JPH09302007A - Rubber-like polymer latex, rubber-reinforced vinyl polymer, and thermoplastic polymer composition - Google Patents

Abstract

(57) 【Abstract】 PROBLEM TO BE SOLVED: A molded product having excellent polymerization stability and mechanical stability at the time of polymerization, coagulation property at the time of acid precipitation and salting-out, impact resistance, surface glossiness, thermal stability, color tone and the like. Of rubber-like polymer latex, which has excellent appearance and mold non-staining property, little eye tarnish (thermal discoloration), and a small load of polluted wastewater during production, and a rubber-reinforced vinyl type obtained using the rubber-like polymer To obtain a polymer, as well as its composition. SOLUTION: (a) A monomer component having a glass transition point of 10 ° C. or lower when converted to a polymer is (b) a carboxylate-based reactive emulsifier (b-1), and further, if necessary. A rubber-like polymer latex obtained by emulsion polymerization in the presence of an emulsifier containing another emulsifier, and a rubber-reinforced vinyl polymer obtained by polymerizing a vinyl monomer in the presence of this rubber-like polymer latex. And a thermoplastic polymer composition in which a thermoplastic polymer or the like is blended with the rubber-reinforced vinyl polymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is excellent in polymerization stability and mechanical stability at the time of polymerization, coagulability at the time of acid precipitation and salting out, and has impact resistance, surface glossiness, thermal stability, color tone and the like. A rubber-like polymer latex used as a raw material for the production of rubber-reinforced vinyl polymers, which has excellent appearance and non-contamination properties of molded products, has little eye blemishes (thermal discoloration), and has a low load of wastewater pollution during production. , A rubber-reinforced vinyl polymer obtained by using the rubber-like polymer, and a composition thereof.

[0002]

2. Description of the Related Art Polybutadiene rubber latex, SBR
A rubber-like polymer latex such as latex is used as a base rubber for a rubber-reinforced vinyl polymer such as ABS resin and MBS resin. These latexes are transported to the reactor during the production of the rubber-reinforced vinyl polymer, but if the stability of the latex against the mechanical share is insufficient at that time, the share in the pipe or the share by the pump will increase. For example, the rubber-reinforced vinyl polymer obtained can change the particle size of latex due to mechanical shear that causes stability and other problems that cause coagulation to precipitate, causing problems such as clogging, and even when coagulation does not precipitate. Cause the problem of changing the quality of. Therefore, the stability of the latex against mechanical shear is extremely important in the production of the latex.

Conventionally, as a method of ensuring the stability of the latex against mechanical shear, a method of increasing the amount of emulsifier during polymerization or a method of adding an emulsifier to the latex after polymerization is generally used. On the other hand, in recent years, rubber-reinforced vinyl polymers obtained by using these latexes as base rubber have become problems of mold contamination / corrosion during resin molding and corrosion of extrusion screw. Quality such as sex tends to be emphasized.

Therefore, it is preferable to reduce as much as possible the emulsifier which is one of the causes of these corrosion and poor quality. Therefore, a method of reducing the amount of the emulsifier in the product in the washing step in the manufacturing process of the rubber-reinforced vinyl polymer by appropriately limiting the type of the emulsifier can be considered, but this method has a problem of wastewater treatment and is not preferable. . As described above, none of the above methods can satisfy the demand of the age of reducing emulsifiers.

ABS resins and MBS resins, which are representative of rubber-reinforced vinyl polymers, are obtained by emulsion-polymerizing a vinyl monomer constituting a resin component in the presence of the rubber-like polymer latex. ing. The advantages of this emulsion polymerization method include that it is easy to control the polymerization temperature to obtain a polymer of excellent quality, that the polymerization equipment is not complicated, that safety is high, etc. Polymerization method.

However, in the emulsion polymerization of the rubber-reinforced vinyl polymer, the rubber-like polymer latex used does not have sufficient stability as described above, and therefore mechanical shear or monomer by stirring is used. Upon contact with the latex, the rubber component in the latex precipitates and becomes a coagulated substance, which is attached to the inner wall of the reactor and becomes a heat insulating material, which is a great obstacle to the control of the polymerization temperature. Therefore, in the on-site production of the rubber-reinforced vinyl polymer, it is necessary to frequently remove the solidified substance adhered to the inner wall of the reactor, which requires a great deal of labor to remove it, and the productivity of the polymerization is remarkably increased. Lower.

As a method for suppressing the generation of the above coagulated substance, a method of increasing the amount of the emulsifier in the latex or the emulsifier in the emulsion polymerization of the rubber-reinforced vinyl polymer is generally used. However, these emulsifiers are contained as impurities in the rubber-reinforced vinyl polymer product, and when the content of this emulsifier increases, the mold or the corrosion of the mold, the corrosion of the extrusion screw during the molding of the rubber-reinforced vinyl polymer. This has become a major problem in recent years. Further, in the quality of the rubber-reinforced vinyl polymer, it causes deterioration of heat resistance, color change due to deterioration of thermal stability, and transparency of the transparent rubber-reinforced vinyl polymer. Furthermore, when the rubber-reinforced vinyl polymer is recovered, this emulsifier is mixed in the waste water, which also causes the pollution of the waste water. Therefore, it is preferable to reduce the amount of the emulsifier causing these generations as much as possible.

On the other hand, the emulsion polymerization method is superior to other polymerization methods.
Although a rubber-reinforced vinyl polymer having a high graft ratio can be obtained, it is required to further increase the graft ratio.
This is because increasing the graft ratio improves the thermal stability, color tone, gloss and impact resistance. Conventionally, in order to increase the graft ratio, a polymerization method has been adopted in which productivity is sacrificed by using means such as lengthening the polymerization time. If the graft rate can be increased by a simple method, the productivity is improved. Therefore, it is required to improve the graft rate without sacrificing the productivity.

[0009]

SUMMARY OF THE INVENTION The present invention uses a reactive emulsifier having a carboxylic acid salt, which has never been used in emulsion polymerization, to obtain polymerization stability and mechanical stability at the time of polymerization. It has excellent coagulability during precipitation and salting-out, and also has excellent impact resistance, surface gloss, thermal stability, appearance of molded products such as color tone, excellent mold non-contamination property, and little eye blemishes (thermal discoloration). Small pollution load of wastewater during manufacturing,
It is intended to obtain a rubber-like polymer latex for a base rubber used as a raw material for producing a rubber-reinforced vinyl polymer, a rubber-reinforced vinyl polymer obtained by using the rubber-like polymer, and a composition thereof.

[0010]

According to the present invention, (b) 100 parts by weight of a monomer component having a glass transition point of 10 ° C. or lower when converted to a polymer is (b) a carboxylate-based reactive compound. Emulsifier (b-1) / other emulsifier (b-2) = 1 to 100/9
Obtained by emulsion polymerization in the presence of 0.01 to 10 parts by weight of an emulsifier consisting of 9 to 0% by weight. The rubber-like polymer has a gel content of 20 to 100% by weight and a Mooney viscosity (ML _{1 + 4} , 10
The rubbery polymer latex has a temperature of 0 to 10 ° C.

In the present invention, (c) in the presence of 3 to 80 parts by weight (as solid content) of the rubber-like polymer latex,
(D) 97 to 20 parts by weight of vinyl-based monomer [however,
(C) + (d) = 100 parts by weight], and 0.01 to 10 parts by weight of an emulsifier comprising (b) a carboxylate-based reactive emulsifier (b-1) and / or another emulsifier (b-2). Obtained by emulsion polymerization with a graft ratio of 5 to 200
A rubber-reinforced vinyl-based polymer, which is used in a weight percentage, is provided.

Further, according to the present invention, 1 to 99 parts by weight of (e) rubber-reinforced vinyl polymer and 99 to 1 parts by weight of another thermoplastic polymer (wherein (e) + (e) = 100 parts by weight] as the main component (hereinafter, also referred to as “(to) thermoplastic polymer composition”).

Further, the present invention provides the following (h-1) to (h-4) based on 100 parts by weight of the (e) rubber-reinforced vinyl polymer or the (v) thermoplastic polymer composition. The present invention provides a thermoplastic polymer composition (hereinafter also referred to as "(ri) thermoplastic polymer composition") in which at least one selected from the group is blended in the following amount. (Ch-1); 1 to 30 parts by weight of flame retardant (Ch-2); 0.01 to antibacterial agent and / or antifungal agent
10 parts by weight (h-3); antistatic agent 0.1 to 30 parts by weight (h-4); foaming agent 0.1 to 20 parts by weight

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION (c) The monomer component (b) used in the production of the rubber-like polymer latex (c) of the present invention has a glass transition point of not higher than 10 ° C. when it becomes a polymer. A quantity,
Alternatively, it is a combination of monomers. (I) The monomer used in the monomer component is a conjugated diene compound, an aromatic vinyl compound, a vinyl cyanide compound, a meta (acrylic) acid ester, a meta (acrylic) acid, a graft crossing agent and the like. In the monomer component (a), the glass transition point when it becomes a polymer is 10 ° C. or lower, that is, the rubber-forming monomer is the conjugated diene compound or the meth (acrylic) acid ester.

Among these, the conjugated diene compounds include 1,3-butadiene, isoprene and 2-chloro-
1,3-Butadiene, chloroprene and the like can be mentioned, with 1,3-butadiene being particularly preferred. As the aromatic vinyl compound, styrene, p-methylstyrene, o-
Methylstyrene, m-methylstyrene, t-butylstyrene, α-methylstyrene, 1,1-diphenylstyrene, N, N-diethyl-p-aminostyrene, N, N-
Diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, ethylstyrene,
Vinyl naphthalene and the like.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. As the meth (acrylic) ester, an ester of meth (acrylic) acid and a monohydric alcohol having 1 to 12, preferably 4 to 8 carbon atoms is suitable. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, butyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate,
Examples include isobonyl (meth) acrylate, and butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are particularly preferable.

