JPH09316138A - Rubbery polymer latex, rubber-reinforced vinyl polymer, and thermoplastic polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rubber polymer latex excellent in polymerization stability, mechanical stability, coagulability in acidification out and salting out, reduced in the thermal discoloration and waste water contamination load during production, and excellent in molding properties such as impact resistance, surface gloss, heat stability and hue, a rubber-reinforced vinyl polymer, and a thermoplastic polymer composition containing the same. SOLUTION: This invention provides a rubber polymer latex obtained by emulsion-polymerizing 100 pts.wt. monomer component (i) capable of forming a rubber in the presence of 0.01-10 pts.wt. emulsifier (ii) comprising a reactive emulsifier (ii-1) and another emulsifier (ii-2) in a ratio of (1-100)/(99-0)(wt.%) and having a content of the copolymerized reactive emulsifier (ii-1) of 50wt.% or below, a rubber-reinforced vinyl polymer, and a thermoplastic polymer composition comprising the rubber-reinforced vinyl polymer and another thermoplastic polymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to excellent polymerization stability and mechanical stability during polymerization, excellent coagulability during acid precipitation and salting-out, a small load of wastewater pollution during production, and impact resistance. Excellent in appearance of molded products such as surface gloss, thermal stability, color tone, and non-contamination of molds, and little eye blemishes (thermal discoloration).
The present invention relates to a rubber-like polymer latex, a rubber-reinforced vinyl polymer using the rubber-like polymer latex, and a thermoplastic polymer composition in which the rubber-reinforced vinyl polymer is blended with another thermoplastic polymer.

[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]

DISCLOSURE OF THE INVENTION The present invention uses a reactive emulsifier as at least a part of an emulsifier when producing a rubbery polymer latex, and copolymerizes the reactive emulsifier with the polymer. By keeping the rate below a certain value, it has excellent polymerization stability and mechanical stability during polymerization, excellent coagulability during acid precipitation and salting-out, and has a small load of wastewater pollution during manufacturing, as well as impact resistance and surface. Rubber-like polymer latex with excellent appearance of molded products such as glossiness, heat stability, and color tone, non-staining property of molds, and little eye blemishes (thermal discoloration), and rubber reinforcement using this rubber-like polymer latex The object is to obtain a vinyl polymer and a thermoplastic polymer composition using the rubber-reinforced vinyl polymer.

[0009]

According to the present invention, (a) 100 parts by weight of a monomer component capable of forming a rubber, (b) a reactive emulsifier (b-1) / another emulsifier (b-2). = 1-100 /
Obtained by emulsion polymerization in the presence of 0.01 to 10 parts by weight of an emulsifier consisting of 99 to 0% by weight, and a reactive emulsifier (low
The rubbery polymer latex has a copolymerization ratio of 1) of 50% by weight or less. The above-mentioned (a) monomer component is preferably the following (a-1) or (a-2). (A-1); (a) 30 to 100% by weight of conjugated diene compound, (b) aromatic vinyl compound, (c) vinyl cyanide compound, (d) (meth) acrylic acid alkyl ester and (e) ( 70 to 0% by weight of at least one other monomer selected from the group of (meth) acrylic acid
(A) + (b) + (c) + (d) + (e) = 100% by weight], and has a glass transition point of 1 when it becomes a polymer.
A monomer component having a temperature of 0 ° C. or lower. (A-2); (d) 30 to 100% by weight of (meth) acrylic acid alkyl ester, and (a) a conjugated diene compound,
At least one other monomer 70 selected from the group consisting of (b) aromatic vinyl compound, (c) vinyl cyanide compound, (e) (meth) acrylic acid, and (f) graft crossing agent 70.
~ 0 wt% [(d) + (a) + (b) + (c)
+ (E) + (f) = 100% by weight] and has a glass transition point of not higher than 10 ° C. when it becomes a polymer.

Further, the present invention uses an emulsifier composed of (b) a reactive emulsifier (b-1) and / or another emulsifier (b-2), wherein the (c) rubbery polymer latex (hereinafter referred to as "( C) Also referred to as "rubbery 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 is obtained by emulsion polymerization, and the graft ratio is 5 to 20.
A rubber-reinforced vinyl polymer having a content of 0% by weight is provided.

