilled water 5 parts The above composition is prepared by adding an acrylic acid alkyl ester rubbery copolymer (a- Polymerization was performed by the same operation as in the synthesis of 1). As a result, the monomer conversion rate was 97% and the particle size was 0.07.
As a result, an acrylic acid alkyl ester-based rubbery copolymer (a-2) latex having a thickness of μm was obtained.

Synthesis of alkyl acrylate rubber copolymer (a-3) n-butyl acrylate 99 parts allyl methacrylate 0.8 parts divinylbenzene 0.2 parts diisopropylbenzene hydroperoxide 0.02 parts potassium oleate 1.2 parts Sodium N-lauroyl sarcosinate 0.8 parts Rongalit 0.4 parts Distilled water 198 parts The above composition was charged in a 50 liter polymerization vessel, and the oxygen in the vessel was completely replaced with nitrogen and then up to 50 ° C. The temperature was raised. The following mixture was added thereto, and polymerization was carried out at 50 ° C. for 5 hours. As a result, an alkyl acrylate-based rubbery copolymer (a-3) latex having a monomer conversion rate of 98% and a particle diameter of 0.14 μm was obtained.

Disodium ethylenediaminetetraacetate dihydrate 0.000015 parts Ferrous sulfate heptahydrate 0.000005 parts Distilled water 2 parts Synthesis of conjugated diene rubbery copolymer (c-1) 1,3 -Butadiene 100 parts Diisopropylbenzene hydroperoxide 0.2 parts tert-dodecyl mercaptan 0.5 parts Potassium oleate 1 part Disproportionated potassium rosinate 1 part Dextrose 0.3 parts Anhydrous sodium sulfate 0.18 parts Sodium hydroxide 0 .02 parts Distilled water 195 parts and sodium pyrophosphate decahydrate 0.5 parts Ferrous sulfate heptahydrate heptahydrate 0.005 parts Distilled water 5 parts The above composition is treated with an alkyl acrylate rubber-like copolymer Polymerization was performed for 9 hours by the same operation as the synthesis of the combined product (a-1). As a result, a conjugated diene rubbery copolymer (c- having a monomer conversion of 97% and a particle diameter of 0.08 μm)
1) A latex was obtained.

Synthesis of latex containing acid group-containing copolymer (i-1) 2.5 parts potassium oleate 2.5 parts potassium dioctylsulfosuccinate 2.5 parts ethylenediaminetetraacetic acid disodium dihydrate 0.012 parts ferrous sulfate 7-hydrated salt 0.004 parts Rongalit 0.5 parts distilled water 200 parts The above composition was charged into a 5 liter glass separable flask, the oxygen in the system was replaced with nitrogen while stirring, and the temperature was raised to 70 ° C. . The following monomer mixture, which had been subjected to nitrogen substitution, was added dropwise to the mixture over 4 hours for polymerization.

85 parts of n-butyl acrylate 15 parts of methacrylic acid 0.5 parts of cumene hydroperoxide Then, by holding at 70 ° C. for 1 hour, the acid group-containing copolymer (i-1) having a monomer conversion rate of 97% was obtained. ) A latex was obtained.

Synthesis of acid group-containing copolymer (i-2) Synthesis of acid group-containing copolymer (i-1) latex except that the composition of the monomer mixture to be dropped is changed as follows. Polymerization was performed by the same operation. As a result, an acid group-containing copolymer (i-2) latex having a monomer conversion rate of 96% was obtained.

N-Butyl acrylate 80 parts Methacrylic acid 20 parts Cumene hydroperoxide 0.5 parts Synthetic rubber-like copolymer (a-1) latex of graft copolymer (A-1) 50 parts (as solid content) Into a 20 liter separable flask,
After adding 0.4 parts of a 10% sodium sulfate aqueous solution with a solid content while stirring, the acid group-containing copolymer (i-1) was further added.
The latex was added in an amount of 1.3 parts by solid content, and the mixture was kept for 30 minutes while stirring as it was, and then 95 parts of distilled water was added.
As a result, an enlarged rubber-like copolymer (a'-1) latex having an average particle diameter of 0.27 µm was obtained.

