JPH08333489A - Rubberlike polymer latex for base rubber of rubber-reinforced vinyl polymer, rubber-reinforced vinyl polymer, and thermoplastic polymer composition - Google Patents

Abstract

PURPOSE: To obtain a rubberlike polymer latex which is used for the base polymer of a rubber-reinforced vinyl polymer, gives a molded article excellent in impact resistance and appearance properties such as surface gloss, thermal stability, and color tone, does not stain a mold, hardly causes deposition of resinous matters (thermal discoloration), and keeps the pollutant loading of waste water in the production process at a low level. CONSTITUTION: This latex is obtd. by subjecting 100 pts.wt. monomer component polymerizable into a rubber to emulsion polymn. in the presence of 0.01-10 pts.wt. emulsifier comprising 1-100wt.% reactive emulsifier and 99-0wt.% other emulsifier. A rubber-reinforced vinyl polymer is obtd. by polymerizing a vinyl monomer in the presence of the latex, and this thermoplastic polymer compsn. is obtd. by compounding the rubber-reinforced vinyl polymer with a thermoplastic polymer.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is excellent in impact resistance, surface glossiness, thermal stability, appearance of molded products such as color tone, and non-staining property of molds, has less eye blemishes (thermal discoloration), and is manufactured. A rubber-like polymer latex for a base rubber used as a raw material for the production of a rubber-reinforced vinyl polymer having a small wastewater pollution load at the time, a rubber-reinforced vinyl polymer obtained by using the rubber-like polymer, and the same. It relates to a composition.

[0002]

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

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

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

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

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

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

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

[0009]

DISCLOSURE OF THE INVENTION The present invention uses a reactive emulsifier which has never been used in emulsion polymerization, so that impact resistance, surface glossiness, thermal stability,
A base rubber used as a raw material for the production of rubber-reinforced vinyl polymers, which has excellent appearance of molded products such as color tone, non-staining property of molds, little eye tarnish (thermal discoloration), and a small load of wastewater pollution during production. To obtain a rubber-like polymer latex for use, a rubber-reinforced vinyl polymer obtained by using the rubber-like polymer, and a composition thereof.

[Means for Solving the Problems]

In the present invention, (b) 100 parts by weight of a monomer component capable of forming a rubber are mixed with (b) a reactive emulsifier (b-1) /
Other emulsifier (b-2) = rubber for base rubber of rubber-reinforced vinyl polymer obtained by emulsion polymerization in the presence of 0.01 to 10 parts by weight of an emulsifier consisting of 1 to 100/99 to 0% by weight. Polymer latex (hereinafter, also referred to as “(c) rubber-like polymer latex”).

The present invention also provides (c) 3 to 80 parts by weight of the rubber-like polymer latex (as solid content), (b) reactive emulsifier (b-1) and / or other emulsifier (b). In the presence of the emulsifier consisting of 2), 97 to 20 parts by weight of (d) vinyl-based monomer [where (c) + (d) =
100 parts by weight] to obtain a graft ratio of 5
200% by weight of rubber-reinforced vinyl polymer (hereinafter referred to as “(e)
(Also referred to as "rubber reinforced vinyl polymer").

Furthermore, the present invention provides 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 (to) (however, (e) + (e)). = 100
Parts by weight] as a main component (hereinafter, also referred to as “(to) thermoplastic polymer composition”).

The monomer used in the (a) monomer component used in the production of the (c) rubber-like polymer latex of the present invention includes (a) a conjugated diene compound and (b) an aromatic vinyl compound. , (C) vinyl cyanide compound, (d) meta (acrylic) acid ester, (e) meta (acrylic) acid,
(F) A graft crossing agent and the like. In addition, as the rubber-forming monomer in the monomer component (a), the conjugated diene compound (a) and the meta (acrylic) acid ester (d) are used.

Among 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. Examples of the aromatic vinyl compound (b) include 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,
Examples include ethylstyrene and vinylnaphthalene.

Examples of the vinyl cyanide compound (c) include acrylonitrile and methacrylonitrile. As the (d) meth (acrylic) acid 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 (meta)
Examples thereof include acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. Butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are particularly preferable.