Further, in the present invention, 1 to 99 parts by weight of the above (e) rubber-reinforced vinyl polymer and 99 to 1 parts by weight of another thermoplastic polymer [(e) + (e)] = 100
Parts by weight] as a main component.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION (a) The monomer component capable of forming the rubber of the present invention has a glass transition point of 1 when it becomes a polymer.
A monomer having a temperature of 0 ° C. or lower or a combination of monomers is preferable. (A) The monomer used in the monomer component includes (a) a conjugated diene compound, (b) an aromatic vinyl compound, (c) a vinyl cyanide compound, (d) a meta (acrylic) acid ester, and ( e) meth (acrylic) acid, (f) graft crossing agent and the like. In addition, in the (a) monomer component,
The glass transition point of the polymer is 10 ° C. or lower, that is, the rubber-forming monomer is the above-mentioned (a) conjugated diene compound or (d) meth (acrylic) acid ester.

Of these, the conjugated diene compound (a) includes 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, chloroprene, and the like.
Particularly preferred is 1,3-butadiene. (B) As aromatic vinyl compounds, styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, t-butylstyrene, α-methylstyrene, 1,1-diphenylstyrene, N, N-diethyl- p-aminostyrene,
Examples thereof include N, N-diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene and the like.

Examples of the vinyl cyanide compound (c) include acrylonitrile and methacrylonitrile. The (d) meth (acrylic) acid ester has 1 to 12 carbon atoms, preferably 4 to 12 carbon atoms, together with meth (acrylic) acid.
Esters with eight monohydric alcohols are 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, isobornyl (meth) acrylate and the like, Butyl (meth) acrylate, 2-
Ethylhexyl (meth) acrylate is preferred.

Examples of (e) meth (acrylic) acid include acrylic acid and methacrylic acid. (F) 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. In addition,
The (f) graft crossing agent facilitates intermolecular cross-linking of, for example, a (meth) acrylic acid alkyl ester polymer, and graft bond with a matrix, thereby improving the impact resistance of the obtained rubber-reinforced vinyl polymer. .

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) an aromatic vinyl compound,
70 to 0% by weight of at least one other monomer selected from the group of (c) vinyl cyanide compound, (d) (meth) acrylic acid alkyl ester and (e) (meth) acrylic acid, preferably 50 to 0% by weight, more preferably 4
0 to 0% by weight [(a) + (b) + (c) +
(D) + (e) = 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 preferred 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 / (c) Vinyl cyanide compound (a) Conjugated diene compound / (d) (Meth) acrylic acid Alkyl ester

(A-2); (d) 30 to 100% by weight of (meth) acrylic acid alkyl ester, preferably 50 to
100% by weight, more preferably 60-100% by weight
And at least one selected from the group consisting of (a) conjugated diene compound, (b) aromatic vinyl compound, (c) vinyl cyanide compound, (e) (meth) acrylic acid, and (f) graft crossing agent. Other monomers 70 to 0% by weight, preferably 50 to 0% by weight, more preferably 40 to 0% by weight [(d) + (a) + (b) + (c) + (e) +
(F) = 100% by weight], and the glass transition point when it becomes a polymer is 10 ° C. or lower, preferably 5 ° C. or lower, more preferably 0 ° C. or lower. In addition, in the monomer component (a-2), the alkyl group in (d) (meth) acrylic acid alkyl ester has 2 to 2 carbon atoms.
12 are preferable, 3-8 are more preferable, 4-6 are especially preferable.

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

In the component (a-1) or (a-2), when the rubber-forming monomer (a) conjugated diene compound or (d) (meth) acrylic acid alkyl ester is less than 30% by weight. However, the rubber elastic modulus is lowered, the impact resistance of the obtained rubber-reinforced vinyl polymer is lowered, and the desired physical properties are not obtained, which is not preferable. Further, when the glass transition point (measured by DSC) of the component (a-1) or (a-2) becomes a polymer, the rubber elastic modulus is lowered and the obtained rubber-reinforced vinyl is obtained. The impact resistance and fluidity of the polymer are lowered, and the desired physical properties cannot be obtained, which is not preferable.