Sodium N-lauroyl sarcosinate 1.25 parts Ethylenediaminetetraacetic acid disodium dihydrate 0.003 parts Ferrous sulfate heptahydrate 0.001 part Rongalit 0.5 parts Enlarged rubbery copolymer The above composition was added to the latex (a′-1), and the temperature was raised to 75 ° C. with stirring. Graft polymerization was carried out by dropwise adding the following monomer mixture over 120 minutes.

Acrylonitrile 15 parts Styrene 35 parts tert-Butyl hydroperoxide 0.3 parts n-Octyl mercaptan 0.1 parts After completion of dropping the monomer mixture, the mixture is kept for another 1 hour to obtain a graft copolymer latex. Was given. The graft copolymer latex was put into a dilute sulfuric acid aqueous solution to coagulate, and then dehydrated, washed, and dried to obtain a graft copolymer (A-1).

Synthesis of Graft Copolymer (A-2) The rubber-like copolymer (a-2) is used as the rubber-like polymer, and the acid group-containing copolymer is used as the bloating agent used in the bloat-up operation. (I-1) The graft copolymer (A) except that the acid group-containing copolymer (i-2) is used instead of the latex.
-1) is carried out in the same manner as in the synthesis of the graft copolymer (A-
2) was obtained. At this time, the enlarged rubber-like copolymer (a'-
The average particle diameter of 2) was 0.30 μm.

Synthesis of Graft Copolymer (A-3) Up to the point of obtaining an enlarged rubbery copolymer, the same procedure as in the synthesis of graft copolymer (A-1) was carried out.

Enlarged rubbery copolymer (a'-1) latex (as solid content) 60 parts Sodium N-lauroyl sarcosinate 0.75 parts Ethylenediaminetetraacetic acid disodium dihydrate 0.0015 parts Sulfuric acid first Iron heptahydrate 0.0005 parts Rongalit 0.4 parts The above composition was charged into a 20 liter separable flask and heated to 75 ° C with stirring, and then the following monomer mixture was added dropwise over 90 minutes. The graft polymerization was carried out.

Methyl methacrylate 36 parts Ethyl acrylate 4 parts Cumene hydroperoxide 0.15 parts n-octyl mercaptan 0.05 parts After completion of dropwise addition of the monomer mixture, the mixture is kept for 1 hour to obtain a graft copolymer latex. Was given. The graft copolymer latex was put into a dilute sulfuric acid aqueous solution to coagulate it, and then dehydrated, washed and dried to obtain a graft copolymer (A-3).

Synthesis of Graft Copolymer (A-4) The rubber-like copolymer (a-3) is used as the rubber-like polymer, and the acid group-containing copolymer is used as the swelling agent used in the swelling operation. (I-1) Graft copolymer (A) except that acid group-containing copolymer (i-2) was used instead of latex.
-1) is carried out in the same manner as in the synthesis of the graft copolymer (A-
4) was obtained. At this time, the enlarged rubber-like copolymer (a'-
The average particle diameter of 4) was 0.31 μm.

Synthesis of composite rubbery polymer (b'-1) The rubbery copolymer (c) was placed in a 20 liter separable flask.
-1) Charge 20 parts of latex in solid content. To this, 0.5 part of the acid group-containing copolymer (i-2) latex was added as a solid component while stirring, and the mixture was kept for 30 minutes as it was, and then 160 parts of distilled water was added to carry out the enlargement operation. .
As a result, an enlarged rubber-like copolymer having an average particle diameter of 0.37 μm was obtained.

N-Butyl acrylate 79.25 parts Allyl methacrylate 0.5 parts Ethylene glycol dimethacrylate 0.25 parts tert-Butyl hydroperoxide 0.2 parts To this, the above monomer mixture was added and sufficiently stirred. rear,
0.5 part of sodium N-lauroyl sarcosinate is dissolved, and the system is replaced with nitrogen to remove oxygen. Internal temperature 45
At the time when the temperature was raised to ° C, the following composition was added.