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

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)
Grafting cross-linking 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 consisting of vinyl cyanide compounds, (e) (meth) acrylic acid and (f) graft cross-linking 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 thermoplastic polymer composition is lowered, and the desired physical properties cannot be obtained, which is not preferable. When the glass transition point (measured by DSC) of the component (a-1) or (a-2) becomes a polymer, the rubber elastic modulus decreases, and the thermoplastic polymer composition In that case, the impact resistance and fluidity are lowered, and the desired physical properties cannot be obtained, which is not preferable.

The rubber-like polymer latex (c) of the present invention requires a reactive emulsifier (b-1) as an (b) emulsifier, and may optionally be combined with another emulsifier (b-2). To be done. The reactive emulsifier (b-1) has a double bond copolymerizable with the monomer, and the (c) rubbery polymer latex for a base rubber of the present invention obtained by using the double emulsifier is
Since the monomer component capable of forming the rubber (a) and the reactive emulsifier undergo a polymerization reaction and are copolymerized in the rubber-like polymer, there is little low-molecular-weight free emulsifier and thermoplasticity When a polymer composition is used, residual organic acid,
The deterioration of physical properties due to soap is improved.

Here, the reactive emulsifier (b-1) is an emulsifier having a polymerizable unsaturated bond showing high reactivity such as vinyl group, acryloyl group, methacryloyl group, allyl group and propenyl group. Compounds particularly suitable as such a reactive emulsifier (b-1) include the following (formula 1)
It can be shown in (Chemical Formula 6).

[0024]

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[Chemical 4]

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[Chemical 6]

[In (Formula 1) to (Formula 6), R ^{1 to} R
⁵ is the same or different, higher alkyl group, n is 0 to 50
, M is a monovalent cation. Of these reactive emulsifiers (b-1), preferred are the compounds represented by the above (formula 1) and (formula 6). In particular, in (Chemical formula 1), R ¹ is C ₉ H ₁₉ , and M is NH ₄ ; in (Chemical formula 6), R ⁵ is C
₉ H ₁₉ and a compound in which M is represented by NH ₄ have excellent copolymerizability with monomers, and the resulting copolymer latex has stability in polymerization, leaving (low temperature, high temperature), and mechanical stability. Is preferred.

On the other hand, as the (b) emulsifier, other emulsifiers (b-2) which may be used in combination with the above reactive emulsifier (b-1) include anionic surfactants, nonionic surfactants, 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 ordinary polyethylene glycol alkyl ester type, alkyl ether type, alkyl phenyl ether type or the like 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 the anion portion and an amine salt or a quaternary ammonium salt as the cation portion. To be Specific examples of the amphoteric surfactant include betaines such as lauryl betaine and stearyl betaine, amino acid types such as lauryl-β-alanine, stearyl-β-alanine, lauryl di (aminoethyl) glycine, and octyl di (aminoethyl) glycine. The thing etc. are used. These other emulsifiers (B-2) can be used alone or in combination of two or more.

(B) The ratio of the emulsifier 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 above, a large amount of free emulsifier remains, which is not preferable because it causes mold contamination when the composition is a thermoplastic polymer composition and lowers thermal stability.

The total amount of the (b) emulsifier used is
(A) 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 rubber-forming monomer component. 0.1
If it is less than 10 parts by weight, the stability during emulsion polymerization is poor, while 10
If it exceeds the weight part, the elasticity of the obtained rubber-like polymer is lowered and the impact resistance becomes poor.

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

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

Examples of the molecular weight regulator include chloroform, halogenated hydrocarbons such as carbon tetrabromide, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid. 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 30 hours.

The average particle diameter of the (c) rubbery polymer latex emulsion-polymerized in this manner is preferably 500.
~ 20,000Å, more preferably 800 to 10,0
00Å, particularly preferably 1,000 to 5,000Å, and within this range, the thermoplastic polymer composition obtained has excellent Izod impact strength and gloss.