In the production of the (c) rubber-like polymer latex of the present invention, the reactive emulsifier (ro-
1) and / or other emulsifiers (b-2) are used. The reactive emulsifier (b-1) has a double bond copolymerizable with the monomer, and the rubber-like polymer latex (c) obtained by using this reacts with the above-mentioned monomer component. Because of the polymerization reaction with the hydrophilic emulsifier and copolymerization in the rubber-like polymer,
There are few low molecular weight free emulsifiers in the latex obtained, and as a result, the residual organic acid in the rubber-reinforced vinyl polymer or thermoplastic polymer composition obtained, physical property deterioration due to soap is improved, and heat discoloration resistance is improved. improves.

As the reactive emulsifier (b-1), a carboxylate-based reactive emulsifier is preferable. The carboxylate-based reactive emulsifier has a double bond copolymerizable with a monomer, and the rubber-like polymer latex (c) of the present invention obtained by using the same is the monomer (a) above. Since the monomer component and the carboxylate-based reactive emulsifier undergo a polymerization reaction and are copolymerized in the rubber-like polymer, the obtained latex contains few free low-molecular-weight emulsifiers, and the obtained rubber-reinforced vinyl polymer Also, the deterioration of physical properties of the thermoplastic polymer composition due to residual organic acid and soap is improved. Since the carboxylate-based reactive emulsifier has a carboxylate, a latex having excellent polymerization stability and mechanical stability and excellent coagulability during acid precipitation and salting-out can be obtained.

Here, the carboxylic acid salt-based reactive emulsifier is an emulsifier having a highly unsaturated polymerizable unsaturated bond and a carboxylic acid salt. Among the carboxylate-based reactive emulsifiers, compounds having an amide structure are particularly preferable.
Examples of such a carboxylate-based reactive emulsifier include compounds represented by 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 , and Z is H or C.
H ₃ and R are alkyl groups, alkenyl groups or aralkyl groups having 6 to 18 carbon atoms, n is 0 to 30 and 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 a carboxylate-based reactive emulsifier, the following formula (5)
The compound represented by these is mentioned. These formulas (2) to
In (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.

[0024]

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The carboxylic acid salt-based reactive emulsifier includes
Other reactive emulsifiers (hereinafter also referred to as "other reactive emulsifiers"), preferably 5% by weight or less, more preferably 3
It is also possible to use them together in an amount of not more than about wt%. 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. Such other reactive emulsifiers can be represented by the following formulas (6) to (11).

[0026]

[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, examples of the other emulsifier (B-2) include anionic surfactants, nonionic surfactants and amphoteric surfactants.

Among these, examples of the anionic surfactant include sulfates of higher alcohols, alkylbenzene sulfonates, aliphatic sulfonates, and sulfates 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 can be used alone or in combination of two or more.

(B) The ratio of the emulsifier to be used is such that the reactive emulsifier (B-1) / other emulsifier (B-2) is 1 to 100/99.
Is 0 to 0% by weight, preferably 20 to 100/80 to 0% by weight, and more preferably 50 to 100/50 to 0% by weight. Use ratio of reactive emulsifier (b-1) is 1% by weight
When the amount is less than, 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 resulting rubber-reinforced vinyl polymer or thermoplastic polymer Mold contamination of the combined composition occurs,
It is not preferable because the thermal stability is lowered.

The total amount of the (b) emulsifier is preferably 0. 0 with respect to 100 parts by weight of the (a) monomer component.
The amount is 01 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, and particularly preferably 0.5 to 8 parts by weight. 0.01
If it is less than 10 parts by weight, the stability during emulsion polymerization is poor, while 10
If the amount is more than parts by weight, the resulting rubber-reinforced vinyl polymer or thermoplastic polymer composition will have poor impact resistance.

(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 modifier 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) a method of charging all of the monomer components at once and polymerizing, or (a) a part of the monomer components are polymerized and the rest thereof 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 size of the rubber-like polymer latex (c) 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 the (c) 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. 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, while it exceeds 95% by weight. If so, rubber elasticity is high and impact resistance and fluidity are 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. Further, when the gel content is 20 to 95% by weight, the obtained rubber-reinforced vinyl polymer or thermoplastic polymer composition has a grade required to have appearances such as impact resistance, weld and gloss, for example, electrical products. , OA equipment, etc.

Here, the gel content means (c) a film (Ag) of a rubber-like polymer latex is immersed in 100 ml of toluene at 50 ° C. for 2 hours with stirring, and then filtered using a 120 mesh wire mesh. 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 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 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 or thermoplastic polymer composition has good impact resistance. To adjust the Mooney viscosity,
It can be easily carried out by selecting the kind and amount of the molecular weight regulator, 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 300, more preferably 30 to 250, particularly preferably 50 to 2 in the conjugated diene rubber [when the monomer component is the above (a-1)].
00. Further, in the case of acrylic rubber [when the monomer component is the above-mentioned (a-2)], preferably 10 to 200, more preferably 20 to 180, and particularly preferably 20 to 1
50.

