JPH093142A - Rubber-reinforced vinyl polymer and thermoplastic polymer composition - Google Patents

Abstract

(57) [Summary] [Purpose] Excellent in appearance of molded products such as impact resistance, surface gloss, thermal stability, and color tone, and excellent in non-contamination of molds, and causes eye foreign matter (caused at the exit of the ruder). To obtain a rubber-reinforced vinyl polymer and a composition thereof, which have less heat discoloration products and a smaller wastewater pollution load during production. [Structure] (c) In the presence of 3 to 80 parts by weight of rubber-like polymer latex (as solid content), (d) vinyl-based monomer 9
7 to 20 parts by weight (however, (c) + (d) = 100 parts by weight) is polymerized using (b) 0.1 to 10 parts by weight of an emulsifier containing at least a reactive emulsifier (b-1). Obtained,
A rubber-reinforced vinyl polymer having a graft ratio of 5 to 200% by weight, and this (e) rubber-reinforced vinyl polymer 1 to 9
A thermoplastic polymer composition comprising 9 parts by weight and 99 to 1 part by weight of another thermoplastic polymer (wherein (e) + (f) = 100 parts by weight) as main components.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in appearance of molded products such as impact resistance, surface glossiness, thermal stability, and color tone, and excellent in non-contamination of molds. The present invention relates to a rubber-reinforced vinyl polymer and a composition thereof, in which the amount of heat discoloration that occurs in (1) is small and the load of pollution of wastewater during production is small.

[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 amount of the emulsifier that 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. .

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 In the present invention, when a rubber-reinforced vinyl polymer is produced by emulsion polymerization, impact resistance and surface glossiness are improved by using a reactive emulsifier which has never been used. It has excellent heat stability, appearance of molded products such as color tone, and non-contamination of molds, there are few eye tars (thermochromic substances generated at the ruder outlet) that cause foreign matter, and the load of wastewater pollution during manufacturing is small. To obtain a rubber-reinforced vinyl polymer and its composition.

[Means for Solving the Problems]

In the present invention, (c) 97 to 20 parts by weight of a vinyl monomer (d) in the presence of 3 to 80 parts by weight of a rubber-like polymer latex (as solid content) (however, (c) + (D)
= 100 parts by weight] is used to polymerize (B) at least 0.1 to 10 parts by weight of an emulsifier containing a reactive emulsifier (B-1), and the graft ratio is 5 to 200% by weight. A polymer (hereinafter also referred to as “(e) rubber-reinforced vinyl polymer”) is provided.

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 (to) (however, (e) + (e)) = 100 parts by weight] as a main component.

Examples of the (c) rubbery polymer used in the present invention include (a) a monomer component 10 capable of forming a rubber.
0.01 part by weight of 0 part by weight of (b) reactive emulsifier (b-1) and / or other emulsifier (b-2)
Examples thereof include a rubber-like polymer latex for a base rubber, which is a rubber-reinforced vinyl polymer obtained by emulsion polymerization in the presence of 0 part by weight.

As the monomer used in the (a) monomer component used in the production of the (c) rubbery polymer latex, (a) a conjugated diene compound, (b) an aromatic vinyl compound, ( Examples include c) vinyl cyanide compound, (d) meta (acrylic) acid ester, (e) meta (acrylic) acid, and (f) graft crossing agent. In addition, in the (a) monomer component,
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. 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 2 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 a matrix, so that the resulting rubber-reinforced vinyl polymer has impact resistance. Is improved.

Among these (a) monomer components, preferred combinations include the following (a-1) or (a-2). (A-1); (a) 30 to 100% by weight, preferably 50 to 100% by weight, more preferably 60 to 100% by weight of a conjugated diene compound, and (b) 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. here,
The alkyl group of the (meth) acrylic acid alkyl ester preferably has 2 to 12 carbon atoms, and more preferably 3 carbon atoms.
-8, particularly preferably 4-6.

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, and the desired impact resistance cannot be obtained, which is not preferable. Also,
If 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 impact resistance and the fluidity are low. The desired product cannot be obtained, which is not preferable.

In the production of the (c) rubbery polymer latex, a reactive emulsifier (b-1) and / or another emulsifier (b-2) is used as the (b) emulsifier. The reactive emulsifier (b-1) has a double bond copolymerizable with the monomer, and the rubber-like polymer latex (c) obtained by using this has few free emulsifiers. , The residual organic acid in the obtained rubber-reinforced vinyl polymer or thermoplastic polymer composition, the deterioration of physical properties due to soap is improved,
Heat discoloration resistance 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, allyl group, propenyl group and methacryloyl group. Particularly preferable compounds as the reactive emulsifier (b-1) include sodium isoprene sulfonate, its (co) polymer (salt), and the compounds shown in the following (Chemical formula 1) to (Chemical formula 6). .