Rongalit 0.5 parts Ferrous sulfate heptahydrate 0.0003 parts Disodium ethylenediaminetetraacetate dihydrate 0.0009 parts Distilled water 10 parts As a result, polymerization starts and the internal temperature is up to about 70 ° C. Rose.
Then, the composite rubbery polymer (b'-1) latex was obtained by holding the mixture at 75 ° C for 90 minutes with stirring.

Synthesis of graft copolymer (B-1) Composite rubbery polymer (b'-1) latex (as solid content) 50 parts Sodium N-lauroyl sarcosinate 1.2 parts Rongalit 0.4 parts Sulfuric acid No. Monoiron / heptahydrate 0.001 part Ethylenediaminetetraacetic acid disodium / dihydrate 0.003 part Distilled water 100 parts The above composition was charged into a 20 liter separable flask and heated to 75 ° C with stirring. . Graft polymerization was carried out by dropwise adding the following monomer mixture over 120 minutes.

Acrylonitrile 15 parts Styrene 35 parts tert-Butyl hydroperoxide 0.3 parts n-Octyl mercaptan 0.1 parts After completion of dropping the monomer mixture, the mixture is further stirred for 1 hour to maintain the graft copolymerization. A coalesced latex was obtained. The graft copolymer latex was obtained as a powdery graft copolymer (B-1) by adding it to a dilute sulfuric acid aqueous solution to coagulate it, followed by dehydration, washing and drying.

Synthesis of composite rubbery polymer (b'-2) Dodecylbenzenesulfonic acid 1 part Sodium dodecylbenzenesulfonate 1 part Distilled water 200 parts To the above composition, a siloxane mixture having the following composition was added and added to a homomixer. After premixing at 10,000 rpm, it was emulsified and dispersed at a pressure of 300 kg / cm ² by a homogenizer to obtain an organosiloxane latex.

Tetraethoxysilane 1.2 parts γ-methacryloyloxypropyldimethoxymethylsilane 0.3 parts Octamethylcyclotetrasiloxane 58.5 parts This mixed solution is transferred to a 20 liter separable flask and stirred at 80 ° C. After heating for 5 hours, the mixture was allowed to stand at 20 ° C. for 48 hours, and then the pH of this latex was neutralized to 7.5 with an aqueous sodium hydroxide solution to obtain a polyorganosiloxane (b-2) latex. The average particle diameter was 0.16 μm. To this, 70 parts of distilled water was added, and the following monomer mixture was added while further stirring, and they were mixed sufficiently.

N-Butyl acrylate 38.4 parts Allyl methacrylate 1.2 parts Ethylene glycol dimethacrylate 0.4 parts tert-Butyl hydroperoxide 0.3 parts After the system was replaced with nitrogen to remove oxygen, the internal temperature was changed. Was heated to 50 ° C., and the following mixture was added to initiate polymerization.

Rongalit 0.3 parts Ferrous sulfate heptahydrate 0.002 parts Disodium ethylenediaminetetraacetate dihydrate 0.006 parts Distilled water 10 parts As a result, the internal temperature was raised to about 65 ° C. . Then 70
The composite rubbery polymer (b'-2) latex was obtained by keeping it at 2 ° C for 2 hours.

Synthesis of graft copolymer (B-2) Composite rubber-like polymer (b'-2) latex (as solid content) 60 parts Sodium dodecylbenzenesulfonate 0.3 parts Distilled water 80 parts , 20 liter separable flask and heated to 70 ° C. with stirring. The following monomer mixture was added dropwise to this over 60 minutes for graft polymerization.

Acrylonitrile 12 parts Styrene 28 parts Cumene hydroperoxide 0.2 parts tert-Dodecyl mercaptan 0.1 parts After completion of dropping and adding, a graft copolymer latex was obtained by holding for 2 hours while stirring. This graft copolymer latex was put into a calcium chloride aqueous solution to coagulate, dehydrated, washed, and dried to obtain a powdered graft copolymer (B-2).