In the present invention, the rubber-like polymer latex (c) thus obtained has a copolymerization content of the reactive emulsifier (b-1) copolymerized with the rubber-like polymer,
It is preferably 0.01 to 100 parts by weight of the component (a).
The amount is 10 parts by weight, more preferably 0.1 to 10 parts by weight, and particularly preferably 0.5 to 10 parts by weight. If the amount is less than 0.01 part by weight, a large amount of free emulsifier remains, the desired polymerization stability and coagulation are excellent, there is little mold contamination, and the rubber reinforced vinyl polymer or thermoplastic polymer has good thermal stability. The composition cannot be obtained.

In the present invention, the reactive emulsifier (b-1)
The copolymerization rate of 50% by weight or less, preferably 3%, with respect to the obtained rubber-like polymer latex (solid content conversion).
0 to 40% by weight. When it exceeds 50% by weight, the free emulsifier in the polymerization system decreases, the polymerization system becomes unstable, and the mechanical stability by a pump after the polymerization is deteriorated, and the reactivity of the rubbery polymer is highly polar. The emulsifier (B-1) is copolymerized too much, rubber elasticity is lowered, and impact resistance is lowered. In addition, (c) the reactive emulsifier (b-1) remaining during the production of the rubbery polymer latex is
(E) It is preferable that the rubber-reinforced vinyl polymer is copolymerized during the graft emulsion polymerization at the time of production, and is finally left almost in the polymerization system. The copolymerization content (rate) of this reactive emulsifier (b-1) is the kind, amount, addition method of polymerization initiator, polymerization temperature, polymerization rate, kind of emulsifier, combination, addition method (batch, multi-stage, increment). It can be adjusted by

The (e) rubber-reinforced vinyl polymer latex of the present invention uses an emulsifier consisting of (b) reactive emulsifier (b-1) and / or other emulsifier (b-2),
(C) In the presence of 3 to 80 parts by weight of rubber-like polymer latex (as solid content), (D) 97 to 20 parts by weight of vinyl-based monomer [(C) + (D) = 100 parts by weight) ] By emulsion polymerization.

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 (d) vinyl-based monomer. 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 (d) 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 (d) 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 7 in the (d) vinyl monomer.
It is 0% by weight, preferably 0 to 60% by weight. These copolymerizable vinyl compound monomers are used for imparting special properties to the (e) 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.

(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 reactive emulsifier (b-1) and / or the same as used in the above (c) rubber-like polymer latex. Alternatively, another emulsifier (B-2) can be used. (B) The ratio of the reactive emulsifier (b-1) to the other emulsifier (b-2) in the emulsifier is not particularly limited,
Preferably (b-1) / (b-2) = 1 to 100/99
To 0% by weight, more preferably 20 to 100/80 to 0
% By weight, particularly preferably 50-100 / 50-0% by weight
It is. If the proportion of the reactive emulsifier (B-1) used is less than 1% by weight, the polymerization stability and mechanical stability during emulsion polymerization will be poor, and the coagulability during acid precipitation and salting-out will be poor, and it will remain. Since there are many free emulsifiers, when a rubber-reinforced vinyl polymer or a thermoplastic polymer composition is used, mold contamination occurs and thermal stability is reduced, 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.

In the present invention, the copolymerization content of the reactive emulsifier (b-1) copolymerized in the thus obtained (e) rubber-reinforced vinyl polymer is 100 parts by weight of latex ( Relative to solid content), preferably 0.0
The amount is 1 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, and particularly preferably 1 to 10 parts by weight. If the amount is less than 0.01 parts by weight, a large amount of free emulsifier remains, the target drainage load value is small, the mold is less contaminated, and the rubber-reinforced vinyl polymer or thermoplastic polymer composition has good thermal stability. I can't get things. Further, it is preferable that the reactive emulsifier (b-1) is copolymerized at the time of graft emulsion polymerization during the production of the (e) rubber-reinforced vinyl polymer, and is not substantially left in the polymerization system finally. The copolymerization content (ratio) of this reactive emulsifier (b-1) depends on the kind of the polymerization initiator,
It can be adjusted by the amount, addition method, polymerization temperature, polymerization rate, type of emulsifier, combination, addition method (batch, multi-stage, increment) and the like.