[0023]

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[Chemical 6]

[In (Chemical Formula 1) to (Chemical 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
A compound in which ₉ H ₁₉ and M ₄ are represented by NH ₄ is excellent in copolymerizability with a monomer, and the copolymer latex obtained is preferable in terms of polymerization stability, leaving stability, 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 sulfuric acid ester of higher alcohol, alkylbenzene sulfonate, aliphatic sulfonate, and sulfuric acid ester of polyethylene glycol alkyl ether.

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

(B) The total amount of the emulsifier used is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, relative to 100 parts by weight of the monomer component (a) capable of forming rubber.
Parts by weight, particularly preferably 0.5 to 8 parts by weight. 0.
If it is less than 1 part by weight, the stability during emulsion polymerization is poor, while 1
If it exceeds 0 parts by weight, the resulting rubber-reinforced vinyl polymer or thermoplastic polymer composition may have poor impact resistance.

(C) The rubber-like polymer latex is dissolved in water,
While stirring the above-mentioned (a) monomer component, (b) emulsifier, a polymerization initiator to be described later, a molecular weight modifier, etc., while stirring,
It can be obtained by emulsion polymerization according to a conventional method.

Here, as the polymerization initiator, water-soluble polymerization initiators such as sodium persulfate, potassium persulfate and ammonium persulfate, paramenthane hydroperoxide,
Combination with diisopropylbenzene hydroperoxide, benzoyl peroxide, lauryl peroxide, oil-soluble polymerization initiator such as 2,2'-azobisisobutyronitrile, reducing agent such as sugar-containing pyrophosphate formulation or sulfoxylate formulation Redox type polymerization initiator by
Each is 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 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 the monomer components in a batch 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 in this range, the rubber-reinforced vinyl polymer or thermoplastic polymer composition obtained has excellent Izod impact strength and gloss.

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

The gel content of the (c) rubbery polymer latex is preferably 20 to 95% by weight, more preferably 50 to 90% by weight. Gel content is 20% by weight
If it is less than 1, 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. On the other hand, if it exceeds 95% by weight,
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. Also, the gel content is 20-100
In the case of 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.
Suitable for 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 under 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 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 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 rubber-reinforced vinyl polymer or thermoplastic polymer composition has good impact resistance. The adjustment of the Mooney viscosity can be easily carried out by selecting the kind and amount of the molecular weight modifier, the amount of the polymerization initiator, and the addition of the crosslinking agent.

In the present invention, when the reactive emulsifier obtained is used, (c) the rubber-like polymer latex has a reactive emulsifier (b-1) unit copolymerized with the rubber-like polymer which is a polymerization reaction. 1 to 100% by weight of the reactive emulsifier (B-1) unit used in.

The reactive emulsifier unit means the residue of the reactive emulsifier copolymerized with the rubber strip polymer. The reactive emulsifier (b-1) unit copolymerized with the rubber-like polymer is 1 to 100% by weight, preferably 10 to 100% by weight as described above.
100% by weight, more preferably 30 to 100% by weight. If it is less than 1% by weight, a large amount of free emulsifying agent remains, the target mold contamination is small, and a rubber-reinforced vinyl polymer having good thermal stability and It is not possible to obtain a thermoplastic polymer composition. 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.

On the other hand, as the rubber-like polymer used in the (c) rubber-like polymer latex used in the present invention, polybutadiene, polyisoprene, butyl rubber, styrene-butadiene copolymer (styrene content other than the above-mentioned ones can be used. 5-
60% by weight is preferable), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, ethylene-α-olefin copolymer, ethylene-α-olefin-polyene copolymer, silicone rubber, acrylic rubber,
Butadiene- (meth) acrylic acid ester copolymer, polyisoprene, styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated butadiene-based polymer, ethylene-based Examples include ionomers.

The styrene-butadiene block copolymer and the styrene-isoprene block copolymer have A
Those having structures of B type, ABA type, taper type, radial teleblock type and the like are included. Further, the hydrogenated butadiene-based polymer has, in addition to the hydrogenated product of the block copolymer, a hydrogenated product of a styrene block and a styrene-butadiene random copolymer block, and a 1,2-vinyl bond content in polybutadiene. It includes a hydride of a polymer comprising a block of not more than 20% by weight and a polybutadiene block having a 1,2-vinyl bond content of more than 20% by weight. Further, among the above rubber-like polymers, those not in a latex state can be used after being re-emulsified by a known method such as a high pressure homogenizer or an ultrasonic homogenizer. These (c) rubbery polymer latexes may be used alone or in combination of two or more.