Examples of meth (acrylic) acid include acrylic acid and methacrylic acid. The graft crossing agent is a polyfunctional vinyl monomer, that is, a monomer having a plurality of ethylenic double bonds. Examples of the graft crosslinking agent include divinylbenzene, ethylene glycol dimethacrylate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, trimethylolpropane triacrylate, allyl methacrylate, and the like. The graft crossing agent facilitates intermolecular cross-linking of, for example, a (meth) acrylic acid alkyl ester polymer and graft bond with the matrix, and the impact resistance of the obtained rubber-reinforced vinyl polymer is improved.

Among these (a) monomer components, preferred combinations include the following (a-1) or (a-2). (A-1); (a) 30 to 100% by weight, preferably 50 to 100% by weight, more preferably 60 to 100% by weight of a conjugated diene compound, and (b) other than the above (a) component copolymerizable 70% by weight of at least one other monomer selected from the group of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid alkyl esters and (meth) acrylic acid. , Preferably 50-
0% by weight, more preferably 40 to 0% by weight
(A) + (b) = 100% by weight] and has a glass transition point of 10 ° C. or lower, preferably 5 ° C., when it becomes a polymer.
The following monomer components are more preferably 0 ° C. or less.

Further preferable combinations of the monomer component (A-1) are as follows. (A) conjugated diene compound alone (a) conjugated diene compound / (b) aromatic vinyl compound (a) conjugated diene compound / (b) vinyl cyanide compound (a) conjugated diene compound / (b) (meth) acrylic acid Alkyl ester

(A-2); (c) 30 to 100% by weight of (meth) acrylic acid alkyl ester, preferably 50 to
100% by weight, more preferably 60-100% by weight
And (d) another monomer copolymerizable with the above-mentioned component (c),
For example, at least one other monomer 7 selected from the group consisting of a conjugated diene compound, an aromatic vinyl compound, a vinyl cyanide compound, (meth) acrylic acid and a graft crossing agent.
0 to 0% by weight, preferably 50 to 0% by weight, more preferably 40 to 0% by weight [(c) + (d) = 10
0% by weight] and has a glass transition point of 10 ° C. or lower, preferably 5 ° C. or lower, and more preferably 0 ° C. or lower when it becomes a polymer. The monomer component (a-
In 2), the alkyl group in (c) (meth) acrylic acid alkyl ester preferably has 2 to 12 carbon atoms, more preferably 3 to 8 and particularly preferably 4 to 6 carbon atoms.

Further preferred combinations of the monomer component (a-2) are as follows. (C) Alkyl (meth) acrylate / (d)
Graft crossing agent (c) (meth) acrylic acid alkyl ester / (d)
Conjugated diene compound (c) (meth) acrylic acid alkyl ester / (d)
At least one selected from the group of graft crossing agent / (d) aromatic vinyl compound, (d) vinyl cyanide compound, (d) (meth) acrylic acid and (d) conjugated diene compound.
Species (c) (meth) acrylic acid alkyl ester / (d)
Conjugated diene compound / (d) aromatic vinyl compound, (d)
At least one selected from the group of vinyl cyanide compounds, (d) (meth) acrylic acid and (d) graft crossing agents.
seed

When the amount of the rubber-forming monomer (a) conjugated diene compound or (c) (meth) acrylic acid alkyl ester in the component (a-1) or (a-2) is less than 30% by weight. However, the rubber elastic modulus decreases, the impact resistance of the obtained rubber-reinforced vinyl polymer or thermoplastic polymer composition decreases, and the desired physical properties cannot be obtained, which is not preferable. Further, the component (A-1) or (B-2) has a glass transition point (measured by DSC) of 10 when it becomes a polymer.
When the temperature is higher than 0 ° C, the rubber elastic modulus is lowered, the impact resistance and the fluidity of the obtained rubber-reinforced vinyl polymer or thermoplastic polymer composition are lowered, and the desired physical properties cannot be obtained, which is not preferable.

The rubber-like polymer latex (c) of the present invention requires a carboxylate-based reactive emulsifier (b-1) as an (b) emulsifier, and if necessary, other emulsifiers (b). 2) is used together. The carboxylate-based reactive emulsifier (b-1) has a double bond copolymerizable with the monomer, and the (c) rubbery polymer latex of the present invention obtained by using the double bond is Since the monomer component (a) and the carboxylate-based reactive emulsifier (b-1) are polymerized and copolymerized in the rubber-like polymer, a low-molecular-weight free emulsifier is contained in the obtained latex. It is possible to improve the deterioration of physical properties of the obtained rubber-reinforced vinyl polymer or thermoplastic polymer composition due to residual organic acid or soap. Since the carboxylate-based reactive emulsifier (b-1) has a carboxylate, it is possible to obtain a latex having excellent polymerization stability and mechanical stability and excellent coagulability during acid precipitation and salting out. To be

Here, the carboxylate-based reactive emulsifier (b-1) is an emulsifier having a highly unsaturated polymerizable unsaturated bond and a carboxylate. Among the carboxylate-based reactive emulsifiers (b-1), compounds having an amide structure are particularly preferable. Examples of such a carboxylate-based reactive emulsifier (b-1) include compounds of the following formula (1), but the present invention is not limited thereto.
In the following formula (1), X is H or CH ₃ , Y is CH or CH ₂ , Z is H or CH ₃ , and R is a carbon number of 6 to 1.
8 alkyl group, alkenyl group or aralkyl group,
n is 0 to 30, M is K or Na. Specific examples of the above formula (1) include compounds represented by the following formulas (2) to (4). In addition, as the carboxylate-based reactive emulsifier (b-1), a compound represented by the following formula (5) can be given. In these formulas (2) to (5), R, n and M are the same as above. These carboxylate-based reactive emulsifiers (b-1) may be used alone or in combination of two or more.

[0025]

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The carboxylate-based reactive emulsifier (low
In (1), a reactive emulsifier other than (b-1) (hereinafter also referred to as "other reactive emulsifier") may be used in combination, preferably in an amount of 5% by weight or less, more preferably 3% by weight or less. it can. The other reactive emulsifier is an emulsifier having a polymerizable unsaturated bond showing high reactivity such as vinyl group, acryloyl group, methacryloyl group, allyl group and propenyl group. As such other reactive emulsifiers,
It can be represented by the following formulas (6) to (11).

[0027]

[Chemical 6]

[Chemical 7]

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[In the formulas (6) to (11), R ^{1 to} R ^1
5 is the same or different and is an alkyl group having 6 to 18 carbon atoms,
Alkenyl group or aralkyl group, n'is an integer of 0 to 50, and M is a monovalent cation. Among these other reactive emulsifiers, preferred ones are
The compounds represented by the above formulas (6) and (11).
Particularly, in the formula (6), R ¹ is C ₉ H ₁₉ and M is NH ₄
In the compound represented by the formula (11), R ⁵ is C ₉ H
₁₉ , a compound in which M is NH ₄ is excellent in copolymerizability with a monomer, and the polymerization stability of the obtained copolymer latex is
It is preferable from the standpoint of leaving (low temperature, high temperature) and mechanical stability.

On the other hand, as the (b) emulsifier, other emulsifiers (b-2) which may be used in combination with the above carboxylate-based reactive emulsifier (b-1) include anionic surfactants and nonionic surfactants. Examples thereof include surfactants and amphoteric surfactants.

Among these, examples of anionic surfactants include sulfuric acid esters of higher alcohols, alkylbenzene sulfonates, aliphatic sulfonates, and sulfuric acid esters of polyethylene glycol alkyl ethers. As the nonionic surfactant, an alkyl ester type, an alkyl ether type, an alkyl phenyl ether type or the like of ordinary polyethylene glycol is used.

Further, examples of the amphoteric surfactant include those having a carboxylate salt, a sulfate ester salt, a sulfonate salt or a phosphate ester salt as an anion portion and an amine salt or a quaternary ammonium salt as a cation portion. To be Specific examples of the amphoteric surfactant include betaines such as lauryl betaine and stearyl betaine, amino acid types such as lauryl-β-alanine, stearyl-β-alanine, lauryl di (aminoethyl) glycine, and octyl di (aminoethyl) glycine. The thing etc. are used. These other emulsifiers (B-2) can be used alone or in combination of two or more.

(B) The ratio of the emulsifier used is 1 for the carboxylate-based reactive emulsifier (b-1) / the other emulsifier (b-2).
~ 100 / 99-0% by weight, preferably 20-100 /
80 to 0% by weight, more preferably 50 to 100/50
~ 0% by weight. Carboxylate reactive emulsifier (low
When the proportion of 1) used is less than 1% by weight, the polymerization stability and mechanical stability during emulsion polymerization are poor, the coagulability during acid precipitation and salting out is poor, and more free emulsifiers remain,
The obtained rubber-reinforced vinyl polymer or thermoplastic polymer composition is not preferable because it causes mold contamination and lowers thermal stability.

The total amount of the (b) emulsifier used is
(A) 0.01 to 10 with respect to 100 parts by weight of the monomer component
The amount is preferably 0.1 to 8 parts by weight, more preferably 0.5 to 8 parts by weight. Below 0.01 parts by weight,
On the other hand, the stability during emulsion polymerization is inferior. On the other hand, when it exceeds 10 parts by weight, the elasticity of the rubber-like polymer obtained is lowered and the impact resistance is deteriorated.

(C) The rubber-like polymer latex is added to water,
It can be obtained by emulsion polymerization according to a conventional method while stirring a mixture of the above (a) monomer component, (b) emulsifier, a polymerization initiator to be described later, a molecular weight modifier, an electrolyte and the like.