The thus obtained (e) latex of the rubber-reinforced vinyl polymer is coagulated with a usual coagulant and recovered as a rubber-reinforced vinyl polymer.

The graft ratio of the obtained (e) rubber-reinforced vinyl polymer 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 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 (e) 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 (e) rubber-reinforced vinyl polymer of the present invention is used alone as a molding material.
Other thermoplastic polymers, for example, the following (he-1) to (he-
Blended with at least one selected from the group of 6),
(G) As a thermoplastic polymer composition, it can be used as an impact modifier, a compatibilizer, etc. of these polymers.

(F-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 (he) other thermoplastic polymers include (he-1); AS resin, MS resin, styrene-
Maleic anhydride copolymer, maleimide copolymer, etc.,
(He-2); aromatic polycarbonate, (He-3); polyester such as polybutylene terephthalate and polyethylene terephthalate, (He-4); polyamide such as nylon 6, nylon 6,6 and nylon 4,6, (He −
5); polyethylene, polypropylene, (to-6); other ABS resin, AES resin, HIPS, styrene resin such as AS resin, and others; PPS resin, liquid crystal polyester resin, polyarylate resin, polysulfone resin, 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 [however,
(E) + (to) = 100 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.

The (e) rubber-reinforced vinyl polymer or (g) thermoplastic polymer composition of the present invention contains a flame retardant, an antibacterial agent and / or an antifungal agent, an antistatic agent, a foaming agent, etc. By blending, it is possible to obtain a thermoplastic polymer composition imparted with functionality such as flame retardancy, antibacterial / mold resistance, antistatic properties, foamability and the like. In addition, the (e) rubber-reinforced vinyl polymer or (g) 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, graphite, wood powder, molybdenum disulfide, magnesium oxide, zinc oxide whiskers, potassium titanate whiskers, glass balloons, ceramic balloons, etc. They 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 (e) or the component (g) of the present invention.

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

The (e) rubber-reinforced vinyl polymer or (g) thermoplastic polymer composition may contain the (e) component alone or the (g) component, if necessary, with the above additives.
It can be prepared by kneading each component 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 may be injection molded, sheet extruded, vacuum molded, profiled,
Various molded products can be molded by 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 the rubbery polymer latex is produced, the reactive emulsifier is used as at least a part of the emulsifier, and the copolymerization rate of the reactive emulsifier is set to a certain value or less. The resulting polymer has excellent polymerization stability and mechanical stability, and also has excellent coagulability at the time of acid precipitation and salting out.The graft ratio is improved by the change in the degree of swelling of the rubber-like polymer with respect to the vinyl monomer. In addition, this reactive emulsifier is incorporated into the vinyl polymer constituting the copolymer or matrix constituting the above latex (grafting).
Copolymerization reduces emulsifier incorporation in wastewater. 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.

[0074]

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.

[0075] The coagulated amount latex was filtered through a 100 mesh screen, drying the coagulum remaining on a mesh drier, dry coagulum weight percentage relative to the resulting polymer weight (%) was solidified quantity. Mechanical stability 500 g of latex filtered with 100 mesh wire mesh,
Put it in a 1,000 liter container and keep it at 70 ℃.
Using a homomixer, high speed stirring was performed at 6,000 rpm, and the solidification time (minutes) was measured. 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 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.

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.

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.