The (v) rubber-reinforced vinyl polymer of the present invention comprises (d) vinyl monomer 97 in the presence of 3 to 80 parts by weight (as solid content) of the (c) rubber-like polymer latex.
To 20 parts by weight (however, (c) + (d) = 100 parts by weight) are polymerized with (b) 0.1 to 10 parts by weight of an emulsifier containing at least a reactive emulsifier (b-1). The
The graft ratio is 5 to 200% by weight. here,
(E) Rubber-reinforced vinyl polymers include those obtained by emulsion-polymerizing (d) vinyl-based monomers in the presence of (iii) rubber-like polymer latex, and (iii) rubber-reinforced vinyl polymers. It may be a mixture of vinyl polymers obtained by polymerizing (d) vinyl monomers in the absence of vinyl polymers.

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

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

Other copolymerizable vinyl compound monomers are exemplified in (e) above as the monomer component.
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 An imide compound of an α- or β-unsaturated dicarboxylic acid such as phenylmaleimide or N-cyclohexylmaleimide, an epoxy group-containing monomer such as glycidyl methacrylate or allyl glycidyl ether; an amide group-containing monomer such as acrylamide or 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% by weight.
(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) As the (b) emulsifier used in the emulsion polymerization of the rubber-reinforced vinyl polymer, an emulsifier containing at least a reactive emulsifier (b-1) is used, but another emulsifier (b-2) is used. Can be used together. Examples of (b) emulsifiers include the same reactive emulsifiers (b-1) and other emulsifiers (b-2) which are the same as those used in the production of the (c) rubbery polymer latex.

The ratio of (b) emulsifier used is preferably 1 to 1 of the reactive emulsifier (b-1) / other emulsifier (b-2).
00/99 to 0% by weight, more preferably 20 to 100
/ 80 to 0% by weight, particularly preferably 50 to 100/50
~ 0% by weight. When the proportion of the reactive emulsifier (B-1) used is less than 1% by weight, a large amount of low molecular weight free emulsifiers remain, and a desired rubber-reinforced vinyl polymer or thermoplastic polymer composition having good thermal stability is obtained. Can't get

The total amount of the (b) emulsifier used is
(C) 0.1 to 10 parts by weight, preferably 0.1 to 8 parts by weight, more preferably 100 parts by weight of the total amount of the rubber-like polymer (solid content) and (d) vinyl monomer. It is 0.5 to 8 parts by weight. If it is less than 0.1 part by weight, the stability during emulsion polymerization will be inferior, while if it exceeds 10 parts by weight, the impact resistance of the resulting rubber-reinforced vinyl polymer or thermoplastic polymer composition will be inferior.

In the present invention, the (e) rubber-reinforced vinyl polymer thus obtained is a reaction in which the reactive emulsifier (b-1) unit copolymerized with the polymer is used in the polymerization reaction. The amount of the reactive emulsifier (B-1) is preferably 1 to 100% by weight, and the amount of the reactive emulsifier (B-1) is preferably 0.00 based on 100 parts by weight of the rubber-reinforced vinyl polymer.
01 to 10 parts by weight, and other emulsifier (b-2) are preferably contained in 9.9999 to 0 parts by weight.

Here, the reactive emulsifier unit means the residue of the reactive emulsifier copolymerized as described above. Reactive emulsifier copolymerized with rubber-reinforced vinyl polymer
1) The unit is, as described above, preferably 1 to 100% by weight, more preferably 30 to 100% by weight, and particularly preferably 50 to 100% by weight. If it is less than 1% by weight, the amount of residual low-molecular free emulsifiers is large, and the desired rubber-reinforced vinyl polymer or thermoplastic polymer composition having good thermal stability cannot be obtained. The copolymerization amount of this reactive agent (b-1) unit can be adjusted by the addition method of the emulsifier, the amount and type of the initiator, and the polymerization temperature.

The (b) emulsifier not copolymerized is
The reactive emulsifier (b-1) unit is preferably 0.0001 to 10 parts by weight, more preferably 0.001 to 8 parts by weight, and particularly preferably 0.005 to 100 parts by weight of the rubber-reinforced vinyl polymer. 8 parts by weight, other emulsifier (b-2)
Is contained in an amount of 9.9999 parts by weight, preferably 9.999 to 2 parts by weight, particularly preferably 9.995 to 2 parts by weight. Reactive emulsifier (b-1) unit is less than 0.0001 parts by weight [that is, other emulsifier (b-2) is 9.999).
If it exceeds 9 parts by weight], the amount of residual low-molecular free emulsifiers is large, and the desired rubber-reinforced vinyl polymer or thermoplastic polymer composition with good thermal stability cannot be obtained.