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

The gel content of the rubber-like polymer latex (c) is preferably 20 to 95% by weight, more preferably 50 to 90% by weight. Gel content is 20% by weight
When it is less than 1, the rubber elasticity is lowered, and the impact resistance of the obtained thermoplastic polymer composition is lowered, which is not preferable. While 9
If it exceeds 5% by weight, the rubber elasticity is high, and the impact resistance and fluidity are deteriorated, which is not preferable. Especially, the gel content is 3
When the content is 0% by weight or less, the thermoplastic polymer composition obtained is excellent in extruding grade, for example, elongation in vacuum forming of a sheet and uniformity of product thickness, and is suitable for an inner box for electric refrigerators and the like. There is. Further, the gel content is 20 to 10
In the case of 0% by weight, the obtained thermoplastic polymer composition is suitable for grades requiring appearance such as impact resistance, weld, and gloss, such as electric appliances and OA equipment.

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

The gel content can be easily and easily adjusted 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,
The amount of the polymerization initiator at the time of polymerization, the temperature at which the polymerization starts, and the like are selected, and by combining these, the desired rubber-like polymer latex can be obtained.

Further, (c) the rubber-like polymer latex has a Mooney viscosity (ML) when converted into solid rubber.
_{1 + 4} , 100 ° C.) is preferably 10 to 300, and 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 decreases, which is not preferable. . When the Mooney viscosity is within the above numerical range, the resulting thermoplastic polymer composition has good impact resistance. The adjustment of the Mooney viscosity can be easily carried out by selecting the kind and amount of the molecular weight modifier, the amount of the polymerization initiator, and the addition of the crosslinking agent.

In the present invention, in the rubber-like polymer latex (c) thus obtained, the reactive emulsifier (b-1) unit copolymerized with the rubber-like polymer is used for the polymerization reaction. 1 to 100% by weight of the reactive emulsifier (B-1) unit and 0.0001 to 10 parts by weight of the reactive emulsifier (B-1) unit to 100 parts by weight of the rubbery polymer and other emulsifiers (Ro- 2) is contained in an amount of 9.9999 parts by weight to 0 parts by weight.

The reactive emulsifier (B-1) unit copolymerized with the rubber-like polymer is 1 to 100% by weight as described above.
Preferably 10 to 100% by weight, more preferably 30
If it is less than 1% by weight, a large amount of free emulsifier remains, the target mold contamination is small, and a thermoplastic polymer composition having good thermal stability cannot be obtained. The copolymerization amount of this reactive emulsifier (b-1) unit can be adjusted by the amount of the polymerization initiator, the polymerization temperature, the method of charging the emulsifier, and the like.

The (b) emulsifier not copolymerized is
To 100 parts by weight of the rubbery polymer, a reactive emulsifier (low
1) Unit is 0.0001 to 10 parts by weight, preferably 0.1.
001 to 8 parts by weight, more preferably 0.005 to 8 parts by weight, other emulsifier (b-2) is 9.9999 to 0 parts by weight, preferably 9.999 to 2 parts by weight, and more preferably 9.995. ~ 2 parts by weight are contained. If the reactive emulsifier (B-1) unit is less than 0.0001 parts by weight (that is, if the other emulsifier (B-2) exceeds 9.9999 parts by weight), there are many free emulsifiers remaining, and the object is to be achieved. It is not possible to obtain a thermoplastic polymer composition having a low mold contamination and a good thermal stability. The content of the non-copolymerized (B) emulsifier is adjusted by the type of polymerization initiator, the polymerization
It can be adjusted by the temperature , the method of adding an emulsifier, and the like.

(C) Mooney of rubber-like polymer constituting the rubber-like polymer latex (ML _{1 + 4} , 100 ° C.)
Is a conjugated diene rubber [(a) the monomer component is (a-
In the case of 1)], it is preferably 10 to 300, more preferably 30 to 250, and particularly preferably 50 to 200. Further, in the case of acrylic rubber [(a) when the monomer component is (a-2) above], preferably 10 to 200, more preferably 20 to 180, and particularly preferably 20 to 1
50.

Next, the (c) rubbery polymer latex is used in an amount of 3 to 80 parts by weight of the latex (as solid content), (b) reactive emulsifier (b-1) and / or other emulsifier (b). -2) in the presence of an emulsifier consisting of (d) vinyl monomer 97 to 20 parts by weight [however, (c) +
(D) = 100 parts by weight] to obtain a (v) rubber-reinforced vinyl polymer having a graft ratio of 5 to 200% by weight.

