JPH09316125A - Method for recovering rubber-reinforced vinyl polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rubber-reinforced vinyl polymer excellent in polymerization stability, mechanical stability, coagulability in acidification out and salting out, and molding properties, such as impact resistance, surface gloss, heat stability and hue, and reduced in the deposition of thermal (discoloration) and the waste water contamination load during production. SOLUTION: Ninety-seven (97) to 20 pts.wt. vinyl monomer (i) is emulsion- polymerized in the presence of 3-80 pts.wt. (in terms of solid matter) (the total of (i) and (ii) being 100 pts.wt.) rubbery polymer latex (ii) by using 0.01-10 pts.wt. emulsifier containing a sulfonate-base reactive emulsifier having an ethylene oxide molar ratio of 10 or below, and the obtained rubber-reinforced polymer latex is coagulated with a coagulant based on a divalent metal salt.

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. The present invention relates to a method for recovering a rubber-reinforced vinyl polymer, which is excellent in the appearance of molded products, has a non-staining property for molds, has a small amount of eye blemishes (thermal discoloration), and has a small load of polluting wastewater during manufacturing.

[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 post-adding the emulsifier to the latex after polymerization is generally used.

On the other hand, rubber-reinforced vinyl polymers obtained by using these latexes as base rubbers have recently become problems of mold contamination / corrosion during resin molding and corrosion of extrusion screw. Quality such as color tone and transparency tends to be emphasized. Therefore, it is preferable to reduce as much as possible the amount of the emulsifier that is one of the causes of these corrosion and poor quality. For this reason,
A method of reducing the amount of the emulsifier in the product in the washing step in the production step of the rubber-reinforced vinyl polymer by appropriately limiting the type of the emulsifier can be considered, but this method is not preferable because of the problem of wastewater treatment. 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 typical rubber-reinforced vinyl polymers, are obtained by emulsion polymerization of vinyl monomers constituting the 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, so that 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.

[0008]

SUMMARY OF THE INVENTION The present invention uses a specific sulfonate-based reactive emulsifier as at least a part of the emulsifier when producing a rubber-reinforced vinyl polymer latex and latex coagulation. By specifying the coagulant during the polymerization, the polymerization stability and mechanical stability during polymerization, the coagulability during acid precipitation and salting out, and the impact resistance, surface gloss, thermal stability, color tone, etc. To obtain a rubber-reinforced vinyl polymer having excellent appearance and non-staining property of a mold, having less eye blemishes (thermal discoloration), and having a small load of polluted waste water during production.

[0009]

The present invention provides (a) 97 to 20 parts by weight of a vinyl-based monomer (b) in the presence of 3 to 80 parts by weight of a rubber-like polymer latex (as solid content). However, (a) + (b) = 100 parts by weight] is added to (c) a sulfonate-based reactive emulsifier in which the number of moles of ethylene oxide is 10 or less (hereinafter also referred to as “sulfonate-based reactive emulsifier”) ( (D) A rubber-reinforced vinyl polymer latex obtained by emulsion polymerization using 0.01 to 10 parts by weight of an emulsifier containing (c-1), and (e) a coagulant containing a divalent metal salt as a main component. The present invention provides a method for recovering a rubber-reinforced vinyl-based polymer, which is characterized in that it is solidified by using. here,
(A) The rubber-like polymer latex has a gel content of 20-9.
5% by weight, Mooney viscosity (M
L _{1 + 4} , 100 ° C.) is preferably 10 to 300. The (c) emulsifier is a sulfonate-based reactive emulsifier (c-1) / other emulsifier (c-2) = 1 to 100/9.
It is preferably composed of 9 to 0% by weight.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION (a) The monomer component (hereinafter, also referred to as "monomer component") used for producing the rubbery polymer latex of the present invention has a glass transition when it becomes a polymer. A monomer having a point of 10 ° C. or lower, or a combination of monomers is preferable. Examples of the monomer used as the monomer component include a conjugated diene compound, an aromatic vinyl compound, a vinyl cyanide compound, a meta (acrylic) acid ester, a meta (acrylic) acid, and a graft crossing agent. In the monomer component, the glass transition point when it becomes a polymer is 10 ° C. or lower, that is, the rubber-forming monomer is the above conjugated diene compound or meth (acrylic acid) ester.

Of these, 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 vinyl cyanide compounds 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 monomer components, preferred combinations include the following (i) or (ii). (I) (a) 30 to 100% by weight, preferably 50 to 100% by weight, more preferably 60 to 100% by weight of the conjugated diene compound
100% by weight of (b) another monomer copolymerizable with the component (a), such as an aromatic vinyl compound, a cyanide vinyl compound, a (meth) acrylic acid alkyl ester and a (meth) acrylic acid. 70 to 0% by weight of at least one other monomer selected from the group, preferably 50 to 0% by weight, more preferably 40 to 0% by weight (however, (a)
+ (B) = 100% by weight], and has a glass transition point of 10 ° C. or lower, preferably 5 ° C. or lower when the polymer is obtained.
More preferably, a monomer component having a temperature of 0 ° C. or lower.

