JPH1171433A - Thermoplastic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin having a high molecular weight, a broad molecular weight distribution and improved dispersibility in another thermoplastic polymer by (co)polymerizing an aromatic vinyl compound with a vinyl cyanide compound and/or a vinyl compound copolymerizable therewith. SOLUTION: 95-50 1/5-50 wt.%, desirably 75-65 125-35 wt.%, more desirably 73-69 127-31 wt.% aromatic vinyl compound is copolymerized with 5-50 wt.%, desirably 25-35 wt.%, more desirably 27-31 wt. % vinyl cyanide compound and 0-30 wt.%, desirably 0-20 wt.%, more desirably 0-10 wt.% another vinyl compound copolymerizable therewith to obtain a thermoplastic resin having an intrinsic viscosity of 1.5 dl/g or above, desirably 2.0 dl/g or above, more desirably 2.5-10.0 dl/g, a weight-average molecular weight/number-average molecular weight ratio of 3.0 or above, desirably 4.0 or above, more desirably 5.0-15.0 and a storage modulus at 150-190 deg.C of 1.5×10<5> Pa or above, desirably 2.0×10<5> Pa or above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin having a high molecular weight, excellent dispersibility in other thermoplastic polymers, and suitable as a modifier for other thermoplastic polymers.

[0002]

2. Description of the Related Art When a thermoplastic resin such as an ABS resin is used for blow molding, vacuum molding, extrusion (foaming), calendering, etc., the viscosity at the time of melting is remarkably reduced. Problems such as worsening of drawdown during vacuum forming, lowering of the retention rate of foaming gas during (foaming) extrusion forming, and adhesion to rolls during calendering have occurred. For this reason, as a resin modifier with a small decrease in viscosity at the time of melting, when a strong polar component is copolymerized in a large amount and the decrease in viscosity is suppressed, crosslinking of such a strong polar component may cause heat. There are problems such as a decrease in stability.

[0003] In order to solve this problem, the molecular weight is high and the molecular weight distribution determined by gel permeation chromatography (GPC) [weight average molecular weight (Mw)]
/ Number average molecular weight (Mn)] is blended with a thermoplastic resin to suppress the decrease in viscosity. However, these resins have a high molecular weight and a narrow molecular weight distribution (GP
The thermoplastic resin (which has a small Mw / Mn by C) generally has a new problem that it is hard to mix with other polymers, and it takes a long time for dispersion in the case of melt-kneading.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has a high molecular weight, a wide molecular weight distribution (Mw / Mn), and a modification of other thermoplastic polymers. The present invention provides a thermoplastic resin suitable as an agent.

[0005]

According to the present invention, at least one compound selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and another vinyl monomer copolymerizable therewith is provided.
A seed (hereinafter also referred to as a “monomer component”) obtained by (co) polymerization, having an intrinsic viscosity of 1.5 dl / g or more and a weight average molecular weight / number average molecular weight ratio of more than 3.0. To provide a thermoplastic resin.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin of the present invention contains at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds and other vinyl monomers copolymerizable therewith. ) It is a thermoplastic (co) polymer obtained by polymerization and having a high molecular weight and a wide molecular weight distribution. here,
Examples of the aromatic vinyl compound include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene,
N, N-diethyl-p-aminoethylstyrene, N, N
-Diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, etc., with styrene and α-methylstyrene being particularly preferred. These aromatic vinyl compounds can be used alone or in combination of two or more. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and these can be used alone or as a mixture of two or more. Preferably, it is acrylonitrile.

Further, other copolymerizable vinyl monomers include alkyl (meth) acrylate, maleimide monomer, unsaturated acid, unsaturated monomer containing an acid anhydride group, and unsaturated monomer containing an epoxy group. Examples thereof include a saturated monomer, a hydroxyl group-containing unsaturated monomer, an amide group-containing unsaturated monomer, an amino group-containing unsaturated monomer, and an oxazoline group-containing unsaturated monomer. Among them, examples of the alkyl (meth) acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, Acrylic esters such as benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-
Examples include methacrylic acid esters such as ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate. Methyl methacrylate and butyl acrylate are preferable.