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

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

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

Other copolymerizable vinyl compound monomers are exemplified in the above (a) monomer component (e).
In addition to (meth) acrylic acid, unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; maleimide, N-methylmaleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide, N -Phenylmaleimide; α- or β-unsaturated dicarboxylic acid imide compounds such as N-cyclohexylmaleimide, epoxy group-containing monomers such as glycidyl methacrylate and allyl glycidyl ether; amide group-containing monomers such as acrylamide and methacrylamide.
Amino group-containing monomers such as acrylic amine, aminomethyl methacrylate, aminoether methacrylate, aminopropyl methacrylate; 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, Trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, 2-
Examples thereof include hydroxyl group-containing monomers such as hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and hydroxystyrene; and oxazoline group-containing monomers such as vinyl oxazoline.

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

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

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

(C) Rubber-like polymer latex (A) 20-80 obtained by polymerizing a monomer component having a composition ratio of conjugated diene compound / aromatic vinyl compound of 60-90 / 10-40% by weight. In the presence of parts by weight, the aromatic vinyl compound / (meth) acrylic acid alkyl ester is 10 to 90
(D) Vinyl monomer 80 consisting of / 10 to 90% by weight
A rubber-reinforced vinyl polymer obtained by polymerizing 20 to 20 parts by weight [(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, other emulsifiers (B-2) may be mentioned. The use ratio of these (b-1) and (b-2) components is not particularly limited.

The amount of the (b) emulsifier is preferably 0 based on 100 parts by weight of the total amount of the (c) and (d) components.
-10 parts by weight, more preferably 0 to 8 parts by weight, and particularly preferably 0 to 6 parts by weight. If it exceeds 10 parts by weight,
The desired impact resistance cannot be obtained, which is not preferable.

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

The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) 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.

Next, the (e) rubber-reinforced vinyl-based polymer of the present invention is used alone as a molding material. In addition, (v) another thermoplastic polymer such as another ABS resin, A
Styrene resin such as ES resin, HIPS, AS resin,
Polyamide such as nylon 6, nylon 6,6, nylon 4,6, polyester such as polybutylene terephthalate, polyethylene terephthalate, aromatic polycarbonate, PPS resin, liquid crystal polyester resin, polyarylate resin, polysulfone resin, AS resin, MS resin,
Blended with a polymer such as a PVC resin, a styrene-maleic anhydride copolymer, a maleimide-based copolymer, etc., and as a (g) thermoplastic polymer composition, an impact modifier and a compatibilizing agent for these polymers. It can be used as an agent.

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

(E) Rubber-reinforced vinyl polymer of the present invention,
Alternatively, an antistatic agent may be added to the (g) thermoplastic polymer composition. Examples of this antistatic agent include polyethylene oxide, polyethylene glycol-containing polymers, and other antistatic agents.

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

Further, as the other antistatic agents, all of the commonly used antistatic agents can be used. As the antistatic agent, there are anionic type, cationic type, nonionic type, amphoteric type and the like, and any of them can be used. Particularly preferred are anionic type and nonionic type, and of these, sodium sulfonate type and monoglyceride type are preferable. These antistatic agents are
With respect to 100 parts by weight of the component (e) or the component (g),
Usually, it is used in the range of 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight.

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 (e) of the present invention.

The (e) rubber-reinforced vinyl polymer or (g) thermoplastic polymer composition of the present invention includes known coupling agents, antibacterial agents, antifungal agents, flame retardants, and flame retardant aids. ,
Antioxidants, weathering (light) agents, plasticizers, colorants (pigments, dyes, etc.), lubricants, metal powders and the like can be added.

The (e) rubber-reinforced vinyl polymer or the (e) thermoplastic polymer composition may contain the (e) component alone or the (e) to (e) components, if necessary, with the above additives. , Various extruders, Banbury mixers, kneaders,
It can be prepared by kneading each component using a roll or the like. A preferred manufacturing method is a method using an extruder. Moreover, when kneading each component, you may knead all components collectively, and you may knead them by a multistage addition system.

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

Various molded articles obtained by the above-mentioned molding method, utilizing their excellent properties, can be used for large televisions, 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.