Further preferred combinations of the monomer component (i) 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

(Ii) (c) (meth) acrylic acid alkyl ester 30 to 100% by weight, preferably 50 to 100
% By weight, more preferably 60 to 100% by weight,
(D) Another monomer copolymerizable with the above-mentioned component (c), for example, a conjugated diene compound, an aromatic vinyl compound, a vinyl cyanide compound, (meth) acrylic acid, and a graft crossing agent. At least one other monomer 70-
0% by weight, preferably 50 to 0% by weight, more preferably 40 to 0% by weight (however, (c) + (d) = 100% by weight), and has a glass transition point of 10 when formed into a polymer. ℃ or less, preferably 5 ℃ or less, more preferably 0
A monomer component having a temperature of ℃ or less. In the monomer component (ii), 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. is there.

Further preferred combinations of the monomer component (ii) 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

In the component (i) or (ii), if the (a) conjugated diene compound or (c) (meth) acrylic acid alkyl ester, which is a rubber-forming monomer, is less than 30% by weight, the rubber elastic modulus is reduced. Is deteriorated, the impact resistance of the obtained rubber-reinforced vinyl polymer is deteriorated, and the desired physical properties are not obtained, which is not preferable. If the glass transition point (measured by DSC) of the component (i) or (ii) exceeds 10 ° C., the rubber elastic modulus decreases, and the resulting rubber-reinforced vinyl polymer is Impact resistance and fluidity are lowered, and desired physical properties are not obtained, which is not preferable.

In the production of the rubber-like polymer latex (a) of the present invention, a reactive emulsifier and / or
Or other emulsifiers are used. Here, examples of the reactive emulsifier include sulfonate-based reactive emulsifiers and other reactive emulsifiers. Among them, the sulfonate-based reactive emulsifier has a double bond copolymerizable with the monomer, and the rubber-like polymer latex obtained by using the same is the above-mentioned monomer component and sulfonic acid. Polymerization reaction with the salt-based reactive emulsifier and copolymerization in the rubber-like polymer, there are few low molecular weight free emulsifiers in the latex obtained,
The deterioration of the physical properties of the obtained rubber-reinforced vinyl polymer due to the residual organic acid and soap is improved. Since the sulfonate-based reactive emulsifier has a sulfonate, a latex having excellent polymerization stability and mechanical stability and excellent coagulability during acid precipitation and salting-out can be obtained.

Here, the sulfonate reactive emulsifier means a vinyl group, an acryloyl group, a methacryloyl group,
It is an emulsifier having a polymerizable unsaturated bond having a high reactivity such as an allyl group and a propenyl group, and a sulfonate. Examples of such a sulfonate-based reactive emulsifier include compounds represented by the following formulas (1) to (4), but the present invention is not limited thereto.

[0021]

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In the above formulas (1) to (4), R has 8 to 8 carbon atoms.
30 alkyl groups, alkenyl groups or aralkyl groups, n is an integer from 0 to 10, M is K, Na or NH ₄
It is. Here, n, that is, the number of moles of ethylene oxide, is 10 or less, preferably 5 or less. When the molar number n of ethylene oxide exceeds 10, coagulation becomes difficult when the obtained rubber-reinforced vinyl polymer latex is coagulated using a coagulant containing a divalent metal salt as a main component. These sulfonate-based reactive emulsifiers can be used alone or in combination of two or more.

As the reactive emulsifier, a reactive emulsifier other than the sulfonate-based reactive emulsifier, preferably 5
It is also possible to use them together in an amount of not more than 5% by weight, more preferably not more than 3% by weight. Other reactive emulsifiers include vinyl groups,
It is an emulsifier having a polymerizable unsaturated bond such as an acryloyl group, a methacryloyl group, an allyl group, a propenyl group, an amide group and the like, and a sulfonate or a carboxylate. Such other reactive emulsifiers can be represented by the following formulas (5) to (12).

[0024]

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[Chemical 6]

[Chemical 7]

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[Chemical 12]

[In the formulas (5) to (12), R'is an alkyl group, an alkenyl group or an aralkyl group having 6 to 18 carbon atoms, 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 (5) and (12).
In particular, in the formula (5), R ′ is C ₉ H ₁₉ and M is NH ₄
In the compound represented by the formula (12), R ′ 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 an emulsifier other than the reactive emulsifier, an anionic surfactant, a nonionic surfactant,
Examples include amphoteric surfactants.