The graft ratio of the (e) rubber-reinforced vinyl polymer of the present invention is 5 to 200% by weight, preferably 5 to 18%.
It is 0% by weight, more preferably 10 to 170% 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 (measured at 30 ° C. using methyl ethyl ketone as a solvent) of the (v) rubber reinforced vinyl polymer soluble in methyl ethyl ketone is preferably 0.1 to 1.0 dl / g, more preferably 0.1.
It is 1 to 0.7 dl / g. This intrinsic viscosity is 0.1 dl
If it is less than 1.0 g / g, the impact resistance is lowered, while if it exceeds 1.0 dl / g, the moldability is lowered, which is not preferable.

Next, the (e) rubber-reinforced vinyl-based polymer of the present invention is used alone as a molding material, and further (f) other thermoplastic polymer such as other ABS resin, A
Styrene resin such as ES resin, HIPS, AS resin;
Polyamides such as nylon 6, nylon 6,6 and nylon 4,6; polyesters such as polybutylene terephthalate and polyethylene terephthalate; other aromatic polycarbonates, PPS resins, liquid crystal polyester resins,
Polyarylate resin, polysulfone resin, AS resin, M
Blended with polymers such as S resin, PVC resin, styrene-maleic anhydride copolymer and maleimide copolymer,
(G) As a thermoplastic polymer composition, it can be used as an impact modifier, a compatibilizer, etc. of these polymers.

(G) In the thermoplastic polymer composition,
The ratio of (e) rubber-reinforced vinyl polymer and (e) other thermoplastic polymer is 1 to 99 parts by weight of (e) component, preferably 5 to 90 parts by weight, more preferably 10 to 80 parts by weight,
(He) component 99 to 1 part by weight, preferably 95 to 10 parts by weight, more preferably 90 to 20 parts by weight. (E)
When the ratio of the rubber-reinforced vinyl polymer is less than 1 part by weight,
The impact resistance decreases, while if it exceeds 99 parts by weight, the moldability decreases, which is not preferable.

(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.

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

Further, as the other antistatic agents, all of the commonly used antistatic agents can be used. As the antistatic agent, there are anionic type, cationic type, nonionic type, amphoteric type and the like, and any of them can be used. Particularly preferred are anionic type and nonionic type, and of these, sodium sulfonate type and monoglyceride type are preferable. These 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 and 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 (v) rubber-reinforced vinyl polymer or (v) thermoplastic polymer composition may contain the above-mentioned additives, if necessary, in the (v) component alone or in the (v) to (v) components. , 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. When kneading the components, the components may be kneaded at once, or may be kneaded by a multi-stage addition method.

The composition thus obtained is injection molded, sheet extruded, vacuum molded, profiled, 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 take advantage of their excellent properties and can be used for large televisions, video
Refrigerators, calculators, air conditioners, lighting fixtures, rice cookers, home appliances such as telephones, light appliances, computers, copying machines,
Office equipment such as facsimiles, office equipment, cars
Exterior parts, motorcycle parts, various leisure products, toys, extruded sheets, pipe products, building material parts, machinery / tool parts, industrial equipment / parts, medical equipment, food containers, stationery / daily necessities, pachinko machines, family computers, etc. Used for parts of game machines.

[0074]

The rubber-reinforced vinyl polymer of the present invention uses a reactive emulsifier as at least a part of the emulsifier when emulsion-polymerizing the vinyl monomer in the presence of the rubber-like polymer latex. , The grafting rate is improved by facilitating the formation of a polymerization field between the rubber serving as a graft base point, the interface, and the monomer micelle, and the reactive emulsifier is a vinyl constituting the copolymer or matrix constituting the latex. (Graft) copolymerization in the system polymer, and mixing of the emulsifier in the waste water 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.

[0075]

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.

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.

Reference Example 1 (Production of polybutadiene rubber latex) In a reactor equipped with a stirrer and having a capacity of 100 liters, 100 parts of 1,3-butadiene, 60 parts of water, 2.4 parts of potassium rosinate as an ordinary emulsifier, and potassium carbonate. 1.0 part, potassium hydroxide 0.1 part, t-dodecyl mercaptan 0.3 part as a chain transfer agent, and potassium persulfate 0.3 part as a polymerization initiator were added, and the mixture was batched at 60 to 70 ° C. for 30 hours. Polymerized. The polymerization conversion rate was 96%. 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 referred to as latex (A-1).
The evaluation results of this latex (A-1) are shown in Table 1.