[0073]

In the emulsion polymerization of the rubber-like polymer latex for the base rubber of the rubber-reinforced vinyl polymer, the reactive emulsifier is used as at least a part of the emulsifier, so that the reactive emulsifier is copolymerized in the polymer. After the completion of the polymerization, the residual free emulsifier is suppressed, so that the mixing of the emulsifier in the waste water is reduced. Further, when a rubber-reinforced vinyl polymer is produced by emulsion-polymerizing a vinyl-based monomer using this rubber-like polymer latex, if a reactive emulsifier is used as at least a part of the emulsifier, the rubber-like polymer is obtained. The graft ratio is improved by changing the degree of swelling of the vinyl monomer with respect to the vinyl monomer, and the reactive emulsifier is (grafted) copolymerized in the copolymer forming the latex or the vinyl polymer forming the matrix. , The mixing of emulsifiers in the wastewater is reduced. 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]

EXAMPLES The present invention will be described in more detail below 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.

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)] × [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 using 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.

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

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

Example 1 (Production of polybutadiene rubber latex) In a reactor equipped with a stirrer having a capacity of 100 liters, 100 parts of 1,3-butadiene, 60 parts of water, and as a reactive emulsifier, Aqualon HS-05 [Daiichi Kogyo Seiyaku Co., Ltd. ) Made] 2.4
Parts, potassium phosphate 0.5 parts, potassium hydroxide 0.1
Parts, t-dodecyl mercaptan as a chain transfer agent was added in an amount of 0.
Add 3 parts and 0.3 parts of potassium persulfate, 60-70 ° C
Batch polymerized for 30 hours. The polymerization conversion rate was 95%. To this polymerization system, 0.2 part of N, N-diethylhydroxylamine was added as a polymerization terminator to stop the reaction. Then, 1,3-butadiene was removed under reduced pressure to obtain a polybutadiene rubber latex. This is designated as latex (A-1) (solid content 56.2%). The evaluation results of this latex (A-1) are shown in Table 1.

Example 2 (Production of Acrylic Rubber Latex) 99 parts of butyl acrylate as an emulsion polymerization formulation, 1.0 part of allyl methacrylate as a graft crossing agent, and 12 parts of water.
5 parts, 2.4 parts of the above-mentioned Aqualon HS-05 as a reactive emulsifier, 0.1 part of potassium hydroxide, 0.5 part of potassium phosphate, 0.1 part of t-dodecyl mercaptan as a chain transfer agent, potassium persulfate Polymerization temperature 6 with 0.3 part
Emulsion polymerization was performed in the same manner as in Example 1 except that three-stage batch polymerization [monomer (weight ratio) = 33/33/34] was performed at 0 to 70 ° C. for 5 hours. Polymerization conversion rate is 99.5%
Met. 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 rubber latex. This is latex (A-2)
(Solid content 42.3%). This latex (A-
The evaluation results of 2) are shown in Table 1.

Example 3 (Production of rubber-like polymer latex) 1.2 parts of the above-mentioned Aqualon HS-05 was used as a reactive emulsifier.
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) 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 referred to as latex (A-4). This latex (A-
The evaluation results of 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 2 except that 90 parts of butyl acrylate and 9 parts of 1,3-butadiene were used. This is designated as latex (A-5). The evaluation results of this latex (A-5) 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. This is latex (A-
6). The evaluation results of this latex (A-6) are shown in Table 1.

Comparative Example 2 (Production of Rubbery Polymer Latex) A latex was obtained in the same manner as in Example 1 except that 4.8 parts of potassium rosinate was used. This is latex (A-
7). The evaluation results of this latex (A-7) are shown in Table 1.

Comparative Example 3 (Production of Rubbery Polymer Latex) A latex was obtained in the same manner as in Example 2 except that 2.4 parts of potassium rosinate was used. This is latex (A-
8). The evaluation results of this latex (A-8) are shown in Table 1.

Example 6 (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 of HS-05,
0.05 part of potassium hydroxide, 80 parts of water, 0.06 part of cumene hydroperoxide (hereinafter sometimes abbreviated as "CHPO"), 0.8 part of sodium alkyldiphenyl ether disulfonate, 7.9 parts of water, t -0.2 parts of dodecyl mercaptan was added and batch-polymerized at 70 ° C for 1 hour. Subsequently, 23 parts of styrene, 10 parts of acrylonitrile, 0.6 part of the above-mentioned Aqualon HS-05 as a reactive emulsifier, 0.1 part of potassium hydroxide, 20 parts of water, cumene hydroper were added to the polymerization system kept at 70 ° C. Increment polymerization was carried out by adding 0.1 part of oxide and 0.3 part of t-dodecyl mercaptan over 2 hours.