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, 80 parts of water, and as a reactive emulsifier, Aqualon HS05 [manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] ] For 2.4 copies,
1.2 parts of potassium phosphate, 0.1 part of potassium hydroxide, t-dodecyl mercaptan as a chain transfer agent (hereinafter referred to as "t-
DMC)) 0.3 parts, potassium persulfate 0.1
Parts were added and batch polymerization was carried out at 60 to 70 ° C. for 30 hours.
The polymerization conversion rate was 95%. To this polymerization system, N, N-diethylhydroxylamine as a polymerization terminator was added.
Two parts were added to stop the reaction. After that, depressurize 1,3-
The butadiene was removed to obtain a polybutadiene latex. This is designated as latex (A-1) (solid content 53.
8%). 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 having a capacity of 100 liters, 99 parts of butyl acrylate, 1.0 part of allyl methacrylate as a graft crossing agent, 125 parts of water, and Aqualon HS05 as a reactive emulsifier. [Daiichi Kogyo Seiyaku Co., Ltd.] 0.6 part, potassium phosphate 0.5 part, potassium hydroxide 0.1 part, t-dodecyl mercaptan 0.1 part as a chain transfer agent, potassium persulfate 0 1 part, and polymerization temperature of 60 to 70 ° C. for 5 hours, three-stage batch polymerization [monomer (weight ratio) 33/3
3/34], and 1.2 parts (boost) of the reactive emulsifier AQUALON HS05 in a reaction time of 4 hours,
Emulsion polymerization was carried out in the same manner as in Example 1. The polymerization conversion rate was 99.5%. To this polymerization system, 0.2 part of N, N-diethylhydroxylamine was added as a polymerization terminator to stop the reaction. Then, the monomer was removed under reduced pressure to obtain an acrylic rubber latex. This is designated as latex (A-2) (solid content 44.9%). The evaluation results of this latex (A-2) are shown in Table 1.

Example 3 (Production of rubbery polymer latex) The above-mentioned Aqualon HS05 was used as a reactive emulsifier in an amount of 1.2.
Latex was obtained in the same manner as in Example 1 except that 1.2 parts of potassium rosinate was used. This is referred to as latex (A-3). The evaluation results of this latex (A-3) are shown in Table 1. Example 4 (Production of rubber-like polymer latex) 60 parts of water, 0.5 part of potassium phosphate, 1.2 parts of the above-mentioned Aqualon HS05 as a reactive emulsifier, and 1.2 parts (boost for 15 hours of polymerization time). A latex was obtained in the same manner as in Example 1 except that (1) was used. This is referred to as latex (A-4). The evaluation results of this latex (A-4) are shown in Table 1.

Example 5 (Production of rubber-like polymer latex) A latex was obtained in the same manner as in Example 1 except that 90 parts of 1,3 butadiene and 10 parts of styrene were used. This is designated as latex (A-5). This latex (A-5)
Table 1 shows the evaluation results. Example 6 (Production of rubbery polymer latex) 90 parts of butyl acrylate, 10 parts of 1,3 butadiene,
A latex was obtained in the same manner as in Example 2 except that allyl methacrylate was omitted. This is latex (A-
6). The evaluation results of this latex (A-6) are shown in Table 1. Example 7 (Production of rubbery polymer latex) 60 parts of water, 0.5 part of potassium phosphate, a compound of the above formula (2) as a reactive emulsifier (R = alkyl group having 10 carbon atoms, n = 5, M = K) 1.2 parts, polymerization time 15
A latex was obtained in the same manner as in Example 1 except that 1.2 parts (boost) was used per hour. This is designated as latex (A-7). The evaluation results of this latex (A-7) are shown in Table 1.

Comparative Example 1 (Production of Rubbery Polymer Latex) A latex was obtained in the same manner as in Example 1 except that 2.4 parts of potassium rosinate was used as an emulsifier. This is designated as latex (A-8). This latex (A-8)
The evaluation results of are shown in Table 2. Comparative Example 2 (Production of rubber-like polymer latex) Example except that 60 parts of water, 0.5 part of potassium phosphate, 0.5 part of potassium persulfate and 2.4 parts of AQUARON HS05 as a reactive emulsifier were used. A latex was obtained in the same manner as in 1. This is designated as latex (A-9). The evaluation results of this latex (A-9) are shown in Table 2.

Comparative Example 3 (Production of Rubbery Polymer Latex) Same as Example 1 except that 4.8 parts of Aqualon HS05, 1.8 parts of potassium phosphate and 0.5 parts of potassium persulfate were used as emulsifiers. To obtain a latex. This is designated as latex (A-10). This latex (A-1
Table 2 shows the evaluation results of 0).

Example 8 (Production of Rubber Reinforced Vinyl Polymer) 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 of HS05, 0.05 parts of potassium hydroxide, 80 parts of water, 0.06 parts of cumene hydroperoxide (hereinafter sometimes abbreviated as "CHPO"), 0.8 parts of sodium alkyldiphenyl ether sulfonate, Water (7.9 parts) and t-dodecyl mercaptan (0.2 parts) were added, and the mixture was subjected to batch polymerization 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 and subjected to increment 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 (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, salting out or acidifying washing and drying were carried out to obtain a powder. The physical properties of the obtained powder were evaluated. The results are shown in Table 3.