Here, as the polymerization initiator, water-soluble polymerization initiators such as sodium persulfate, potassium persulfate and ammonium persulfate, paramenthane hydroperoxide,
By combination with oil-soluble polymerization initiators such as diisopropylbenzene hydroperoxide, benzoyl peroxide, lauryl peroxide, 2,2'-azobisisobutyronitrile, reducing agents such as sugar-containing pyrophosphate formulation or sulfoxylate formulation Redox-based polymerization initiators and the like are used alone or in combination.

Examples of the molecular weight regulator include chloroform, halogenated hydrocarbons such as carbon tetrabromide, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid and the like. Xanthogens such as mercaptans, dimethylxanthogen disulfide, and diisopropylxanthogen disulfide, terpinolene, α
All those used in normal emulsion polymerization can be used, such as methylstyrene dimer. Further, as the electrolyte, potassium sulfate, potassium carbonate, sodium carbonate, potassium hydroxide, sodium bicarbonate, potassium phosphate and the like can be used alone or in combination of two or more. .

As the emulsion polymerization method, for example, (a) a method in which all the monomer components are charged at once and polymerized, or (a) a part of the monomer components is polymerized and the rest is continuously or intermittently A method of adding, a method of continuously adding the monomer component (a) from the beginning of the polymerization, a method of using seed particles, or the like can be adopted. The polymerization temperature is usually
0 to 95 ° C, preferably 30 to 90 ° C, more preferably 40 to 90 ° C, and the polymerization time is usually 10 to 50 hours.

The average particle size of the (c) rubbery polymer latex emulsion-polymerized in this manner is preferably 50 to 50.
2,000 nm, more preferably 80 to 1,000 n
m, particularly preferably 100 to 500 nm. Within this range, the rubber-reinforced vinyl polymer or thermoplastic polymer composition obtained will have excellent Izod impact strength and gloss.

Here, the average particle diameter is (c) a rubber-like polymer latex treated with osmic acid, and this is, for example, manufactured by Otsuka Electronics Co., Ltd., Laser Particle Size Analysis System LPA-3.
It is a value calculated from the number average of 100 or more particles by taking an electron micrograph (magnification: 30,000 times) using 100. The average particle diameter of the rubber-like polymer latex can be obtained by combining these by selecting the amount of emulsifier, the amount of polymerization initiator, the polymerization temperature and the like.

The gel content of the (c) rubbery polymer latex is 20 to 100% by weight, preferably 20 to 95%.
%, More preferably 50 to 90% by weight. When the gel content is less than 20% by weight, the rubber elasticity is lowered, and the impact resistance of the obtained rubber-reinforced vinyl polymer or thermoplastic polymer composition is lowered, which is not preferable. In particular, when the gel content is 30% by weight or less, the obtained rubber-reinforced vinyl polymer or thermoplastic polymer composition has an extruding grade, for example, elongation during vacuum forming of a sheet and uniformity of product thickness. Excellent and suitable for inner boxes for electric refrigerators. When the gel content is 20 to 100% by weight,
The rubber-reinforced vinyl polymer or thermoplastic polymer composition obtained is suitable for grades requiring appearance such as impact resistance, weld, and gloss, such as electric appliances and OA equipment.

Here, the gel content means (c) the rubber-like polymer latex film (Ag) is immersed in 100 ml of toluene at 50 ° C. for 2 hours with stirring, and then filtered using a 120 mesh wire net, A part (Cml) of the filtrate was accurately sampled and evaporated to dryness, and the obtained residual solid content (toluene-soluble content; Bg) was weighed and the gel content was calculated according to the following formula. Gel content (% by weight) = {[A−B × (100 / C)] /
A｝ × 100

The adjustment of the gel content can be easily and easily carried out by selecting the kind and amount of the molecular weight adjusting agent. In addition, the gel content can be adjusted by adding a cross-linking agent,
The amount of the polymerization initiator at the time of polymerization, the polymerization initiation temperature, and the like are selected, and by combining these, the objective (c) rubber-like polymer latex can be obtained.

Further, (c) the rubber-like polymer latex is
Mooney viscosity when converted to solid rubber (ML _{1 + 4} , 1
(00 ° C.) is 10 to 300, preferably 10 to 250. If it is less than 10, the desired impact resistance cannot be obtained, while if it exceeds 300, the fluidity is lowered, which is not preferable. When the Mooney viscosity is within the above numerical range, the resulting rubber-reinforced vinyl polymer or thermoplastic polymer composition has good impact resistance. The adjustment of the Mooney viscosity can be easily carried out by selecting the kind and amount of the molecular weight modifier, the amount of the polymerization initiator, and the addition of the crosslinking agent.

(C) The Mooney viscosity (ML _{1 + 4} , when converted into the solid rubber of the rubber-like polymer latex,
100 ° C.) is preferably 10 to 30 in the conjugated diene rubber [(a) when the monomer component is (a-1) above].
0, more preferably 30 to 250, particularly preferably 5
0 to 200. In addition, in the case of the acrylic rubber [(a) the monomer component is the above (a-2)], preferably 10
To 200, more preferably 20 to 180, particularly preferably 20 to 150.

In the present invention, the rubber-like polymer latex (c) thus obtained has a copolymerization content of the carboxylate-based reactive emulsifier (b-1) copolymerized with the rubber-like polymer. , (C) 0.01 with respect to 100 parts by weight of the component
10 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight. If it is less than 0.01 parts by weight, a large amount of free emulsifier remains, the desired polymer latex having excellent polymerization stability and coagulation property, and rubber-reinforced vinyl polymer having little mold contamination and good thermal stability. And a thermoplastic polymer composition cannot be obtained. The copolymerization content of this carboxylate-based reactive emulsifier (b-1) is
It can be adjusted by the amount of polymerization initiator, the polymerization temperature, the method of charging the emulsifier and the like.

Next, the above (c) rubber-like polymer latex is added in an amount of 3 to 80 parts by weight of the latex (as solid content) to 97 to 20 parts by weight of the (d) vinyl monomer (however, (C) + (D) = 100 parts by weight], and the above (B) carboxylate-based reactive emulsifier (B-1) and /
Alternatively, by emulsion polymerization using another emulsifier (b-2), a (v) rubber-reinforced vinyl polymer having a graft ratio of 5 to 200% by weight can be obtained.

Here, the amount of the rubber-like polymer latex (c) used is 3 to 80 parts by weight, preferably 5 in terms of solid content.
It is ˜75 parts by weight, more preferably 10 to 70 parts by weight. If it is less than 3 parts by weight, sufficient impact resistance cannot be obtained.

Examples of the (d) vinyl-based monomer include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid alkyl esters, and other copolymerizable vinyl compound monomers.

Here, the aromatic vinyl compound is the same as the compounds exemplified in the above (a) monomer component. The amount of the aromatic vinyl compound used is usually 0 to 100% by weight, preferably 30 to 100% by weight in the vinyl monomer.
It is. When an aromatic vinyl compound is used, molding processability can be improved.

The vinyl cyanide compound is the same as the compounds exemplified in the above (a) monomer component. The amount of the vinyl cyanide compound used is usually 0 to 70% by weight, preferably 10 to 50% by weight in the vinyl monomer. Use of a vinyl cyanide compound improves chemical resistance, impact resistance, compatibility with a polar polymer, and the like. If it exceeds 70% by weight, the color tone may be deteriorated.

The (meth) acrylic acid alkyl ester is the same as the compounds exemplified in the above (a) monomer component. The amount of the (meth) acrylic acid alkyl ester used is usually 0 to 100% by weight, preferably 30 to 100% by weight in the vinyl monomer. Use of (meth) acrylic acid alkyl ester improves chemical resistance, weather resistance, and compatibility with polar polymers.

Other copolymerizable vinyl compound monomers include (meth) acrylic acid exemplified in the above (a) monomer component, and unsaturated compounds such as maleic anhydride, itaconic anhydride and citraconic anhydride. Acid anhydride; maleimide, N-methylmaleimide, N-butylmaleimide, N
-(P-methylphenyl) maleimide, N-phenylmaleimide; N-cyclohexylmaleimide and other α- or β-unsaturated dicarboxylic acid imide compounds, and further epoxy group-containing monomers such as glycidyl methacrylate and allyl glycidyl ether; acrylamide; Amido group-containing monomers such as methacrylamide; amino group-containing monomers such as acrylic amine, aminomethyl methacrylate, amino acid methacrylate, aminopropyl methacrylate; 3-hydroxy-1-propene, 4-
Hydroxy-1-butene, cis-4-hydroxy-2-
Butene, trans-4-hydroxy-2-butene, 3-
Examples thereof include hydroxyl group-containing monomers such as hydroxy-2-methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and hydroxystyrene; and oxazoline group-containing monomers such as vinyl oxazoline.

The amount of the other copolymerizable vinyl compound monomer used is usually 0 to 70% by weight, preferably 0 to 60% by weight in the vinyl monomer. These copolymerizable vinyl compound monomers are used to impart special properties to the rubber-reinforced vinyl polymer. If the amount used exceeds 70% by weight, the effect of the above-mentioned monomer is reduced, which is not preferable.

(D) The amount of vinyl monomer used is (c)
3-80 parts by weight of rubber-like polymer latex (solid content conversion)
On the other hand, it is 97 to 20 parts by weight, preferably 95 to 25 parts by weight, and more preferably 90 to 30 parts by weight.