Among these, examples of the anionic surfactant 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, a phosphate ester salt as an anion portion and an amine salt, a quaternary ammonium salt or the like 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 can be used alone or in combination of two or more.

The ratio of the emulsifier used is 1 to 100/99 to 0% by weight of sulfonate-based reactive emulsifier / other emulsifier,
It is preferably 20 to 100/80 to 0% by weight, and more preferably 50 to 100/50 to 0% by weight. If the proportion of the sulfonate-based reactive emulsifier used is less than 1% by weight,
Poor polymerization stability and mechanical stability during emulsion polymerization, poor coagulability during acid precipitation and salting out, and a large amount of residual free emulsifier, resulting in mold contamination of the rubber-reinforced vinyl polymer obtained. And the thermal stability is lowered, which is not preferable.

The total amount of the emulsifier used is 0.01 to 10 parts by weight, preferably 0.1 to 8 parts by weight, and more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the above monomer component.
Parts by weight. If it is less than 0.01 part by weight, the stability during emulsion polymerization is poor, while if it is more than 10 parts by weight, the elasticity of the obtained rubber-like polymer is lowered and the impact resistance is poor. The amount of other emulsifiers used is 10
It is preferably 3 parts by weight or less, more preferably 2 parts by weight or less, particularly preferably 1.5 parts by weight or less with respect to 0 parts by weight, and when it exceeds 3 parts by weight, a large amount of free emulsifier remains and the resulting rubber is obtained. Mold reinforcement of the reinforced vinyl polymer or the thermoplastic polymer composition occurs, and the thermal stability decreases, which is not preferable.

(A) 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-mentioned monomer component, an emulsifier, a polymerization initiator described below, 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 halogenated hydrocarbons such as chloroform and 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 method of charging all of the monomer components in a batch and polymerizing, a method of polymerizing a part of the monomer components and then continuously or intermittently adding the rest, a single amount A method of continuously adding body components from the beginning of 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 rubber-like polymer latex thus emulsion-polymerized (a) is preferably 50 to 50.
2,000 nm, more preferably 80 to 1,000 n
m, particularly preferably 100 to 500 nm, and in this range, the rubber-reinforced vinyl polymer obtained has excellent Izod impact strength and gloss.

Here, the average particle size is as follows: (a) A rubber-like polymer latex is treated with osmic acid, which 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.

In the present invention, the gel content of (a) the rubber-like polymer latex is preferably 20 to 95% by weight, more preferably 30 to 95% by weight, and particularly preferably 50.
~ 90% by weight. If the gel content is less than 20% by weight, the rubber strength is lowered and the impact resistance of the obtained rubber-reinforced vinyl polymer is lowered, which is not preferable, while if it exceeds 95% by weight, the rubber elasticity is lowered. However, 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 is excellent in extruding grade, for example, the elongation during vacuum forming of a sheet and the uniformity of product thickness, and is excellent in an electric refrigerator. Suitable for boxes. Further, when the gel content is 20 to 95% by weight, the obtained rubber-reinforced vinyl polymer is suitable for grades required to have appearances such as impact resistance, weld, and gloss, such as electric appliances and OA equipment. There is.

Here, the gel content means (a) the rubber-like polymer latex film (Ag) was 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 gel content can be adjusted easily and easily by selecting the kind and amount of the molecular weight modifier. In addition, the gel content can be adjusted by adding a cross-linking agent,
There are selections of the amount of polymerization initiator at the time of polymerization, the polymerization initiation temperature, etc., and by combining these, the desired rubber polymer latex (a) can be obtained.

Further, (a) the rubber-like polymer latex is
Mooney viscosity when converted to solid rubber (ML _{1 + 4} , 1
(00 ° C.) is preferably 10 to 300, more 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 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.

Incidentally, (a) the Mooney viscosity (ML _{1 + 4} , when converted into the solid rubber of the rubber-like polymer latex,
100 ° C.) is preferably 10 to 300, more preferably 30 to 250, particularly preferably 50 to 200 in the conjugated diene rubber [when the monomer component is the above (i)].
It is. In addition, acrylic rubber (the monomer component is
In the case of i)], it is preferably 10 to 200, more preferably 20 to 180, and particularly preferably 20 to 150.

In the present invention, the rubber-like polymer latex (a) thus obtained has a copolymerization content of the reactive emulsifier copolymerized with the rubber-like polymer, which is (a) Component 1
With respect to 00 parts by weight, preferably 0.01 to 10 parts by weight,
It is more preferably 0.1 to 10 parts by weight, and particularly preferably 0.5 to 10 parts by weight. Below 0.01 parts by weight,
There are many free emulsifiers remaining, and the desired polymerization stability,
It is not possible to obtain a rubber-reinforced vinyl polymer having excellent coagulability, little mold contamination, and good thermal stability. The copolymerization content of the reactive emulsifier can be adjusted by the amount of the polymerization initiator, the polymerization temperature, the method of charging the emulsifier, and the like.