Example 9 (Production of Rubber-Reinforced Vinyl Polymer) Using latex (A-1), the above-mentioned Aqualon HS05 and potassium rosinate were added 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 8 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 3. Example 10 (Production of rubber-reinforced vinyl polymer) Polymerization was carried out in the same manner as in Example 8 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 3.
Shown in

Example 11 (Production of rubber-reinforced vinyl polymer) Polymerization was carried out in the same manner as in Example 8 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 3.
Shown in Example 12 (Production of rubber-reinforced vinyl polymer) Polymerization was carried out in the same manner as in Example 8 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 3.
Shown in

Example 13 (Production of rubber-reinforced vinyl polymer) Polymerization was carried out in the same manner as in Example 8 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 Example 14 (Production of rubber-reinforced vinyl polymer) Polymerization was carried out in the same manner as in Example 8 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 Example 15 (Production of rubber-reinforced vinyl polymer) Except that latex (A-7) was used and 0.3 part of the above formula (2) was used as a reactive emulsifier during batch polymerization and 0.6 part during incremental polymerization. Polymerization was carried out in the same manner as in Example 8. This is referred to as latex (B-8). The evaluation results of this latex (B-8) 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 8 except that the latex (A-8) was used. This is latex (B-9)
And The evaluation results of this latex (B-9) are shown in Table 4.
Shown in Comparative Example 5 (Production of Rubber Reinforced Vinyl Polymer) Polymerization was carried out in the same manner as in Example 8 except that the latex (A-9) was used. This is latex (B-1
0). Table 4 shows the evaluation results of this latex (B-10). Comparative Example 6 (Production of Rubber Reinforced Vinyl Polymer) Polymerization was carried out in the same manner as in Example 8 except that the latex (A-10) was used. This is latex (B-1
1). The evaluation results of this latex (B-11) are shown in Table 4.

Examples 16 to 23, Comparative Examples 7 to 9 (Production 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], and other heat stabilizers, lubricants, etc. are mixed in the formulation shown in Tables 4 to 5 and melt-mixed at a resin temperature of 200 ° C. with a vented extruder. Pellets were produced by kneading 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 5-6.

[0096]

[Table 1]

[0097]

[Table 2]

[0098]

[Table 3]

[0099]

[Table 4]

[0100]

[Table 5]

[0101]

[Table 6]

[0102]

According to the present invention, when a rubbery polymer latex is produced, a reactive emulsifier is used as at least a part of the emulsifier, and the copolymerization rate of the reactive emulsifier is set to a certain value or less. It has excellent polymerization stability and mechanical stability during polymerization, coagulation during acid precipitation and salting out, has a small load of wastewater pollution during manufacturing, and has impact resistance, surface gloss, thermal stability, and color tone. It is possible to obtain a rubber-like polymer latex which is excellent in the appearance of molded articles, has no stain on the mold, and has little eye tarnish (thermal discoloration), a rubber-reinforced vinyl polymer using the same, and a thermoplastic polymer composition.

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

Claims (3)

[Claims] 1. A monomer component 10 capable of forming a rubber.
Emulsifying 0 parts by weight of (b) reactive emulsifier (b-1) / other emulsifier (b-2) in the presence of 0.01 to 10 parts by weight of an emulsifier consisting of 1 to 100/99 to 0% by weight. A rubbery polymer latex obtained by polymerization and having a copolymerization rate of the reactive emulsifier (B-1) of 50% by weight or less. 2. (b) Reactive emulsifier (b-1) and / or
Or using an emulsifier composed of another emulsifier (b-2),
(C) In the presence of 3 to 80 parts by weight (as solid content) of the rubber-like polymer latex according to any one of claims 1 and 2,
(D) 97 to 20 parts by weight of vinyl-based monomer [however,
(C) + (D) = 100 parts by weight], which is obtained by emulsion polymerization and has a graft ratio of 5 to 200% by weight. 3. (e) 1 to 99 parts by weight of the rubber-reinforced vinyl polymer according to claim 2, and (e) another thermoplastic polymer 9
A thermoplastic polymer composition containing 9 to 1 parts by weight (however, (e) + (to) = 100 parts by weight) as a main component.