Examples of preferable (e) rubber-reinforced vinyl polymers are shown below. The composition ratio of conjugated diene compound / aromatic vinyl compound is 5
Aromatic vinyl compound / cyanation in the presence of 10 to 70 parts by weight (solid content) of a rubbery polymer latex (c) obtained by polymerizing a monomer component of 0 to 100/0 to 50% by weight. 1 vinyl compound / other vinyl compound monomer
90 to 30 parts by weight of (d) vinyl-based monomer consisting of 0 to 90/5 to 40/0 to 50% by weight (however, (c) +
(D) = 100 parts by weight] to obtain a rubber-reinforced vinyl polymer.

(C) 20 to 80 parts by weight of a rubber-like polymer latex obtained by polymerizing a monomer component having a composition ratio of conjugated diene compound / aromatic vinyl compound of 60 to 90/10 to 40% by weight. In the presence of an aromatic vinyl compound /
10-90 / 1 alkyl (meth) acrylate
(D) Vinyl monomer 80 to 2 consisting of 0 to 90% by weight
A rubber-reinforced vinyl polymer obtained by polymerizing 0 parts by weight (however, (c) + (d) = 100 parts by weight).

(E) As the emulsion polymerization method of the rubber-reinforced vinyl polymer, a generally well-known method can be used as it is. Examples of the emulsion polymerization method include the method described in the above (c) Rubber-like polymer latex.

(E) The emulsifier (b) used in the emulsion polymerization of the rubber-reinforced vinyl polymer is the same carboxylate-based reactive emulsifier (ro) as that used in the above (c) rubbery polymer latex. 1) and / or other emulsifiers (b-2). The proportions of the components (B-1) and (B-2) used are not particularly limited, but preferably (B-
1) / (B-2) = 1 to 100/99 to 0% by weight, more preferably 20 to 100/80 to 0% by weight, and particularly preferably 50 to 100/50 to 0% by weight. The amount of the carboxylate-based reactive emulsifier (B-1) used is 1% by weight.
When the amount is less than, the polymerization stability and mechanical stability during emulsion polymerization are poor, and the coagulability during acid precipitation and salting out is poor, and more free emulsifiers remain, and rubber-reinforced vinyl polymers and thermoplastic polymers When the composition is used, mold contamination occurs and the thermal stability decreases, which is not preferable.

The total amount of the (b) emulsifier used in the production of the (e) rubber-reinforced vinyl polymer is preferably 0.1 part by weight per 100 parts by weight of the total amount of the (c) and (d) components. 01 to 10 parts by weight, more preferably 0.01 to 8
Parts by weight, particularly preferably 0.5 to 8 parts by weight. 0.
If it is less than 01 parts by weight, the stability during emulsion polymerization will be poor, while if it is more than 10 parts by weight, the rubber-reinforced vinyl polymer obtained will have reduced elasticity and poor impact resistance.

The graft ratio of the (e) rubber-reinforced vinyl polymer of the present invention is 5 to 200% by weight, preferably 10 to 1
It is 80% by weight, more preferably 20 to 150% by weight. When the graft ratio is within this range, a (v) rubber-reinforced vinyl polymer having an excellent balance of physical properties of impact resistance-thermal stability-molding processability can be obtained.

In the present invention, the (e) rubber-reinforced vinyl polymer thus obtained is the carboxylate-based reactive emulsifier (b-1) copolymerized with the rubber-reinforced vinyl polymer. The copolymerization content is 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of the component (e).
Parts by weight, more preferably 1 to 10 parts by weight. 0.
If the amount is less than 01 parts by weight, a large amount of free emulsifier remains, the target drainage load value is small, and the mold contamination is small,
Further, it is impossible to obtain a rubber-reinforced vinyl polymer or a thermoplastic polymer composition having good thermal stability. The copolymerization content of the carboxylate-based reactive emulsifier (b-1) can be adjusted by the amount of the polymerization initiator, the polymerization temperature, the method of charging the emulsifier, and the like.

The intrinsic viscosity [η] (30 ° C. in methyl ethyl ketone) of the rubber-reinforced vinyl polymer (e) is preferably 0.1 to 1.0, more preferably 0.12.
0.7, particularly preferably 0.15 to 0.65.

Next, the (e) rubber-reinforced vinyl-based polymer of the present invention is used alone as a molding material, and (he) other thermoplastic polymers such as the following (he-1) to
It may be blended with at least one selected from the group of (he-6) and used as a (g) thermoplastic polymer composition as an impact modifier, a compatibilizer, etc. of these polymers. it can.

(He-1): At least two kinds selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid esters, acid anhydrides, maleimide monomers and (meth) acrylic acid. A copolymer obtained by copolymerizing the above monomers. (He-2); Polycarbonate (He-3); Thermoplastic polyester (He-4); Polyamide (He-5); Polyolefin (He-6); Other rubber-reinforced vinyl polymer

Specific examples of the above (v) other thermoplastic polymers include (f-1); AS resin, MS resin, styrene-
Maleic anhydride copolymer, maleimide copolymer, etc.,
(F-2); aromatic polycarbonate, (f-3); polyester such as polybutylene terephthalate and polyethylene terephthalate, (f-4); polyamide such as nylon 6, nylon 6,6 and nylon 4,6, (f) −
5); polyethylene, polypropylene, (f-6); other ABS resins, AES resins, HIPS, styrene resins such as AS resins, and others; PPS resins, liquid crystal polyester resins, polyarylate resins, polysulfone resins, P
VC resin etc. are mentioned.

(G) In the thermoplastic polymer composition,
The ratio of (e) the rubber-reinforced vinyl polymer to (e) the other thermoplastic polymer is 1 to 99 parts by weight of the (e) component, preferably 10 to 89 parts by weight, more preferably 20 to 79 parts by weight, (He) component 99 to 1 part by weight, preferably 90 to 11
Parts by weight, more preferably 80 to 21 parts by weight.
(E) If the proportion of the rubber-reinforced vinyl polymer is less than 1 part by weight, the desired impact resistance cannot be obtained, while if it exceeds 99 parts by weight, the moldability is deteriorated.

Next, in the (e) rubber-reinforced vinyl polymer or (g) thermoplastic polymer composition of the present invention, at least one selected from the following groups (h-1) to (h-4): 1
By blending the seeds, a (ri) thermoplastic polymer composition imparted with functionality such as flame retardancy, antibacterial / antifungal properties, antistatic properties and foaming properties can be obtained. (Ch-1); flame retardant (Ch-2); antibacterial agent and / or antifungal agent (Ch-3); antistatic agent (Ch-4); foaming agent

Here, as the (h-1) flame retardant used in the present invention, a flame retardant used for polymers such as general rubber and resin can be used. Examples of the (CH-1) flame retardant include halogen-containing compounds, phosphorus-containing compounds, nitrogen-containing compounds and silicon-containing compounds.
Among the (H-1) flame retardants, examples of the halogen-containing compound include tetrabromobisphenol A or tetrabromobisphenol A-bis (2-hydroxyethyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl). Ether) and other tetrabromobisphenol A derivatives, hexabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, bis (tribromophenoxy)
Examples thereof include ethane and hexabromocyclodecane.

Examples of halogen-containing compounds include monobromophenol, tribromophenol, pentabromophenol, tribromocresol, dibromopropylphenol, tetrabromobisphenol S,
An oligomeric halogen compound obtained by polymerizing cyanuric chloride or the like or by copolymerizing these with one or more halogen compounds selected from the group of the above halogen compounds can be used. Further, examples of the halogen-containing compound include a polycarbonate oligomer of tetrabromobisphenol A, a polycarbonate oligomer of tetrabromobisphenol A and bisphenol A, a polycarbonate oligomer of tetrabromobisphenol S, a polycarbonate oligomer of tetrabromobisphenol S and bisphenol S, and the like. To be further,
Examples of the halogen-containing compound include halogenated epoxy oligomers represented by formula (12).

[0070]

[Chemical 12]

[Wherein, R ⁶ and R ⁷ are the same or different and each is a group selected from the formula (13) (wherein Y represents a bromine atom or a chlorine atom, and j represents an integer of 0 to 5). X is a bromine atom or a chlorine atom, i is an integer of 1 to 4, and m is 0 to 10. ]

[0072]

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Further, as the phosphorus-containing compound in the flame retardant (H-1), an organic phosphate compound represented by the formula (14) can be mentioned.

[0074]

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(In the formula, R ^{8 to} R ¹⁰ are the same or different and each represents an aliphatic, alicyclic or aromatic hydrocarbon residue, and the hydrocarbon residue is substituted with a halogen atom or another substituent. Specific examples of the organic phosphate-based compound include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, triisopropyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, tris-phosphate.
In addition to (dibromopropyl) -phosphate, tris- (chlorophenyl) -phosphate, 4-chlorophenyldiphenylphosphate and the like, bisphenol A phosphate polymer, cresyldiphenylphosphate dimer and the like can be mentioned. Further, as the phosphorus-containing compound, an organic phosphate compound represented by the formula (15) can be mentioned.

[0076]

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(In the formula, R ¹¹ represents an aliphatic or aromatic hydrocarbon residue, the aromatic hydrocarbon residue may be substituted with an alkyl group, and R ^{12 to} R ¹³ may be the same. They may be different and represent an aliphatic or aromatic hydrocarbon residue, which aromatic hydrocarbon residue may be substituted with an alkyl group.)