The (d) rubber-reinforced vinyl polymer latex of the present invention comprises (b) vinyl monomer 97 in the presence of (a) 3 to 80 parts by weight (as solid content) of the rubber-like polymer latex. .About.20 parts by weight (however, (a) + (b) = 100 parts by weight), and (c) an emulsifier containing a sulfonate-based reactive emulsifier (c-1) in which the number of moles of ethylene oxide is 10 or less. It is obtained by emulsion polymerization using 01 to 10 parts by weight.

Here, the amount of the rubber-like polymer latex (a) 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 (b) 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 as the monomer component. The amount of the aromatic vinyl compound used is usually 0 to 10 in the vinyl monomer.
It is 0% by weight, preferably 30 to 100% by weight. When an aromatic vinyl compound is used, molding processability can be improved.

The vinyl cyanide compound is the same as the compounds exemplified as the above monomer components. The amount of the vinyl cyanide compound used is usually 0 to 7 in the vinyl monomer.
0% by weight, preferably 10 to 50% by weight. Use of a vinyl cyanide compound improves chemical resistance, impact resistance, compatibility with a polar polymer, and the like. 70
If it exceeds 5% by weight, the color tone may be deteriorated.

The (meth) acrylic acid alkyl ester is the same as the compounds exemplified as the above monomer components. The amount of alkyl (meth) acrylate used is
Usually, it is 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.

As other copolymerizable vinyl compound monomers, in addition to the (meth) acrylic acid exemplified in the above-mentioned monomer components, unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride. Maleimide, N-
Methyl maleimide, N-butyl maleimide, N- (p-
Methylphenyl) maleimide, N-phenylmaleimide; α- or β such as N-cyclohexylmaleimide
-Unsaturated dicarboxylic acid imide compounds and the like, epoxy group-containing monomers such as glycidyl methacrylate and allyl glycidyl ether; amide group-containing monomers such as acrylamide and methacrylamide; acrylamine, aminomethyl methacrylate, methacrylic acid amino ether, and methacrylic acid Amino group-containing monomers such as aminopropyl; 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2 -Hydroxyl group-containing monomers such as -methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and hydroxystyrene; oxazoline group-containing monomers such as vinyl oxazoline. That.

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 effects of the above-mentioned monomers are reduced, which is not preferable.

(B) The amount of vinyl monomer used is (a)
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.

The preferable (d) rubber-reinforced vinyl polymer latex will be illustrated below. The composition ratio of conjugated diene compound / aromatic vinyl compound is 5
Aromatic vinyl compound / cyanation in the presence of (a) 10 to 70 parts by weight (solid content) of a rubbery polymer latex 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 (B) vinyl-based monomer consisting of 0 to 90/5 to 40/0 to 50% by weight [(A) +
(B) = 100 parts by weight], a rubber-reinforced vinyl polymer latex obtained by polymerization.

20 to 80 parts by weight of (a) 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
(B) vinyl monomer 80 to 2 consisting of 0 to 90% by weight
A rubber-reinforced vinyl polymer latex obtained by polymerizing 0 parts by weight (however, (a) + (b) = 100 parts by weight).

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

(D) The (c) emulsifier used in the emulsion polymerization of the rubber-reinforced vinyl polymer latex must contain at least the sulfonate-based reactive emulsifier (c-1), and other You may use together an emulsifier (C-2). Here, a sulfonate-based reactive emulsifier (C-1),
The other emulsifier (C-2) is the same as the emulsifier used in the rubbery polymer latex. (C) Sulfonate-based reactive emulsifier in emulsifier (
The use ratio of 1) and the other emulsifier (C-2) is not particularly limited, but preferably (C-1) / (C-2) = 1 to 10
0/99 to 0% by weight, more preferably 20 to 100 /
80-0% by weight, particularly preferably 50-100 / 50-
0% by weight. Sulfonate-based reactive emulsifier (ha
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, and the rubber When the reinforced vinyl polymer is used, mold contamination occurs and the thermal stability decreases, which is not preferable.

The sulfonate-based reactive emulsifier (ha
In 1), as described above, the number of moles (n) of ethylene oxide is 10 or less, preferably 5 or less.
When the molar number n of ethylene oxide exceeds 10, coagulation becomes difficult when the obtained rubber-reinforced vinyl polymer latex is coagulated using a coagulant containing a divalent metal salt as a main component.