Synthesis of Graft Copolymer (C-1) Conjugated Diene Rubber Copolymer (c-1) Latex 60
Parts (as solid content) were charged into a 20 liter separable flask, and the acid group-containing copolymer (i-1) was stirred.
The latex was added in an amount of 1.2 parts by solid content, and the mixture was kept for 30 minutes while stirring, and then 80 parts of distilled water was added. As a result, an enlarged rubber-like copolymer (c'-1) latex having an average particle diameter of 0.28 μm was obtained.

Disproportionated potassium rosinate 0.4 parts Sodium pyrophosphate decahydrate 0.02 parts Ferrous sulfate heptahydrate 0.005 parts Dextrose 0.4 parts Sodium hydroxide 0.02 parts Enlargement The above composition was added to the rubbery copolymer (c′-1) latex, and the temperature was raised to 60 ° C. with stirring. Graft polymerization was carried out by dropwise adding the following monomer mixture over 120 minutes.

Acrylonitrile 12 parts Styrene 28 parts Cumene hydroperoxide 0.2 parts tert-Dodecyl mercaptan 0.4 parts After completion of dropwise addition of the monomer mixture, the mixture was kept for an additional 1 hour to obtain a graft copolymer latex. . The graft copolymer latex was put into a dilute sulfuric acid aqueous solution to coagulate, and then dehydrated, washed and dried to obtain a graft copolymer (C-1).

Synthesis of Copolymer (III-1) Acrylonitrile 45 parts Styrene 10 parts Terpene oil 0.50 parts Di-tert-butyl paracresol 0.04 parts Deionized water 90 parts Acrylic acid-octyl acrylate copolymer 03 parts Sodium chloride 0.18 parts A mixture of the above components was charged into a stainless steel reactor, heated to 105 ° C. with stirring under a nitrogen atmosphere, and 1-t-butylazo-1 dissolved in a small amount of styrene. -Cyano-cyclohexane (0.15 part by weight) was added by pressure under nitrogen to initiate the polymerization reaction. Immediately thereafter, 45 parts by weight of styrene was continuously added to the reaction system over 4 hours. During this time,
The reaction temperature was increased from 105 ° C at the start of polymerization to 141 ° C. After the continuous addition of styrene to the reaction system is completed,
The temperature was raised to 145 ° C over 20 minutes, and at this temperature 2.5
Time stripped. Thereafter, the reaction system was cooled, the polymer was separated, and the polymer was washed and dried according to a usual method to obtain a beaded copolymer (III-1).

Synthesis of Copolymer (III-2) Acrylonitrile 50 parts Styrene 8 parts Terpene oil 0.55 parts Di-tert-butylparacresol 0.04 parts Deionized water 90 parts Acrylic acid-octyl acrylate copolymer 03 parts Sodium chloride 0.18 parts A mixture of the above components was charged into a stainless steel reactor, heated to 105 ° C. with stirring under a nitrogen atmosphere, and 1-t-butylazo-1 dissolved in a small amount of styrene. -Cyano-cyclohexane (0.15 part by weight) was added by pressure under nitrogen to initiate the polymerization reaction. Immediately thereafter, 42 parts by weight of styrene was continuously added to the reaction system over 4 hours. During this time,
The reaction temperature was increased from 105 ° C at the start of polymerization to 141 ° C. After the continuous addition of styrene to the reaction system is completed,
The temperature was raised to 145 ° C over 20 minutes, and at this temperature 2.5
Time stripped. Thereafter, the reaction system was cooled, the polymer was separated, and the polymer was washed and dried according to a usual method to obtain a beaded copolymer (III-2).