Specific examples of the organic phosphate compound represented by the above formula (15) include dimethylphosphonate, diethylester, dibutylester, di-n-amylester, diphenylester or di-p-phenylphenylphosphonic acid. -Butylphenyl ester; 4-methylphenylphosphonic acid diethyl ester, diphenyl ester or di-p-tolyl ester; methylphosphonic acid dimethyl ester, diethyl ester, dipropyl ester, diisopropyl ester, diphenyl ester, di- m-tolyl ester or di-p-tolyl ester; ethylphosphonic acid diethyl ester or dibutyl ester; propylphosphonic acid diethyl ester or dipropyl ester; Dimethyl ester or dibutyl ester of phonic acid; Diethyl ester or dibutyl ester of isobutylphosphonic acid; Diethyl ester or diphenyl ester of isoamylphosphonic acid; Diethyl ester or dibutyl ester of n-hexylphosphonic acid; n- Heptylphosphonic acid diethyl ester or dibutyl ester; n-octylphosphonic acid diethyl ester or dibutyl ester; n-nonylphosphonic acid diethyl ester or dibutyl ester; n-decylphosphonic acid diethyl Ester or dibutyl ester; diethyl ester or dibutyl ester of n-dodecylphosphonic acid; n
-Diethyl ester or dibutyl ester of tetradecylphosphonic acid; dibutyl ester of n-octadecylphosphonic acid.

The amount of these (H-1) flame retardants is 1 to 30 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the component (e) or the component (to). If it is less than 1 part by weight, the desired flame retardant effect cannot be obtained, while if it exceeds 30 parts by weight, impact resistance, fluidity and surface gloss are lowered, which is not preferable.

If necessary, a flame retardant aid may be used in combination with the above (h-1) flame retardant. Examples of flame retardant aids include iron oxide, borax, metaboric acid paste, zirconium oxide, and antimony compounds such as antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, and antimony phosphate. Can be used alone or in combination of two or more. Of these flame retardant aids, antimony trioxide and sodium antimonate are preferred. When these flame retardant aids are used together, more excellent flame retardancy can be obtained. The amount of the flame retardant aid used is usually about 10 to 40% by weight based on the flame retardant.

The (e) rubber-reinforced vinyl polymer or (g) thermoplastic polymer composition of the present invention may be mixed with an antibacterial agent and / or an antifungal agent (h-2) to prepare an antibacterial agent. -It can be a mold-resistant (ri) thermoplastic polymer composition.

The component (h-2) is preferably an inorganic antibacterial agent. As the inorganic antibacterial agent, an organic or inorganic metal compound, a substance having a porous structure (porous structure) carrying a metal compound and / or a metal complex salt, or a metal having a porous structure is used. The thing which ion-exchanged the ion etc. is mentioned. The metal ions used here include silver, copper, zinc, magnesium, mercury, tin, lead, bismuth, cadmium, chromium, cobalt, nickel, iron, manganese, arsenic, antimony, barium, etc., preferably silver. , Copper, zinc, magnesium, etc., more preferably silver, copper, zinc, and particularly preferably silver, zinc.

Examples of the silver compound include colloidal silver (colloidal silver), silver carbonate, silver chlorate, silver perchlorate,
Silver bromate, silver iodate, silver periodate, silver phosphate, silver diphosphate, silver nitrate, silver nitrite, silver sulfate, silver tungstate, silver navadate, silver thiocyanate, silver amidosulfate, silver borate, Silver thiosulfate, silver oxide, silver peroxide, silver sulfide, silver fluoride, silver chloride, silver bromide, silver iodide, silver acetate, silver benzoate, silver lactate, silver pyrophosphate, silver citrate, silver behenate ,
Silver diethylcarbamate, silver stearate, silver carboxylate, silver tartrate, silver metasulfonate, silver trifluoroate,
Examples thereof include alkyl ester of phosphoric acid or phosphorous acid, silver salt of phenyl ester or alkylphenyl ester, silver phosphorofluoride, silver phthalocyanine, silver ethylenediaminetetraacetate, and protein silver. Among these, preferred are colloidal silver, silver chlorate, silver perchlorate, silver carbonate, silver bromate, silver iodate, silver periodate, silver phosphate, silver diphosphate, silver nitrate, silver sulfate, and tungsten. They are silver acid salt, silver vanadate, silver citrate, silver thiocyanate, silver carboxylate, silver amidosulfate, silver thiosulfate, silver chloride, silver oxide, and silver peroxide. Further, particularly preferred are colloidal silver, silver oxide, silver phosphate, silver carbonate, silver iodate, silver pyrophosphate, silver citrate, silver tungstate,
It is silver chloride.

As the copper compound, for example, copper (II) nitrate,
Examples thereof include copper sulfate, copper perchlorate, copper acetate, potassium tetracyanocuprate, copper chloride and the like. Examples of the zinc compound include zinc (II) nitrate, zinc sulfate, zinc perchlorate, zinc thiocyanate, zinc acetate, zinc chloride and zinc oxide. These metal compounds are used alone or in combination of two or more.

Of these, colloidal silver is a yellow or reddish brown aqueous colloidal silver, which has a very large antibacterial activity and has little harm to the human body. Also, silver
It is preferable because it has excellent heat resistance, good corrosion resistance in the air, and excellent durability. Such colloidal silver can be easily produced by a method of reducing a metal salt of silver. For example, dilute ammonia water is added to an aqueous solution of silver nitrate to make silver oxide, and then ammonia water is added to form a complex salt, which is diluted with water, and then an aqueous solution of oxalic acid or tannic acid as a reducing agent is added and heated. The method of doing is mentioned. Also, as a reduction method,
There are hydrogen, carbon, or carbon monoxide reduction methods, methods using alkali metals, and other known methods. This colloidal silver usually has a silver content of 0.02 to 1% by weight, a particle size of 50 mμ or less, and a pH of 7.0 ± 1.0.
Preferably, the silver component is 0.05 to 0.2% by weight, and the particle size is 1.
It is 0 mμ or less. The antibacterial activity of silver tends to increase as the particles become finer.

The carboxylic acid salts include the following carboxylic acid salts. Aliphatic saturated monocarboxylic acid having 1 to 30 carbon atoms, preferably 2 to 22, for example, acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid, docosanoic acid, carbon number 2 to 34 , Preferably 2-8 aliphatic saturated dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid, aliphatic unsaturated carboxylic acids having 1-34 carbon atoms, preferably 2-22, such as olein Acids, erucic acid, maleic acid, fumaric acid, carbocyclic carboxylic acids such as benzoic acid, phthalic acid, cinnamic acid, hexahydrobenzoic acid, abietic acid, hydrogenated abietic acid, hydrocarboxylic acids such as lactic acid, malic acid, Tartaric acid,
Citric acid, salicylic acid, aminocarboxylic acids such as aspartic acid, glutamic acid. In the present invention, the preferred carboxylic acid salt is a silver salt, for example, a silver salt of an aliphatic saturated monocarboxylic acid, particularly silver laurate, silver stearate, a silver salt of an aliphatic unsaturated carboxylic acid, especially silver oleate. And silver salts of carbocyclic carboxylic acids, especially silver benzoate and hydrogenated silver abietic acid.

Further, as the salt of an alkyl ester, phenyl ester or alkylphenyl ester of phosphoric acid or phosphorous acid, the following may be mentioned, taking a silver salt as an example. Mono- or di-silver salt of monoalkyl phosphate (C1-22) ester, Mono- or di-silver salt of monoalkyl phosphite (C1-22) ester, Dialkyl phosphate (carbon 1 to 22) mono-silver salt of esulte, mono-silver salt or di-silver salt of phosphoric acid monophenyl ester, mono-silver salt or di-silver salt of phosphorous acid monophenyl ester, mono-silver salt of phosphoric acid diphenyl ester, Monophosphate [alkyl (C1-22) phenyl]
Monosilver salt or disilver salt of ester, monosilver salt or disilver salt of phosphorous acid mono [alkyl (C1-22) phenyl] ester, di [alkyl (C1-22) phenyl] ester of phosphoric acid One silver salt.

Of these, preferred silver salts are monosilver or disilver salts of monoalkyl phosphate esters, particularly those having an alkyl group with 6 to 22 carbon atoms, and more preferably stearyl phosphate disilver salt. Monosilver salt of phosphoric acid dialkyl ester, in particular, alkyl group having 6 to 22 carbon atoms, more preferably dioctyl phosphate monosilver salt, and phosphoric acid di (alkylphenyl) ester monosilver salt, especially alkyl group Is a monosilver salt of di (4-t-butylphenyl) phosphate or a disilver salt of di (nonylphenyl) phosphate.

Further, examples of the porous structure include silica gel, activated carbon, zeolite, zirconium phosphate, calcium phosphate, hydrotalcite, hydroxyapatite, calcium-based ceramics, etc., containing the above metal and the above metal compound, There is also a soluble glass containing silver oxide or the like (JP-A-4-178433). The particle size of these substances is 50 μm
The following is preferable, and 0.1 to 10 μm is more preferable.

Of these, the zeolite can be either a natural product or a synthetic product. For example, as natural zeolite, anarsine (SiO ₂ / Al ₂ O ₃ = 3.6) is used.
5.6), chabazite _{(SiO 2 / Al 2 O 3} =
3.2 to 6.0 and from 6.4 to 7.6), clinoptilolite Petit write _{(SiO 2 / Al 2 O 3} = 8.5~10.5), erionite _{(SiO 2 / Al 2 O 3} = 5 .8 to 7.
4), faujasite (SiO ₂ / Al ₂ O ₃ = 4.2)
To 4.6), mordenite _{(SiO 2 / Al 2 O 3} =
8.34 to 10.0), Phillipsite (SiO ₂ /
Al ₂ O ₃ = 2.6 to 4.4) and the like. These typical natural zeolites are suitable for the present invention.

On the other hand, as a typical synthetic zeolite, A-type zeolite (SiO ₂ / Al ₂ O ₃ = 1.
4 to 2.4), X-type zeolite (SiO ₂ / Al ₂ O ₃
= 2 to 3), Y- type zeolite (SiO ₂ / Al ₂ O ₃
= 3-6), mordenite _{(SiO 2 / Al 2 O 3} = 9
-10) etc., but these synthetic zeolites are suitable as the zeolite used in the present invention.
Particularly preferred are synthetic A-type zeolites, X-type zeolites, Y-type zeolites and synthetic or natural mordenites. There are no particular restrictions on the shape and particle size of the zeolite, but a smaller particle size is preferable, for example 5 μm or less, particularly 0.1 to 2 μm.