Further, (d) the amount of the whole emulsifier (c) used for producing the rubber-reinforced vinyl polymer latex is
With respect to 100 parts by weight of the total amount of the components (a) and (b),
It is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 8 parts by weight, and particularly preferably 0.5 to 8 parts by weight. If it is less than 0.01 part 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.

In the present invention, the copolymer of the sulfonate reactive emulsifier (C-1) copolymerized with the rubber-reinforced vinyl polymer latex (d) thus obtained is copolymerized with the polymer. The polymerization content is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, and particularly preferably 1 to 10 parts by weight, based on 100 parts by weight of the latex (in terms of solid content). Below 0.01 parts by weight,
It is impossible to obtain a rubber-reinforced vinyl polymer having a large amount of free emulsifiers remaining, a desired drainage load value, little mold contamination, and good thermal stability. The copolymerization content of the sulfonate-based reactive emulsifier (C-1) can be adjusted by the amount of the polymerization initiator, the polymerization temperature, the method of charging the emulsifier, and the like.

The (d) rubber-reinforced vinyl-based polymer latex thus obtained is coagulated with (e) a coagulant having a divalent metal salt as a main component, and (d) 'rubber-reinforced vinyl-based polymer latex is obtained. Recovered as a polymer.

The (e) coagulant used in the present invention contains a divalent metal salt as a main component, and examples of the metal salt include calcium chloride and magnesium sulfate. (E) By using a divalent metal salt as a coagulant, the resulting rubber-reinforced vinyl polymer or thermoplastic polymer composition is improved in thermal stability, appearance such as weld and gloss, and cost is reduced. The effect of reduction is obtained. In addition, (e) coagulants include, in addition to divalent metal salts, inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as acetic acid and formic acid, or trivalent metal salts such as these metal salts, aluminum chloride and aluminum sulfate. A metal salt or a polymer coagulant such as polyacrylamide may be used together in an amount of about 3% by weight or less.

In the recovery method of the present invention, a commonly used coagulation method, pressure coagulation method, multistage or continuous coagulation method is used, and the polymer particles can be washed with water and dried to obtain dried polymer particles. Further, a more preferable dry polymer is obtained by coagulating under the coagulation temperature, coagulant concentration, stirring conditions and coagulation conditions shown below. That is,
The solidification temperature (° C) is (Tv-5) <solidification temperature (° C) <
(Tv + 25) (where Tv represents the Vicat softening point (° C.) of the recovered polymer). The coagulant concentration (mmol / l) is C ≦ coagulant concentration ≦ (C + 10)
[However, C represents a coagulation value]. Further, the stirring condition is 100 ≦ peripheral speed (cm / s) ≦ 250.

As the coagulation conditions, heat treatment of the coagulated slurry (coagulated particles) can improve characteristics such as increase in bulk density and reduction of water content in the recovered coagulated particles. The heat treatment condition is (Tv-15) ≦ heat treatment temperature (° C.)
≦ (Tv + 30). In addition, this heat treatment time,
20 ≦ heat treatment time (min) ≦ 120. Further, the heat treatment is preferably carried out while stirring the polymer slurry composed of the coagulated particles, and particularly preferably so as to achieve uniform mixing. As for the stirring speed, the peripheral speed of the stirring blade is 50 to 8
It is 00 cm / s.

Further, the pH condition during the heat treatment is 4 ≦ p
H ≦ 6. This is due to the charged state of the particle surface, and the effect of pH is small even if the pH is lower than 4 or higher than 6. It is preferable to adjust the pH before the heat treatment, that is, at the time of solidification. In addition, hydrochloric acid, sulfuric acid, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc. can be used for pH adjustment. As a separating method, a horizontal belt filter, a centrifugal dehydrator, a vertical pressure filter or the like can be used for dehydration. Furthermore, the dehydrated coagulated particles are
It can be dried with a twin-screw extruder equipped with a dehydration slit.

Since the polymer particles of the rubber-reinforced vinyl polymer obtained according to the present invention have few fine powder particles, the problems usually occurring in the above method can be improved. The clogging of the horizontal belt filter and the filter cloth of the centrifugal dehydrator can be eliminated. A low discharge amount due to defective biting at the entrance of the twin-screw extruder is eliminated. It is possible to perform dehydration and drying without causing leakage of coagulated particles from the dehydration slit of the twin-screw extruder.

Incidentally, it is recovered in this way (d) '
The graft ratio of the rubber-reinforced vinyl polymer is 5 to 200.
%, Preferably 10 to 180%, more preferably 20
１５０150%. When the graft ratio is within this range, a rubber-reinforced vinyl polymer having an excellent balance of physical properties of impact resistance-thermal stability-molding processability can be obtained.