Next, 0.05 part of cumene hydroperoxide, 0.2 part of sodium alkyldiphenyl ether disulfonate and 2.7 parts of water were added to the polymerization system kept at 70 ° C.
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). This latex was salted out or washed with an acid salt and dried to obtain a powder. The physical properties of the obtained powder were evaluated. Table 2 shows the results.

Example 7 (Production of rubber-reinforced vinyl polymer) Polymerization was carried out in the same manner as in Example 6 except that the latex (A-2) (acrylic rubber latex) was used.
The polymerization conversion rate was 99.5%. This is referred to as latex (B-2). The evaluation results of this latex (B-2) are shown in Table 2.

Example 8 (Production of Rubber Reinforced Vinyl Polymer) Using latex (A-3), 0.3 part of the above-mentioned Aqualon HS-05 as an emulsifier is used in batch polymerization and 0.6 part in increment polymerization. Polymerization was performed in the same manner as in Example 6 except for the above. This is referred to as latex (B-3). The evaluation results of this latex (B-3) are shown in Table 2.

Example 9 (Production of Rubber Reinforced Vinyl Polymer) Using Latex (A-1), the above-mentioned Aqualon HS-05 and potassium rosinate were mixed at 0.15 parts / 0.15 during batch polymerization. Parts, the polymerization was carried out in the same manner as in Example 6 except that 0.3 part / 0.3 part was used in the increment polymerization. This is referred to as latex (B-4). The evaluation results of this latex (B-4) are shown in Table 2.

Example 10 (Production of Rubber Reinforced Vinyl Polymer) Using latex (A-4), 0.3 part of the above-mentioned Aqualon HS-05 as an emulsifier is used in batch polymerization and 0.6 part in increment polymerization. Polymerization was performed in the same manner as in Example 6 except for the above. This is designated as latex (B-5). The evaluation results of this latex (B-5) are shown in Table 2.

Example 11 (Production of Rubber Reinforced Vinyl Polymer) Latex (A-5) was used, and the above-mentioned Aqualon HS-05 was used as an emulsifier in an amount of 0.3 part in batch polymerization and 0.6 part in increment polymerization. Polymerization was performed in the same manner as in Example 6 except for the above. This is designated as latex (B-6). The evaluation results of this latex (B-6) are shown in Table 2.

Example 12 (Production of Rubber Reinforced Vinyl Polymer) Using latex (A-1), 0.3 part of the above-mentioned Aqualon HS-05 as an emulsifier is used in batch polymerization and 0.6 part in increment polymerization. In addition, as a vinyl-based monomer, styrene / acrylonitrile / α-methylstyrene (AMS) / methylmethacrylate (parts ratio) = 4/7
Polymerization was carried out in the same manner as in Example 6 except that the ratio was / 4/35. This is designated as latex (B-7). The evaluation results of this latex (B-7) are shown in Table 2.

Comparative Example 4 (Production of Rubber Reinforced Vinyl Polymer) Latex (A-1) was used, except that potassium rosinate was used as an emulsifier in an amount of 0.3 part during batch polymerization and 0.6 part during incremental polymerization. Polymerization was carried out in the same manner as in Example 6. This is referred to as latex (B-8). The evaluation results of this latex (B-8) are shown in Table 3.

Comparative Example 5 (Production of Rubber Reinforced Vinyl Polymer) Except that latex (A-3) was used and potassium rosinate was used as an emulsifier in an amount of 0.3 part during batch polymerization and 0.6 part during incremental polymerization. Polymerization was carried out in the same manner as in Example 6. This is designated as latex (B-9). Table 3 shows the evaluation results of this latex (B-9).

Comparative Example 6 (Production of Rubber Reinforced Vinyl Polymer) Except that latex (A-5) was used and potassium rosinate was used as an emulsifier in an amount of 0.3 part during batch polymerization and 0.6 part during incremental polymerization. Polymerization was carried out in the same manner as in Example 6. This is designated as latex (B-10). Table 3 shows the evaluation results of this latex (B-10).