Synthesis of copolymer (III-3) Acrylonitrile 60 parts Styrene 5 parts Terpene oil 0.58 parts Di-tert-butyl paracresol 0.04 parts Deionized water 90 parts Acrylic acid-octyl acrylate copolymer 0. 03 parts Sodium chloride 0.18 parts A mixture of the above components was charged into a stainless steel reactor, heated to 105 ° C. with stirring under a nitrogen atmosphere, and 1-t-butylazo-1 dissolved in a small amount of styrene. -Cyano-cyclohexane (0.15 part by weight) was added by pressure under nitrogen to initiate the polymerization reaction. Immediately thereafter, 35 parts by weight of styrene was continuously added to the reaction system over 4 hours. During this time,
The reaction temperature was increased from 105 ° C at the start of polymerization to 141 ° C. After the continuous addition of styrene to the reaction system is completed,
The temperature was raised to 145 ° C over 20 minutes, and at this temperature 2.5
Time stripped. Thereafter, the reaction system was cooled, the polymer was separated, and the polymer was washed and dried according to a usual method to obtain a beaded copolymer (III-3).

Synthesis of copolymer (III-4) acrylonitrile 29 parts styrene 55 parts terpene oil 0.58 parts di-tert-butyl paracresol 0.04 parts deionized water 100 parts acrylic acid-octyl acrylate copolymer 0. 02 parts Sodium chloride 0.14 parts A mixture of the above components was charged into a stainless steel reactor, heated to 105 ° C with stirring under a nitrogen atmosphere, and 1-t-butylazo-1 dissolved in a small amount of styrene. -Cyano-cyclohexane (0.15 part by weight) was added by pressure under nitrogen to initiate the polymerization reaction. Immediately thereafter, 16 parts by weight of styrene was continuously added to the reaction system over 1 hour. During this time,
The reaction temperature was increased from 105 ° C at the start of polymerization to 141 ° C. After the continuous addition of styrene to the reaction system is completed,
The temperature was raised to 145 ° C over 20 minutes, and at this temperature 2.5
Time stripped. Thereafter, the reaction system was cooled, the polymer was separated, and the polymer was washed and dried according to a usual method to obtain a beaded copolymer (III-4).

Examples 1 to 14 and Comparative Examples 1 to 2 In the proportions shown in Table 1, antibacterial zeolite (manufactured by Sinanen Zeomic Co., Ltd.), graft copolymer (I), graft copolymer (II) and The copolymer (III) was added to a Henschel mixer together with a stabilizer and blended.

The above mixture is kneaded at 200 to 250 ° C. by using a screw extruder of 120 mm, resin is extruded from a die and cooled by a roll to form a sheet.

A thermoplastic resin sheet containing antibacterial zeolite having a thickness of 2.0 × width of 1040 × 400 was obtained.

Various evaluation test pieces were prepared from the obtained sheets.

The antibacterial resin sheet composition thus obtained was evaluated by the following methods.

(1) Izod impact strength (IZ): AS
It was measured by TM D-256 (unit: kg · cm / cm).

(2) Rockwell hardness (R): ASTM
It was measured by D-785 (R scale).

(3) Vicat softening temperature (VST): IS
It was measured by OR-306 (unit: ° C).

(4) Chemical resistance: 35 × 120 mm test pieces are cut out from a 2 mm thick sheet molding plate of the resin composition and attached to a 1/4 elliptical jig having a major axis of 120 mm and a minor axis of 40 mm. After the chemical was applied to the surface of the test piece, it was covered with a polyethylene film and exposed to the chemical at 25 ° C. for 4 hours.
For low boiling point chemicals, the jig was placed in a desiccator with an opening / closing cock and exposed to the chemicals at 25 ° C. for 24 hours while being filled with the chemical vapor. After the exposure, the surface condition of the test piece was observed, and the maximum stress-strain value at which cracks did not occur was used as an index of chemical resistance.

The following chemicals were used as the chemicals.

-1,1-dichloro-1-fluoroethane (CFC 141b) -Magic phosphorus (manufactured by Kao) -Wax remover (ST-7 manufactured by Yushiro Kagaku) -Salad oil (manufactured by Nisshin Oil) -Dioctyl phthalate (DOP) (5) Antibacterial performance 1.3 × 10 ⁴ E. coli and 7.5 × Staphylococcus aureus on the test piece
The number is adjusted to 10 ^{4 and the} number of surviving cells after 24 hours at 35 ° C. is measured.