The maleimide monomers include maleimide, N-methylmaleimide, N-butylmaleimide, and N-butylmaleimide.
-(P-methylphenyl) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like are preferable, and N-phenylmaleimide and N-cyclohexylmaleimide are preferable. Examples of the unsaturated acid include acrylic acid and methacrylic acid. Examples of the acid anhydride group-containing unsaturated monomer include maleic anhydride, itaconic anhydride, citraconic anhydride and the like, with maleic anhydride being preferred. Examples of the epoxy group-containing unsaturated monomer include glycidyl methacrylate and allyl glycidyl ether, and glycidyl methacrylate is preferred.

The hydroxyl group-containing unsaturated monomers include 3-hydroxy-1-propene and 4-hydroxy-
1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-
2-methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, p-
Hydroxystyrene and the like are preferable, and 2-hydroxyethyl methacrylate is preferable. Examples of the amide group-containing unsaturated monomer include acrylamide and methacrylamide, and acrylamide is preferable.
As the amino group-containing unsaturated monomer, acrylamine,
Examples include dimethylamino methacrylate, diethylamino methacrylate, dimethylamino methacrylate and the like. Examples of the oxazoline group-containing unsaturated monomer include vinyl oxazoline. These other copolymerizable vinyl monomers can be used alone or in combination of two or more.

The ratio of the aromatic vinyl compound to the vinyl cyanide compound used in the thermoplastic resin of the present invention is preferably from aromatic vinyl compound / vinyl cyanide compound to 95 to 50 in view of the balance between the coloring property and the processability. / 5 to 50
%, More preferably 75-65 / 25-35% by weight, particularly preferably 73-69 / 27-31% by weight. When the use ratio of the vinyl cyanide compound exceeds 50% by weight, thermal stability is deteriorated and coloring is caused, which is not preferable. On the other hand, when the use ratio of the vinyl cyanide compound is less than 5% by weight, the ductility is reduced, which is not preferable. The proportion of other copolymerizable vinyl monomers is preferably 0 to 30% by weight, more preferably 0 to 20% by weight, and particularly preferably 0 to 10% by weight in all monomer components. %. If it exceeds 30% by weight, the thermal stability of the obtained thermoplastic resin is undesirably reduced.

The intrinsic viscosity [η] of the thermoplastic resin of the present invention
Is at least 1.5 dl / g, preferably at least 2.0 dl / g, more preferably from 2.5 to 10.0 dl / g, particularly preferably from 2.5 to 5.5 dl / g. If the intrinsic viscosity is less than 1.5 dl / g, the modifying effect using the thermoplastic resin of the present invention is lost, which is not preferable. In addition, 10.
If it exceeds 0 dl / g, poor dispersion may occur, which may be undesirable. Here, the intrinsic viscosity [η] is such that the thermoplastic resin of the present invention is completely dissolved in dimethylformamide,
Five points with different concentrations were made, and using an Ubbelohde viscosity tube,
It is a value obtained from the result of measuring the reduced viscosity at each concentration of 0 ° C.

The thermoplastic resin of the present invention has a molecular weight distribution, that is, a weight average molecular weight / number average molecular weight ratio (Mw /
Mn) must exceed 3.0, preferably 4.0.
Above, more preferably 5.0 or more, particularly preferably 5.0 to 15.0. If it is 3.0 or less, it is not preferable because it takes a long time to disperse the thermoplastic resin of the present invention when mixed with another thermoplastic polymer. In addition, melt kneading for a short time is not preferable because the dispersibility of the thermoplastic resin of the present invention is poor and the effect of modifying other thermoplastic polymers is reduced. Here, the molecular weight distribution (Mw) of the thermoplastic resin of the present invention
/ Mn) uses dimethylformamide as a solvent,
It is a value obtained from a weight average molecular weight (Mw) and a number average molecular weight (Mn) measured by gel permeation chromatography and subjected to molecular weight calibration based on polystyrene.