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

The (d) 'rubber-reinforced vinyl polymer recovered according to the present invention is used alone as a molding material, and (e) other thermoplastic polymers such as the following (e-1) ~ At least 1 selected from the group of (e-6)
Blended with seeds, as a (to) thermoplastic polymer composition,
They can be used as impact modifiers and compatibilizers for these polymers.

(E-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. (E-2); Polycarbonate (e-3); Thermoplastic polyester (e-4); Polyamide (e-5); Polyolefin (e-6); Other rubber-reinforced vinyl polymer

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

(V) In the thermoplastic polymer composition,
The ratio of (d) 'rubber-reinforced vinyl polymer to (e) other thermoplastic polymer is 1 to 99 parts by weight of (d)' component, preferably 10 to 89 parts by weight, more preferably 20 to 79 parts by weight. Parts, (e) component 99 to 1 parts by weight, preferably 90 to 1
It is 1 part by weight, more preferably 80 to 21 parts by weight (however, (d) ′ + (e) = 100 parts by weight).
If the ratio of (d) ′ 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, moldability is deteriorated.

The (d) ′ rubber-reinforced vinyl polymer or (he) thermoplastic polymer composition of the present invention includes a flame retardant, an antibacterial agent and / or an antifungal agent, an antistatic agent, and a foaming agent. By blending, for example, a thermoplastic polymer composition imparted with functionality such as flame retardancy, antibacterial / antifungal properties, antistatic properties and foaming properties. In addition, the (d) ′ rubber-reinforced vinyl polymer or (he) thermoplastic polymer composition of the present invention includes glass fiber, carbon fiber, metal fiber, glass beads, wollastonite, glass milled fiber, Rock filler, glass flakes, calcium carbonate, talc, mica, kaolin, barium sulfate,
Fillers such as graphite, 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 6 to 60 μm fiber diameter 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 (d) 'or the component (he) of the present invention.

The (d) ′ rubber-reinforced vinyl polymer or (he) thermoplastic polymer composition of the present invention includes known coupling agents, antioxidants, weathering (light) agents and plasticizers. , Colorants (pigments, dyes, etc.), lubricants, metal powders, etc. can be added.

The (d) 'rubber-reinforced vinyl polymer or the (v) thermoplastic polymer composition is composed of the (d)' component alone,
Alternatively, if necessary, the above-mentioned additives are added to the component (he), and various extruders, Banbury mixers, kneaders,
It can be prepared by kneading each component using a roll or 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 can be molded into various molded articles by injection molding, sheet extrusion, vacuum molding, modified shape molding, foam molding, 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, videos,
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, when a rubber-reinforced polymer is produced by emulsion-polymerizing a vinyl monomer using a rubber-like polymer latex, at least a part of the emulsifier is sulfonic acid. When a salt-based reactive emulsifier is used, the polymerization stability and mechanical stability are excellent, and the coagulability during acid precipitation and salting-out is also excellent, and the degree of swelling of the rubber-like polymer with respect to the vinyl monomer is changed. As a result, the graft ratio is improved, and this reactive emulsifier is (grafted) copolymerized in the copolymer forming the latex or in the vinyl polymer forming the matrix, thereby reducing the mixture of the emulsifier in the waste water. It Also, the reactive emulsifier contained in the rubber-reinforced vinyl polymer obtained is mainly (graft) -copolymerized, so the mold is unlikely to be contaminated, and molded products such as thermal stability and color tone are obtained. Excellent in appearance. Furthermore, since the rubber-reinforced vinyl-based polymer latex is recovered using a specific coagulant, the resulting rubber-reinforced vinyl-based polymer or thermoplastic polymer composition has a heat stability, weld, and gloss appearance. improves.

[0077]

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.

Mooney viscosity According to JIS K6300, Mooney viscosity (ML _{1 + 4} ,
(100 ° C.) was measured.

Organic acid / soap evaluation 6 g of a rubber-like polymer or a 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)] × [factor of N / 50 NaOH]
(%) 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 Ratio (% ) 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.

Graft ratio A certain amount (x) of the rubber-reinforced vinyl polymer was added to acetone, and the mixture was shaken with a shaker for 2 hours to dissolve the free copolymer. 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 under a temperature condition of 30 ° C. with a Uderode viscometer. 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.

Coagulation test latex 2,000 g (as solid content) was added to an aqueous solution in which 40 g of calcium chloride was dissolved in 8,000 g of water, heated to 85 ° C. to coagulate, and after coagulation, the state of the filtrate. The presence or absence of cloudiness in the coagulated filtrate was visually observed. Powder Properties Test Dry Polymer Sample 50 Using Low Tap Shaker
g was vibrated for 20 minutes, and powder characteristics were measured by JIS standard sieve 16 mesh on% and 200 mesh pass%.