Examples of calcium-based ceramics include calcium phosphate, calcium carbonate, calcium silicate, and hydroxyapatite, and hydroxyapatite is particularly preferable. Hydroxyapatite is C
It has a composition of a ₁₀ (PO ₄ ) ₆ (OH) ₂ , is well adsorbed to proteins and lipids in the main components of bones and teeth, has good affinity with biological components, and has an ion exchange ability. Has been. However, as described above, Ca / P (molar ratio) =
Synthesis of 10/6 hydroxyapatite from calcium and phosphate salts is difficult and uneconomical. On the other hand, it is easy to synthesize a hydroxyapatite analogue having Ca / P (molar ratio) = 1.4 to 1.8 from calcium salt and phosphate, and these analogues are similar to hydroxyapatite. It can be used in the present invention.

The amount of silver supported on the calcium-based ceramics can be arbitrarily selected within the range of adsorption or ion exchange, but in view of the structure retention and antibacterial activity of the calcium-based ceramics, 50% by weight or less based on the ceramics, It is preferably 0.001 to 30% by weight. The antibacterial calcium-based ceramics thus obtained are
Preferably, after calcination at 800 ° C. or higher, it is finely pulverized and used as the component (h-2) of the present invention. Since this antibacterial calcium-based ceramic is fired at a high temperature, the bond between the supported silver and the ceramic is strengthened, and the ceramic itself contracts and stabilizes by firing, so the silver supported by the water treatment is It can be mixed with the components (e) and (g) of the present invention in any amount without elution.

Examples of the organic component (H-2) include benzimidazole compounds, organic iodo compounds, ether compounds, haloalkyl compounds,
Examples thereof include nitrile compounds and sulfone compounds. (H-2) The antibacterial agent and / or antifungal agent is
With respect to 100 parts by weight of the component (e) or the component (g),
The amount is 0.01 to 10 parts by weight, preferably 0.1 to 8 parts by weight. If it is less than 0.01 part by weight, the desired antibacterial effect,
Mold resistance cannot be obtained, and on the other hand, if it exceeds 10 parts by weight, impact resistance, fluidity and surface gloss are deteriorated, which is not preferable.

Further, the (e) rubber-reinforced vinyl polymer or (g) thermoplastic polymer composition of the present invention comprises
(H-3) An antistatic agent may be added to give an antistatic (ii) thermoplastic polymer composition. This (Chi-
3) Examples of antistatic agents include polyethylene oxide, polyethylene glycol-containing polymers, and other antistatic agents.

The polyethylene oxide preferably has an average molecular weight of 50,000 to 500,000, preferably 100,000.
It is 400,000. As the polyethylene glycol-containing polymer, a copolymer of an unsaturated compound having a repeating unit of ethylene oxide and the above aromatic vinyl compound, another monomer copolymerizable with the aromatic vinyl compound, a polyethylene glycol-containing block Copolymer,
Examples thereof include polymers grafted with polyethylene glycol. Polyethylene glycol-containing block copolymers include known polyamide elastomers, polyamideimide elastomers, polyester elastomers, and the like.Polyethylene glycol-grafted polymers include known polyamide polymers grafted with polyethylene glycol. To be As polyethylene glycol, those containing bisphenol A in the molecule are also used.

Further, as the other antistatic agents, all of the commonly used antistatic agents can be used. As the antistatic agent, there are anionic type, cationic type, nonionic type, amphoteric type and the like, and any of them can be used. Particularly preferred are anionic type and nonionic type, and of these, sodium sulfonate type and monoglyceride type are preferable. These (HI-3) antistatic agents are added in an amount of 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the component (e) or the component (e). If it is less than 0.1 part by weight, the desired antistatic property cannot be obtained, while if it exceeds 30 parts by weight, impact resistance, fluidity and surface gloss cannot be obtained, which is not preferable.

Further, the (e) rubber-reinforced vinyl polymer or (g) thermoplastic polymer composition of the present invention comprises
(H-4) A foaming agent can be blended to obtain a foamable (i) thermoplastic polymer composition. Here, examples of the (HI-4) foaming agent include azodicarbonamide, dinitropentamethylenetetramine, and barium azodicarboxylate.

These (h-4) foaming agents were added in an amount of 0.1 parts by weight per 100 parts by weight of the (e) component or (g) component.
˜20 parts by weight, preferably 0.1 to 10 parts by weight. If it is less than 0.1 parts by weight, the heat insulating effect, low temperature effect or soft feeling of the obtained resin surface cannot be obtained, while if it exceeds 20 parts by weight, impact resistance, fluidity and molding processability are deteriorated.

In addition, the (e) rubber-reinforced vinyl polymer of the present invention or the thermoplastic polymer composition of the (g) component and the (g) component includes glass fiber, carbon fiber, metal fiber,
Glass beads, wollastonite, glass milled fiber, rock filler, glass flakes, calcium carbonate, talc, mica, kaolin, barium sulfate, graphite,
Fillers such as wood powder, molybdenum disulfide, magnesium oxide, zinc oxide whiskers, potassium titanate whiskers, glass balloons and ceramic balloons may be used alone or in combination of two or more.

Among these fillers, the shapes of glass fiber and carbon fiber are as follows: fiber diameter of 6 to 60 μm and 30 μm
Those having the above fiber length are preferable. These fillers are usually used in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the component (e) or the component (g) or component (i) of the present invention.

The (e) rubber-reinforced vinyl polymer of the present invention, or the thermoplastic polymer composition of the (g) component or the (g) component is a known coupling agent, antioxidant, weather resistance ( A light agent, a plasticizer, a colorant (a pigment, a dye, etc.), a lubricant, a metal powder and the like can be added.

The (e) rubber-reinforced vinyl polymer, or the thermoplastic polymer composition of the (g) component or (i) component is
(E) component alone, or (to) component and (ri) component,
It can be prepared by blending the above additives as necessary and kneading the components using various extruders, Banbury mixers, kneaders, rolls and the like. A preferable manufacturing method is a method using an extruder. When kneading the components, the components may be kneaded at once, or may be kneaded by a multi-stage addition method.

The composition thus obtained is injection molded, sheet extruded, vacuum molded, deformed, foam molded,
Various molded products can be molded by injection press, gas assist molding, press molding, blow molding, and the like.

Various molded articles obtained by the above-mentioned molding method, utilizing their excellent properties, can be used for large televisions, video
Refrigerators, calculators, air conditioners, lighting fixtures, rice cookers, home appliances such as telephones, light appliances, computers, copying machines,
Office equipment such as facsimiles, office equipment, cars
Exterior parts, motorcycle parts, various leisure products, toys, extruded sheets, pipe products, building material parts, machinery / tool parts, industrial equipment / parts, medical equipment, food containers, stationery / daily necessities, pachinko machines, family computers, etc. Used for parts of game machines.

As described above, in the present invention, since the carboxylate-based reactive emulsifier is used as at least a part of the emulsifier in the emulsion polymerization of the rubber-like polymer latex, the polymerization stability and the mechanical stability are improved. In addition to being excellent, it also has excellent coagulability at the time of acid precipitation and salting out. Furthermore, since the reactive emulsifier is copolymerized in the polymerized polymer and the free emulsifier remaining after the polymerization is suppressed, the emulsifier is mixed in the waste water. Is reduced. Further, using this rubber-like polymer latex, when producing a rubber-reinforced vinyl-based polymer by emulsion polymerization of a vinyl-based monomer, if a carboxylate-based reactive emulsifier is used as at least a part of the emulsifier, In addition to being excellent in polymerization stability and mechanical stability, it is also excellent in coagulability at the time of acid precipitation and salting-out, and the degree of swelling of the rubber-like polymer with respect to the vinyl monomer is improved, so that the graft ratio is improved. This reactive emulsifier is (grafted) copolymerized in the copolymer forming the latex or the vinyl polymer forming the matrix, and the mixing of the emulsifier in the waste water is reduced. Further, since the reactive emulsifier contained in the obtained rubber-reinforced vinyl polymer is mainly (graft) copolymerized, the mold is hardly contaminated, and the thermal stability,
Excellent appearance of molded products such as color tone.

[0107]

The present invention will now be described more specifically with reference to examples. In the examples, parts and% are by weight unless otherwise specified. Further, various evaluations in the examples are values measured as follows.

[0108] The coagulation quantity latex was filtered through a 100 mesh screen, drying the coagulum remaining on a mesh drier, the percentage of dry coagulum weight relative to the produced polymer weight was solidified quantity. Mechanical stability 500 g of latex filtered with 100 mesh wire mesh,
The mixture was placed in a 1,000-liter container and a homomixer maintained at 70 ° C. was used to perform high-speed stirring at 6,000 rpm, and the solidification time was measured (minutes).

Grafting Ratio A certain amount (x) of the rubber-reinforced vinyl polymer was added to acetone, and the mixture was shaken for 2 hours on a shaker to dissolve the free copolymer, and this was separated using a centrifuge. 23,000 solution
After centrifugation at rpm for 30 minutes to obtain the insoluble matter, it was dried at 120 ° C. for 1 hour using a vacuum dryer to obtain the insoluble matter (y) and the free polymer. It was calculated. Graft ratio (%) = [(y−x × rubber fraction in rubber-reinforced vinyl polymer) / (x × rubber fraction in rubber-reinforced vinyl polymer)] × 100

Intrinsic viscosity [η] A free rubber-reinforced vinyl polymer was isolated, dissolved in methyl ethyl ketone, and measured with a Uderode viscometer at a temperature of 30 ° C. Rubber-reinforced vinyl polymer, thermoplastic polymer acryloni
Measurement of tolyl content (B'd-AN ) Rubber-reinforced vinyl polymer, thermoplastic polymer as it is,
Elemental analysis was performed, and the acrylonitrile content (%) was determined from the C, H, and N element ratios.