(6) Chemical resistance of vacuum-formed product The vacuum-formed product shown in FIG. 1 was placed together with Freon 141b in a desiccator with an opening / closing cock, and was filled with steam at 25 ° C.
Exposed to chemicals for 24 hours. After exposure, observe for cracks.

The results are shown in Table 1.

[0105]

[Table 1]

[0106]

The present invention is a thermoplastic resin composition for an extruded sheet, which contains an antibacterial zeolite in a thermoplastic resin,
The resulting sheet has excellent antibacterial properties, chemical resistance and impact resistance. Therefore, the thermoplastic resin composition of the present invention is extremely useful as parts such as urethane foaming agents, home appliances that come into contact with various oils and detergents, toilet parts, building materials, vehicles and the like.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location A01N 59/20 Z C08K 3/34

Claims (2)

[Claims] 1. An antibacterial thermoplastic for an extruded sheet, comprising a thermoplastic resin and an antibacterial zeolite, wherein the antibacterial zeolite is in the range of 0.1 to 5% by weight based on the total weight of the thermoplastic resin. Resin composition. 2. The thermoplastic resin according to claim 1, wherein the thermoplastic resin comprises (I) 15 to 99.9% by weight of an alkyl acrylate and 0.1 to 0.1% of a monomer copolymerizable with a conjugated diene and / or an alkyl acrylate. 85% by weight of an acrylic acid alkyl ester rubbery copolymer (a) latex obtained by emulsion polymerization with an acid group-containing copolymer latex (i) or, if necessary, the acid group-containing copolymer latex ( Enlarged rubber-like copolymer (a ') latex 20 obtained by adding metal salt (ii) of oxygen acid to i) in combination
To 80 parts by weight (as solid content) in the presence of 20 to 80 parts by weight of one or more monomers selected from unsaturated cyan compounds, aromatic vinyl compounds and unsaturated ester compounds Copolymer (A) and conjugated diene rubbery polymer (b-1) latex or polyorganosiloxane (b-2) latex 5 to 80% by weight
A composite rubbery polymer (b) obtained by seed polymerization of 20 to 95% by weight of a monomer mixture consisting of an alkyl acrylate and a monomer copolymerizable therewith in the presence of (as solid content). ′) Graft polymerization of 20 to 80 parts by weight of one or more monomers selected from unsaturated cyan compounds, aromatic vinyl compounds and unsaturated ester compounds in the presence of 20 to 80 parts by weight of latex (as solid content). One or more graft copolymers selected from the graft copolymer (B) thus obtained, (II) 70 to 100% by weight of conjugated diene and 0 to 30% by weight of a monomer copolymerizable therewith. The conjugated diene rubbery copolymer (c) latex obtained by emulsion polymerization is added to the acid group-containing copolymer latex (i) or, if necessary, the acid group-containing copolymer latex to a metal salt of oxygen acid ( ii) together Obtained by adding Te enlarged rubbery copolymer (c ') in the presence of the latex, unsaturated cyano compounds,
A graft copolymer obtained by graft-polymerizing one or more monomers selected from aromatic vinyl compounds and unsaturated ester compounds, and (III) 35-65% by weight of unsaturated cyan compound and 65-65.
A thermoplastic resin composition (D) comprising a copolymer obtained by copolymerizing a monomer comprising 35% by weight of an aromatic vinyl compound, wherein the thermoplastic resin composition (D) comprises: The total of the enlarged rubber-like copolymer (a '), the composite rubber-like polymer (b') and the enlarged rubber-like copolymer (c ') in 100% by weight of the thermoplastic resin composition (D). Is 15 to 30% by weight, and the proportion of acrylic acid alkyl ester units forming a rubber-like polymer is 5 to 25% by weight with respect to 100% by weight of the thermoplastic resin composition (D).
And a thermoplastic resin composition.