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.

It was measured by 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.

Reference Example 1 [Rubber-like polymer latex (A-
Production of 1)] In a reactor equipped with a stirrer and having a capacity of 100 liters, 100 parts of 1,3-butadiene, 60 parts of water, and a sulfonate-based reactive emulsifier (hereinafter, also referred to as "reactive emulsifier") were used as Aqualon HS05 [No. Manufactured by Ichikohyo Pharmaceutical Co., Ltd.] [the above formula (3)
In, R = alkyl group having 9 carbon atoms, K = NH ₄ , n
= 5], 2.4 parts of potassium phosphate, 0.5 parts of potassium phosphate, 0.1 part of potassium hydroxide, 0.3 part of t-dodecyl mercaptan as a chain transfer agent, and 0.3 parts of potassium persulfate are added,
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 latex (A-1) having a solid content of 60.3%. The evaluation results of (A-1) are shown in Table 1.

Reference Example 2 [Rubber-like polymerized latex (A-
Production of 2)] As a reactive emulsifier, AQUALON HS10 [manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] [in the above formula (3), R = C9 alkyl group, K = NH ₄ , n = 10] is 2 Latex (A-) in the same manner as (A-1) except that 4 parts were used.
2) was obtained. The evaluation results of (A-2) are shown in Table 1. Reference Example 3 [Production of rubber-like polymerized latex (A-3)] As the reactive emulsifier, 1.2 parts of the above-mentioned Aqualon HS05 was used.
Part, and 1.2 parts of potassium rosinate are used, (A-
Latex (A-3) was obtained in the same manner as 3). (A-
The evaluation results of 3) are shown in Table 1. Reference Example 4 [Production of rubber-like polymerized latex (A-4)] As a reactive emulsifier, Adecaria Soap SE5N manufactured by Asahi Denka Co., Ltd. [in the above formula (1), R = 9 carbon atoms]
A latex was obtained in the same manner as in (A-4) except that 2.4 parts of the alkyl group of K = NH ₄ , n = 5] were used.
Table 1 shows the evaluation results of (A-4).

Reference Example 5 [Rubber-like polymerized latex (A-
5) (Production of Latex Used in Comparative Examples) As a reactive emulsifier, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Aqualon HS20 [in the above formula (3), R = C9 alkyl group, K = NH ₄ , A latex was obtained in the same manner as in (A-5) except that 2.4 parts of n = 20] was used. (A
The evaluation results of -5) are shown in Table 1. Reference Example 6 [Production of rubber-like polymerized latex (A-6) (latex used in Comparative Example)] As a reactive emulsifier, Adecaria Soap SE20N manufactured by Asahi Denka Kogyo Co., Ltd. [in the above formula (1), R = except that 2.4 parts alkyl group having a carbon number of _{9, K = NH 4, n} = 20 ] was obtained a latex in the same manner as (a-6). Table 1 shows the evaluation results of (A-6). Reference Example 7 [Production of rubber-like polymerized latex (A-7) (latex used in Comparative Example)] A latex was obtained in the same manner as in (A-6) except that 2.4 parts of potassium rosinate was used as an emulsifier. It was (A-
Table 1 shows the evaluation results of 7).

Example 1 (Production of Rubber Reinforced Vinyl Polymer) To 89 parts of latex (A-1) (50 parts of solid content), 12 parts of styrene, 5 parts of acrylonitrile, and the above-mentioned aqualon as a reactive emulsifier 0.3 parts HS05, 0.05 parts potassium hydroxide, 80 parts water, 0.06 parts cumene hydroperoxide (hereinafter sometimes abbreviated as "CHPO"), sodium alkyldiphenyl ether sulfonate 0.8, water 7.9 parts and 0.2 part of t-dodecyl mercaptan were added, and batch polymerization was carried out at 70 ° C. for 1 hour. Subsequently, 23 parts of styrene, 10 parts of acrylonitrile, 0.6 part of the above-mentioned Aqualon HS05 as a reactive emulsifier, 0.1 part of potassium hydroxide, 20 parts of water, and 0 cumene hydroperoxide were added to a polymerization system kept at 70 ° C. 1 part and 0.3 part of t-dodecyl mercaptan,
The mixture was added over 2 hours to carry out incremental polymerization.

Then, to the polymerization system kept at 70 ° C., 0.05 part of cumene hydroperoxide, 0.2 part of sodium alkylphenyl ether disulfonate, 2.7 parts of water were added.
Parts were added all at once 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 with calcium chloride or magnesium sulfate, washing or acid washing and drying were carried out. , Got the powder. The physical properties of the obtained powder were evaluated. Table 2 shows the results.