Organic acid / soap evaluation 6 g of a rubber-like polymer or rubber-reinforced vinyl polymer was dissolved in 75 ml of dimethylformamide (DMF), and 175 ml of methanol was added thereto and stirred for 30 minutes. After standing, 100 ml of the supernatant was sampled at 2 points, and 1 point was subjected to neutralization titration with N / 50 NaOH with a meta-cresol purple indicator, and the organic acid content was calculated according to the following calculation formula. One of them was subjected to neutralization titration with N / 50 HCl with a meta-cresol purple indicator, and the soap content was determined according to the following calculation formula.

Formula for calculating organic acid / soap content Organic acid content = [(A × 0.02 × 2.5 × X) / sample amount (g)] × [N / 50 NaOH factor]
(%) A: Sample titer-blank titer (ml) X: Organic acid molecular weight Soap content = [(B x 0.02 x 2.5 x Y) / sample amount (g)] x [N / 50 Factor of HCl]
(%) B: Sample titer-blank titer (ml) Y: Soap molecular weight

Reactive Emulsifier Copolymerization Rate The unreacted emulsifier not copolymerized was quantified by the HPLC method. Liquid chromatograph; Hewlett-Packard, H
P-1050 set Column name; STR ODS-H 4.6 × 150 mm Column heater temperature; 40.0 ° C. Prepare a standard solution (1,000 ppm) of each reactive emulsifier, collect each spectrum by HPLC, and calibrate. Make a line. As a pretreatment of the measurement sample, 2 g of latex was coagulated with 10 ml of methanol, centrifuged at 2,000 rpm, and the supernatant was measured by HPLC to measure the amount of unreacted emulsifier.

Coagulation test Latex 2,000 g in terms of solid content was added to an aqueous solution in which 40 g of calcium chloride or 40 g of sulfuric acid was dissolved in 8,000 g of water, and the mixture was heated to 85 ° C. to coagulate, and after coagulation, The state of the filtrate (whether turbid or not) was visually observed.

Izod impact strength The Izod impact value was measured according to JIS K7110. The unit is kgf · cm / cm. Melt flow rate: Measured in accordance with JIS K7201 under the conditions of 220 ° C. and 10 kg, and expressed as the number of g flowing out for 10 minutes. Units,
g / 10 minutes.

Measured according to RH ASTM D785 (Rockwell hardness). HDT ASTM D648 (Bending stress 18.5 kgf / cm
² ) was measured. Gloss Suga Tester Co., Ltd. digital variable angle gloss meter (incident angle 60
(°). Evaluation of mold contamination Evaluation was carried out by the disk gas evaluation method. That is, it was evaluated by the number of continuous shots after which the contaminants attached to the mold disappeared after the half shot.

Flame Retardancy (Combustion Test ): UL-94 compliant (V-test). The test piece is 1 /
16 ″ × 1/2 ″ × 5 ″. Escherichia coli was used as an antibacterial bacterium, and the Escherichia coli solution was sprayed onto the surface of a molded body of 5 × 5 cm ² to measure the antibacterial activity against Escherichia coli.

Antistatic surface specific resistance: A disk having a diameter of 100 mm and a thickness of 2 mm was molded and conditioned for 7 days at 23 ° C. and 50% relative humidity, and then 432 manufactured by Yokogawa Hewlett-Packard Co.
The surface specific resistance was measured using a 9A type super insulation resistance tester. Charge voltage: A 40 mm × 40 mm test piece was cut out from the above disc, and a static voltage was applied for 30 seconds at an applied voltage of 10 kV using a static Honest meter manufactured by Shishido Electrostatics Co., Ltd., and then the charged voltage was measured. The density was measured according to the foaming ASTM D1622-59T.

Example 1 (Production of Polybutadiene Rubber Latex) In a reactor equipped with a stirrer having a capacity of 100 liters, 100 parts of 1,3-butadiene, 60 parts of water, and a carboxylate-based reactive emulsifier (hereinafter, also referred to as “reactive emulsifier”). 2.4 parts of the above formula (3), 1.0 part of potassium phosphate, 0.1 part of potassium hydroxide, 0.3 part of t-dodecyl mercaptan as a chain transfer agent, and potassium persulfate of 0.1 part. Add 3 parts,
Batch polymerization was carried out at 60 to 70 ° C. for 30 hours. The polymerization conversion rate was 95%. To this polymerization system, 0.2 parts of N, N-diethylhydroxylamine as a polymerization terminator was added,
The reaction was stopped. Then, 1,3-butadiene was removed under reduced pressure to obtain a polybutadiene rubber latex (A-1) having a solid content of 60.4%. The evaluation results of this latex (A-1) are shown in Table 1.

Example 2 (Production of acrylic rubber latex) In a reactor equipped with a stirrer and having a capacity of 100 liters, 99 parts of butyl acrylate, 1 part of allyl methacrylate as a graft crossing agent, 125 parts of water, and as a reactive emulsifier, the above formula ( 3) 2.4 parts, 1 part of potassium phosphate, 0.1 part of potassium hydroxide, 0.1 part of t-dodecyl mercaptan as a chain transfer agent, and 0.1 part of potassium persulfate were added, and the polymerization temperature was 60 to 70. Three-stage batch polymerization [monomer (weight ratio) = 33/33/34] was carried out at 5 ° C. for 5 hours. Polymerization conversion rate is 9
It was 9%. N, N as a polymerization terminator was added to this polymerization system.
-0.2 parts of diethylhydroxylamine was added to stop the reaction. Then, the monomers were removed under reduced pressure to obtain an acrylic rubber rubber latex (A-2) having a solid content of 44.9%. The evaluation results of this latex (A-2) are shown in Table 1.

Example 3 (Production of rubbery polymer latex) A latex (A) was prepared in the same manner as in Example 1 (A-1) except that 2.4 parts of the above formula (2) was used as the reactive emulsifier. -3) was obtained. The evaluation results of this latex (A-3) are shown in Table 1. Example 4 (Production of rubbery polymer latex) A latex (A-4) was prepared in the same manner as in Example 1 (A-1) except that 2.4 parts of the above formula (4) was used as the reactive emulsifier. Got The evaluation results of this latex (A-4) are shown in Table 1.

Example 5 (Production of rubbery polymer latex) A latex (A) was prepared in the same manner as in Example 1 (A-1) except that 2.4 parts of the above formula (5) was used as the reactive emulsifier. -5) was obtained. The evaluation results of this latex (A-5) are shown in Table 1. Example 6 (Production of rubbery polymer latex) A latex (A- was prepared in the same manner as in Example 3 except that 1.2 parts of the above formula (3) and 1.2 parts of potassium rosinate were used as the reactive emulsifier. 6) was obtained. This latex (A-
The evaluation results of 6) are shown in Table 1.

Example 7 (Production of rubber-like polymer latex) A latex (A) was prepared in the same manner as in Example 1 (A-1) except that 90 parts of 1,3-butadiene and 10 parts of styrene were used.
-7) was obtained. The evaluation results of this latex (A-7) are shown in Table 1. Example 8 (Production of rubbery polymer latex) 90 parts of butyl acrylate, 10 parts of 1,3-butadiene
Part (A) except that no methacrylic acid is used.
A latex (A-8) was obtained in the same manner as in (2). The evaluation results of this latex (A-8) are shown in Table 1.

Comparative Example 1 (Production of Rubbery Polymer Latex) A latex (A- was prepared in the same manner as in Example 1 (A-1) except that 2.4 parts of potassium rosinate was used as an emulsifier.
9) was obtained. The evaluation results of this latex (A-9) are shown in Table 2. Comparative Example 2 (Production of Rubbery Polymer Latex) Latex (A-) was prepared in the same manner as in Example 2 (A-2) except that 2.4 parts of potassium rosinate was used as the emulsifier.
10) was obtained. The evaluation results of this latex (A-10) are shown in Table 2.

Comparative Example 3 (Production of Rubbery Polymer Latex) Example 1 (A- except that 2.4 parts of Aqualon HS20 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. was used as the reactive emulsifier.
A latex (A-11) was obtained in the same manner as in 1). The evaluation results of this latex (A-11) are shown in Table 2. Comparative Example 4 (Production of Rubbery Polymer Latex) Example 1 except that 2.4 parts of Adecaria Soap SE20N manufactured by Asahi Denka Kogyo Co., Ltd. was used as the reactive emulsifier.
A latex (A-12) was obtained in the same manner as (A-1). The evaluation results of this latex (A-12) are shown in Table 2.

Example 9 (Production of Rubber-Reinforced Vinyl Polymer) Latex (A-1) was added to 50 parts in terms of solid content,
Styrene 12 parts, acrylonitrile 5 parts, 0.3 part of the above formula (3) as a reactive emulsifier, potassium hydroxide 0.
05 parts, 80 parts of water, 0.06 parts of cumene hydroperoxide (hereinafter sometimes abbreviated as “CHPO”), sodium alkyldiphenyl ether disulfonate.
8 parts, water 7.9 parts, t-dodecyl mercaptan 0.2
In addition, batch polymerization was performed at 70 ° C. for 1 hour. Subsequently, 23 parts of styrene, 10 parts of acrylonitrile, 0.6 part of the above formula (3) as a reactive emulsifier, 0.1 part of potassium hydroxide, and 20 parts of water were added to the polymerization system kept at 70 ° C.
Part, cumene hydroperoxide 0.1 part and t-
0.3 part of dodecyl mercaptan was added over 2 hours to carry out increment polymerization.