Reference 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 potassium rosinate, 0.1 parts potassium hydroxide, 0.1 parts t-dodecyl mercaptan as a chain transfer agent, 0.3 parts potassium persulfate, polymerization temperature 6
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. The polymerization conversion rate was 99%. 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 designated as latex (A-2). The evaluation results of this latex (A-2) are shown in Table 1.

Reference Examples 3 to 8 (Production of Rubbery Polymer Latex) In Reference Example 3 [latex (A-3)], reactive emulsifier AQUARON HS-05 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used. Reference Example 4 [latex (A-4)] is the same as Reference Example 1 except that 2.4 parts are used, and Reference Example 5 is the same as Reference Example 2 except that 2.4 parts of Aqualon HS-05 is used. [Latex (A-5)] is the above-mentioned Aqualon HS-05 /
Reference Example 6 [latex (A-6)] in the same manner as Reference Example 1 except that potassium rosinate = 1.2 parts / 1.2 parts was used.
Is the above Aqualon HS-05 / potassium rosinate =
As in Reference Example 2, except that 1.2 parts / 1.2 parts were used,
Reference Example 7 [latex (A-7)] is the same as Reference Example 1 except that 1,3-butadiene / styrene = 80 parts / 20 parts is used.
1,3-butadiene / acrylonitrile = 80 parts / 20
Latex was obtained in the same manner as in Reference Example 1 except that parts were used. Table 1 shows the evaluation results of these latexes.

Example 1 (Production of Rubber Reinforced Vinyl Polymer) 82 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-50 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 as a chain transfer agent over 2 hours.

Then, 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 2 (Production of rubber-reinforced vinyl polymer) Polymerization was carried out in the same manner as in Example 1 except that the latex (A-2) (acrylic rubber latex) was used.
The polymerization conversion rate was 100%. This is referred to as latex (B-2). The evaluation results of this latex (B-2) are shown in Table 2.

Examples 3 to 14 and Comparative Examples 1 to 9 (Production of Rubber Reinforced Vinyl Polymer) Rubber reinforced vinyl polymers were obtained in the same manner as in Example 1 using the polymerization formulations shown in Tables 2 to 5. . The results are shown in Tables 2-5.

Examples 15 to 28, Comparative Examples 10 to 18 (Production of Thermoplastic Polymer Composition) The rubber-reinforced vinyl polymer prepared above was added to the thermoplastic polymer [acrylonitrile / styrene = 30 parts / 70 parts]. Acrylonitrile-styrene copolymer consisting of], other lubricants, heat stabilizers, etc. are mixed according to the formulation shown in Tables 6 to 9 or as a single substance, a resin temperature of 200 is obtained by a vented extruder.
Pellets were produced by melt-kneading at ℃ and extruding. 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 6-9.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

[Table 3]

[0094]

[Table 4]

[0095]

[Table 5]

[0096]

[Table 6]

[0097]

[Table 7]

[0098]

[Table 8]

[0099]

[Table 9]

[0100]

According to the present invention, when emulsion-polymerizing a vinyl monomer in the presence of a rubber-like polymer latex, a reactive emulsifier is used as at least a part of the emulsifier to improve impact resistance and surface. Excellent in appearance of molded products such as glossiness, heat stability, and color tone, and non-contamination of molds, and there are few eye tarps (thermochromic substances generated at the exit of the ruder) that cause foreign matter, and the pollution load of wastewater during manufacturing is reduced. Small, rubber-reinforced vinyl polymer,
And a composition thereof.

 ─────────────────────────────────────────────────── ─── 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. (c) Rubber-like polymer latex 3 to 80
In the presence of parts by weight (in terms of solid content), 97 to 20 parts by weight of (d) vinyl-based monomer [where (c) + (d) = 100
Parts by weight], (b) at least the reactive emulsifier (b-1)
A rubber-reinforced vinyl polymer obtained by polymerization using 0.1 to 10 parts by weight of an emulsifier containing 5 to 200% by weight. 2. The (b) emulsifier is a reactive emulsifier (b)
The rubber-reinforced vinyl polymer according to claim 1, wherein 1) / other emulsifier (b-2) = 1 to 100/99 to 0% by weight. 3. 1 to 99 parts by weight of the (e) rubber-reinforced vinyl polymer according to claim 1 or 2 and 99 to 1 parts by weight of another thermoplastic polymer (f) [where (e) + ( F) = 10
0 parts by weight] as a main component.