The thermoplastic resin of the present invention has a viscosity of 150-1.
The storage modulus at 90 ° C. preferably has a value exceeding 1.5 × 10 ⁵ Pa, more preferably 2.0 × 10 ⁵ Pa.
× 10 ⁵ Pa or more, particularly preferably 6.0 × 10 ⁵ Pa or more. When the storage elastic modulus is 1.5 × 10 ⁵ Pa or less, the effect of modifying another thermoplastic polymer by the thermoplastic resin of the present invention may be reduced. Here, the storage modulus is a value measured as follows. Preparation of Test Piece for Storage Elasticity Measurement A thermoplastic resin was melt-pressed and formed into a sheet having a thickness of 1 mm, and this sheet was cut into a strip having a length of 40 mm and a width of 5 mm to obtain a test piece. Measurement conditions for storage modulus Measurement equipment: Polymer Laboratories (Polymer)
Laboratories), Dynamic
Mechanical Thermal Analyss
is (DMTA) device Total sample length; 40 mm Sample thickness; 1 mm Measurement temperature; 150 to 190 ° C. Jig shape; Dual Cantilever
r) Sample length between jigs; 5 mm angular frequency; 2π rad / s (1 Hz)

The intrinsic viscosity, weight average molecular weight and number average molecular weight of the thermoplastic resin of the present invention can be controlled by changing the type and amount of a polymerization initiator, a chain transfer agent, an emulsifier, a solvent and the like. Further, it can be controlled by changing the method of adding the monomer component, the addition time, the polymerization time, the polymerization temperature, and the like. In particular, the intrinsic viscosity of the thermoplastic resin of the present invention can be adjusted by adding a chain transfer agent, but is preferably adjusted by the amount of the polymerization initiator used. In order to obtain the thermoplastic resin of the present invention, particularly in emulsion polymerization using an emulsifier having a low CMC (critical micelle concentration), a small amount of a water-soluble polymerization initiator is used without using a chain transfer agent, and a monomer component is used. It is preferred to employ a polymerization method in which the polymerization is added in multiple stages and the polymerization temperature is controlled at a relatively low polymerization temperature.

The production of the thermoplastic resin of the present invention usually includes suspension polymerization and emulsion polymerization. The thermoplastic resin of the present invention has a considerably higher molecular weight than ordinary styrene resins, but a preferred polymerization method for obtaining such a high molecular weight resin is emulsion polymerization. A more preferred polymerization method is a method in which emulsion polymerization is used as the polymerization method, and the monomer components are added all at once or dividedly and polymerized. For emulsion polymerization,
A radical polymerization initiator, an emulsifier, a chain transfer agent and the like are used. Examples of the radical polymerization initiator include an oxidizing agent composed of organic hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, t-butylperoxylaurate, and sugar-containing iron pyrophosphate. Redox initiators in combination with reducing agents such as formulations, sulfoxylate formulations, and mixed formulations of sugar-containing iron pyrophosphate formulation / sulfoxylate formulation; persulfates such as potassium persulfate and ammonium persulfate; azobisiso Azo compounds such as butyronitrile, dimethyl-2,2'-azobisisobutyrate, and 2-carbamoylazaisobutyronitrile; organic peroxides such as benzoyl peroxide and lauroyl peroxide; Preferably persulfate Umm is a water-soluble initiator such as. At this time, a reducing agent such as iron sulfate or sodium hydrogen sulfite may be used in combination.

The amount of these radical polymerization initiators used is
Usually, 0.1 part by weight per 100 parts by weight of the monomer component used.
01 to 2 parts by weight, preferably 0.03 to 0.5 part by weight,
More preferably, it is about 0.05 to 0.3 parts by weight.
When the amount is less than 0.01 part by weight, the polymerization reaction is not started stably. On the other hand, when the amount is more than 2 parts by weight, the polymerization reaction is rapidly started and the heat generated by the polymerization heat is large, so that it is difficult to control the polymerization temperature. As a result, the molecular weight of the thermoplastic resin is lowered, which is not preferable.