Then, to the polymerization system kept at 70 ° C., 0.05 part of cumene hydroperoxide, 0.2 part of sodium alkyldiphenyl ether disulfonate, water and 2.
7 parts were added all at once (boost), and the polymerization was continued for 1 hour. The polymerization conversion rate was 99%. This is designated as latex (B-1). After adding 1 part of butylated hydroxytoluene as an anti-aging agent to 100 parts of this latex (B-1) in terms of solid content, coagulation is carried out by acid precipitation or salting out, followed by washing or acid washing and drying. , Got the powder. The physical properties of the obtained powder were evaluated. Table 3 shows the results
Shown in

Example 10 (Production of rubber-reinforced vinyl polymer) Polymerization was carried out in the same manner as in Example 9 except that latex (A-1) and potassium rosinate were used as an emulsifier. This is referred to as latex (B-2). The evaluation results of this latex (B-2) are shown in Table 3. Example 11 (Production of Rubber Reinforced Vinyl Polymer) Using latex (A-2), batch / increment t-
Polymerization was carried out in the same manner as in Example 9 except that dodecyl mercaptan = 0.1 / 0.15 part. This is referred to as latex (B-3). This latex (B-3)
The evaluation results of are shown in Table 3.

Example 12 (Production of rubber-reinforced vinyl polymer) Polymerization was carried out in the same manner as in Example 9 except that the latex (A-3) and the above formula (2) were used as the reactive emulsifier. This is referred to as latex (B-4). Table 3 shows the evaluation results of this latex (B-4). Example 13 (Production of rubber-reinforced vinyl polymer) Polymerization was carried out in the same manner as in Example 9 except that the latex (A-4) and the above formula (4) were used as the reactive emulsifier. This is designated as latex (B-5). Table 3 shows the evaluation results of this latex (B-5).

Example 14 (Production of rubber-reinforced vinyl polymer) Polymerization was carried out in the same manner as in Example 9 except that latex (A-5) and the above formula (5) were used as the reactive emulsifier. This is designated as latex (B-6). The evaluation results of this latex (B-6) are shown in Table 3. Example 15 (Production of rubber-reinforced vinyl polymer) Polymerization was carried out in the same manner as in Example 9 except that the latex (A-6) was used. This is latex (B-7)
And Table 3 shows the evaluation results of this latex (B-7).

Example 16 (Production of rubber-reinforced vinyl polymer) Polymerization was carried out in the same manner as in Example 9 except that the latex (A-7) was used. This is latex (B-8)
And Table 4 shows the evaluation results of this latex (B-8). Example 17 (Production of Rubber Reinforced Vinyl Polymer) Using latex (A-8), batch / increment t-
Polymerization was carried out in the same manner as in Example 9 except that dodecyl mercaptan = 0.1 / 0.15 part. This is designated as latex (B-9). This latex (B-9)
Table 4 shows the evaluation results.

Example 18 (Production of Rubber Reinforced Vinyl Polymer) Latex (A-1) was used as a vinyl monomer.
Styrene / acrylonitrile / methyl methacrylate /
Polymerization was carried out in the same manner as in Example 9 except that α-methylstyrene (AMS) = 4/7/35/4 parts.
This is designated as latex (B-10). Table 4 shows the evaluation results of this latex (B-10). Example 19 (Production of Rubber Reinforced Vinyl Polymer) Styrene / acrylonitrile / α-as a vinyl monomer based on 26 parts of the latex (A-1) in terms of solid content.
Methylstyrene (AMS) = 29/22/23 parts, t-
Polymerization was carried out in the same manner as in Example 9 except that 0.75 part of dodecyl mercaptan was used. This is designated as latex (B-11). Table 4 shows the evaluation results of this latex (B-11).

Comparative Example 5 (Production of Rubber Reinforced Vinyl Polymer) Polymerization was carried out in the same manner as in Example 9 except that latex (A-9) was used and potassium rosinate was used as an emulsifier. This is designated as latex (B-12). The evaluation results of this latex (B-12) are shown in Table 5. Comparative Example 6 (Production of Rubber Reinforced Vinyl Polymer) Polymerization was carried out in the same manner as in Example 9 except that the latex (A-9) was used. This is latex (B-1
3). Table 5 shows the evaluation results of this latex (B-13).

Comparative Example 7 (Production of Rubber Reinforced Vinyl Polymer) Latex (A-10), potassium rosinate as an emulsifier, batch / increed t-dodecyl mercaptan =
Polymerization was carried out in the same manner as in Example 9 except that 0.1 / 0.15 part was used. This is latex (B-14)
And The evaluation results of this latex (B-14) are shown in Table 5.
Shown in Comparative Example 8 (Production of Rubber-Reinforced Vinyl Polymer) Polymerization was performed in the same manner as in Example 9 except that latex (A-11) and AQUARON HS20 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. were used as the reactive emulsifier. Carried out. This is designated as latex (B-15). The evaluation results of this latex (B-15) are shown in Table 5. Comparative Example 9 (Production of Rubber Reinforced Vinyl Polymer) Polymerization was carried out in the same manner as in Example 9 except that latex (A-12) and Adecaria Soap SE20N manufactured by Asahi Denka Kogyo Co., Ltd. were used as the reactive emulsifier. Was carried out. This is designated as latex (B-16). This latex (B-1
The evaluation results of 6) are shown in Table 5. The reactive emulsifiers (formulas 2 to 5) used in the above-mentioned examples and comparative examples were R = alkyl group having 10 carbon atoms, n = 5, and M = K.

Examples 20 to 30 and Comparative Examples 10 to 13 (Preparation of Thermoplastic Polymer Composition) The rubber-reinforced vinyl polymer prepared above was mixed with the thermoplastic polymer [acrylonitrile (AN) / styrene (ST)].
(Weight ratio) = 30/70 AN-ST copolymer], other heat stabilizers, lubricants, etc. were mixed in the formulation shown in Tables 6 to 8 and a resin temperature of 200 was obtained using a vented extruder.
Pellets were produced by melt-kneading at ℃ and extruding. Using these pellets, a sheet was prepared with a 300 mmφ extruder at a cylinder temperature of 200 ° C., and each physical property was evaluated. The results are shown in Tables 6 to 8.

Examples 31 to 34 (Preparation of Thermoplastic Polymer Composition) Using the formulation shown in Table 9, the same procedure as in Example 20 was repeated.
A flame retardant, antibacterial / antifungal, antistatic, or foamable polymer composition was obtained. Table 9 shows the results.

[0137]

[Table 1]

[0138]

[Table 2]

[0139]

[Table 3]

[0140]

[Table 4]

[0141]

[Table 5]

[0142]

[Table 6]

[0143]

[Table 7]

[0144]

[Table 8]

[0145]

[Table 9]

[0146]

According to the present invention, by using a carboxylate-based reactive emulsifier as at least a part of the emulsifier,
Excellent impact resistance, surface gloss, thermal stability, appearance of molded products such as color tone, excellent mold non-staining property, less eye blemishes (thermal discoloration), small load of drainage pollution during manufacturing, rubbery weight A combined latex, a rubber-reinforced vinyl polymer obtained by using the rubber-like polymer, and a composition thereof are obtained.

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[Submission date] June 27, 1996

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 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuki Iwai 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (6)

[Claims] 1. (a) 100 parts by weight of a monomer component having a glass transition point of 10 ° C. or lower when converted to a polymer,
(B) Emulsion polymerization in the presence of 0.01 to 10 parts by weight of an emulsifier comprising (b) a carboxylate-based reactive emulsifier (b-1) / another emulsifier (b-2) = 1 to 100/99 to 0% by weight. The rubbery polymer thus obtained has a gel content of 20 to 100% by weight and a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 10 to 30.
0, a rubbery polymer latex. 2. The rubber-like polymer latex according to claim 1, wherein the monomer component (a) is the following (a-1) or (a-2). (A-1); (a) 30 to 100% by weight of the conjugated diene compound, and (b) 70 to 0% by weight of another monomer copolymerizable with the component (a) (provided that (a) + ( b) = 100% by weight]. (A-2); (c) 30 to 100% by weight of (meth) acrylic acid alkyl ester, and (d) 70 to 0% by weight of another monomer copolymerizable with the component (c) [where (( c) +
(D) = 100% by weight]. 3. (C) Rubber-like polymer latex 3 to 80
In the presence of parts by weight (in terms of solid content), 97 to 20 parts by weight of (d) vinyl-based monomer [where (c) + (d) = 100
Parts by weight] and 0.01 to 10 parts by weight of an emulsifier consisting of (b) a carboxylate-based reactive emulsifier (b-1) and / or another emulsifier (b-2). A rubber-reinforced vinyl polymer having a graft ratio of 5 to 200% by weight. 4. The rubber-like polymer latex (c) is the rubber-like polymer latex according to claim 1,
Alternatively, the rubber-reinforced vinyl polymer according to claim 3, which is another rubber-like polymer latex. 5. (e) 1 to 99 parts by weight of the rubber-reinforced vinyl polymer according to any one of claims 3 to 4 and (he) 99 to 1 parts by weight of another thermoplastic polymer [provided that (( E) +
(F) = 100 parts by weight] as a main component. 6. The rubber-reinforced vinyl polymer according to any one of claims 3 to 4 or the following (h-1) to 100 parts by weight of the (g) thermoplastic polymer composition according to claim 5.
A thermoplastic polymer composition comprising the following amounts of at least one selected from the group (H-4). (Ch-1); 1 to 30 parts by weight of flame retardant (Ch-2); 0.01 to antibacterial agent and / or antifungal agent
10 parts by weight (h-3); antistatic agent 0.1 to 30 parts by weight (h-4); foaming agent 0.1 to 20 parts by weight