Comparative Example 7 (Production of Rubber Reinforced Vinyl Polymer) Except that latex (A-6) was used and potassium rosinate was used as an emulsifier in an amount of 0.3 part during batch polymerization and 0.6 part during increment polymerization. Polymerization was carried out in the same manner as in Example 6. This is designated as latex (B-11). Table 3 shows the evaluation results of this latex (B-11).

Comparative Example 8 (Production of Rubber Reinforced Vinyl Polymer) Except that latex (A-7) was used and potassium rosinate was used as an emulsifier in an amount of 0.3 part during batch polymerization and 0.6 part during incremental polymerization. Polymerization was carried out in the same manner as in Example 6. This is designated as latex (B-12). Table 3 shows the evaluation results of this latex (B-12).

Comparative Example 9 (Production of Rubber Reinforced Vinyl Polymer) Except that latex (A-8) was used and potassium rosinate was used as an emulsifier in an amount of 0.3 part during batch polymerization and 0.6 part during incremental polymerization. Polymerization was carried out in the same manner as in Example 6. This is designated as latex (B-13). The evaluation results of this latex (B-13) are shown in Table 3.

Comparative Example 10 (Production of Rubber Reinforced Vinyl Polymer) Except that latex (A-2) was used and potassium rosinate was used as an emulsifier in an amount of 0.3 part during batch polymerization and 0.6 part during increment polymerization. Polymerization was carried out in the same manner as in Example 6. This is designated as latex (B-14). Table 3 shows the evaluation results of this latex (B-14).

Examples 13 to 19 and Comparative Examples 11 to 17 (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. were mixed in the compounding formulations 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 30 mmφ extruder at a cylinder temperature of 200 ° C., and each physical property was evaluated. The results are shown in Tables 4-5.

[0106]

[Table 1]

[0107]

[Table 2]

[0108]

[Table 3]

[0109]

[Table 4]

[0110]

[Table 5]

[0111]

According to the present invention, by using a reactive emulsifier as at least a part of the emulsifier, the appearance of the molded article such as impact resistance, surface gloss, thermal stability, color tone, and mold non-contamination. Of rubber-like polymer latex, rubber-reinforced vinyl polymer obtained by using the rubber-like polymer, and its composition, which have excellent properties, little eye tarnish (thermal discoloration), and small load of wastewater pollution during production. can get.

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

Claims (5)

[Claims] 1. A monomer component 10 capable of forming a rubber.
0 parts by weight in the presence of 0.01 to 10 parts by weight of an emulsifier (b) reactive emulsifier (b-1) / other emulsifier (b-2) = 1 to 100/99 to 0% by weight, A rubber-like polymer latex for a base rubber of a rubber-reinforced vinyl polymer obtained by emulsion polymerization. 2. The rubber-like polymer latex for a base rubber of a rubber-reinforced vinyl polymer according to claim 1, wherein (a) the monomer component is 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. 3. The reactive emulsifier (b-1) unit copolymerized with the rubber-like polymer is 1 to 100% by weight of the reactive emulsifier (b-1) unit used in the polymerization reaction, and Reactive emulsifier (B-1) per 100 parts by weight of the rubber-like polymer
The rubber for a base rubber of a rubber-reinforced vinyl polymer according to claim 1 or 2, which comprises 0.0001 to 10 parts by weight of a unit and 9.9999 to 0 parts by weight of another emulsifier (B-2). Polymer latex. 4. (c) 3 to 80 parts by weight (as solid content) of the rubber-like polymer latex according to any one of claims 1 to 3, and (b) reactive emulsifier (b-1) and / or
Alternatively, in the presence of an emulsifier composed of another emulsifier (b-2), 97 to 20 parts by weight of (d) vinyl monomer [however,
(C) + (D) = 100 parts by weight], and a rubber-reinforced vinyl polymer having a graft ratio of 5 to 200% by weight. 5. (e) 1 to 99 parts by weight of the rubber-reinforced vinyl polymer according to claim 4, and (e) another thermoplastic polymer 9
A thermoplastic polymer composition containing 9 to 1 parts by weight (however, (e) + (f) = 100 parts by weight) as a main component.