Example 2 (Production of Rubber-Reinforced Vinyl Polymer) Using latex (A-1), the above-mentioned Aqualon HS05 and potassium rosinate were mixed at 0.15 parts / 0.15 parts in batch polymerization at the time of batch polymerization. 0.3 parts during polymerization
Polymerization was carried out in the same manner as in Example 1 except that 0.3 part was used. This is referred to as latex (B-2). The evaluation results of this latex (B-2) are shown in Table 2. Example 3 (Production of rubber-reinforced vinyl polymer) Polymerization was carried out in the same manner as in Example 1 except that the latex (A-2) was used. This is latex (B-3)
And The evaluation results of this latex (B-3) are shown in Table 2.
Shown in

Example 4 (Production of rubber-reinforced vinyl polymer) Polymerization was carried out in the same manner as in Example 1 except that the latex (A-3) was used. This is latex (B-4)
And The evaluation results of this latex (B-4) are shown in Table 2.
Shown in Example 5 (Production of rubber-reinforced vinyl polymer) Polymerization was carried out in the same manner as in Example 1 except that the latex (A-4) was used. This is latex (B-5)
And The evaluation results of this latex (B-5) are shown in Table 2.
Shown in

Comparative Example 1 (Production of Rubber Reinforced Vinyl Polymer) Polymerization was carried out in the same manner as in Example 1 except that the latex (A-5) was used. This is latex (B-6)
And The evaluation results of this latex (B-6) are shown in Table 3.
Shown in Comparative Example 2 (Production of Rubber Reinforced Vinyl Polymer) Polymerization was carried out in the same manner as in Example 1 except that the latex (A-6) was used. This is latex (B-7)
And The evaluation results of this latex (B-7) are shown in Table 3.
Shown in

Comparative Example 3 (Production of Rubber Reinforced Vinyl Polymer) Example 1 was repeated except that latex (A-1) was used and Aqualon HS20 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. was used as the reactive emulsifier. Polymerization was carried out in the same manner. This is referred to as latex (B-8). This latex (B-8)
The evaluation results of are shown in Table 3. Comparative Example 4 (Production of Rubber-Reinforced Vinyl Polymer) Polymerization was carried out in the same manner as in Example 1 except that the latex (A-7) was used. This is latex (B-9)
And The evaluation results of this latex (B-9) are shown in Table 3.
Shown in Comparative Example 5 (Production of Rubber Reinforced Vinyl Polymer) The same as in Example 1 except that latex (A-1) was used and ADEKA REASOAP SE20N manufactured by Asahi Denka Co., Ltd. was used as the reactive emulsifier. Polymerization was carried out by the method. This is designated as latex (B-10). The evaluation results of this latex (B-10) are shown in Table 3.

Examples 6 to 10 and Comparative Examples 6 to 9 (Production of Thermoplastic Polymer Composition) The rubber-reinforced vinyl polymer prepared above was added to the thermoplastic polymer [acrylonitrile (AN) / styrene (ST)].
(Polymerization ratio) = 30/70 AN-ST copolymer], other heat stabilizers, lubricants, etc. are mixed in the compounding formulation shown in Tables 4 to 5, and melt-kneaded at a resin temperature of 200 ° C. in an extruder with a vent. Then, pellets were manufactured by extrusion. 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 4-5.

[0097]

[Table 1]

[0098]

[Table 2]

[0099]

[Table 3]

[0100]

[Table 4]

[0101]

[Table 5]

[0102]

INDUSTRIAL APPLICABILITY According to the present invention, impact resistance, surface glossiness, thermal stability, and color tone are improved by using a sulfonate-based reactive emulsifier as at least a part of the emulsifier and a specific coagulant. It is possible to obtain a rubber-reinforced vinyl-based polymer having excellent appearance of molded products, non-staining property of molds, less tarnishing (thermal discoloration), and less burden of wastewater pollution during manufacturing.

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

Claims (2)

[Claims] 1. A rubber polymer latex 3-80.
In the presence of parts by weight (in terms of solid content), 97 to 20 parts by weight of (b) vinyl-based monomer [where (a) + (b) = 100
Parts by weight], and (c) the number of moles of ethylene oxide is 10
(D) A rubber-reinforced vinyl polymer latex obtained by emulsion polymerization using 0.01 to 10 parts by weight of an emulsifier containing the following sulfonate-based reactive emulsifier (C-1),
A method for recovering a rubber-reinforced vinyl-based polymer, which comprises coagulating using a coagulant containing a divalent metal salt as a main component. 2. (a) The rubber-like polymer latex has a gel content of 20 to 95% by weight and a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 10 to 300 when converted into a solid rubber. 1. The method for recovering a rubber-reinforced vinyl polymer according to 1.