Examples of the emulsifier include alkali metal salts of rosin acid, alkali metal salts of fatty acids, alkali metal salts of aliphatic alcohol sulfates, alkali metal salts of alkyl allyl sulfonic acids, alkali metal salts of dialkyl sulfosuccinates, and polyoxygens. Examples thereof include alkali metal salts of sulfates of ethylene alkyl (phenyl) ether and alkali metal salts of phosphates of polyoxyethylene alkyl (ether). Of these, alkali metal salts of fatty acids are preferable.

The amount of the emulsifier used is 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the monomer component used. If the amount is less than 0.1 part by weight, the stability of the latex at the time of emulsion polymerization decreases, while if it exceeds 10 parts by weight, the concentration of the residual emulsifier contained in the thermoplastic resin obtained by the emulsion polymerization increases, and the thermal stability Is worsened and coloring is not preferred.

Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, and tetraethyl. Thiuram sulfide, carbon tetrachloride, ethylene bromide,
Examples thereof include hydrocarbon salts such as pentanephenylethane, terpenes, acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol, and α-methylstyrene dimer. These chain transfer agents can be used alone or in combination of two or more. The amount of the chain transfer agent to be used is generally 0.02 to 1 part by weight based on 100 parts by weight of the monomer component.
If the amount is less than 0.02 parts by weight, it is difficult to exert the effect of the chain transfer agent as a molecular weight modifier, while if it exceeds 1 part by weight, the molecular weight of the obtained thermoplastic resin is undesirably reduced.

The amount of water used in the emulsion polymerization is usually 110 parts by weight based on 100 parts by weight of the monomer component used.
To 330 parts by weight, preferably 120 to 300 parts by weight, more preferably 130 to 270 parts by weight. If the amount is less than 110 parts by weight, the heat generated by the polymerization heat is large, so that it is difficult to control the polymerization temperature, and the molecular weight of the resulting thermoplastic resin is reduced. This is unfavorable because it slows down and requires a long time for the reaction.

On the other hand, if the polymerization temperature is increased, the chain transfer constant to the monomer increases, and the molecular weight cannot be increased. The preferred polymerization temperature is 50 to 98C, more preferably 55 to 98C. In the polymerization, it is preferable to keep the internal temperature constant within this polymerization temperature range. If the polymerization temperature is lower than 50 ° C., decomposition of the polymerization initiator hardly occurs, so that the initiation of polymerization becomes unstable. . Further, the polymerization time is
It is preferable to set it to 3 hours or more. If the heating time is less than 3 hours, the heat generated by the polymerization heat is large, so that it is difficult to control the polymerization temperature, which results in a decrease in the molecular weight of the thermoplastic resin, which is not preferable.

When polymerizing the thermoplastic resin of the present invention,
Since the polymerization activity decreases due to the influence of dissolved oxygen in the latex, it is necessary to sufficiently replace the nitrogen. The oxygen concentration before the polymerization is 3,000 ppm or less, preferably 1,
000 ppm or less. More preferably, the dissolved oxygen is removed with an oxygen remover such as hydrosulfite.

The thermoplastic resin of the present invention is obtained by drying the obtained latex through a recovery process such as coagulation and washing to form a powder after drying. As the coagulant used in the coagulation step, sulfuric acid, magnesium sulfate, calcium chloride, aluminum sulfate or the like is used as an aqueous solution.

The thermoplastic resin of the present invention can be blended as a modifier with other thermoplastic polymers. Here, as other thermoplastic polymers, acrylic rubber, silicone rubber, fluorine-based rubber, butyl rubber, natural rubber,
Polyisoprene rubber, butadiene rubber, ethylene-α-
Olefin rubber, NBR, SBR, SIS, SEP
Rubbery polymers such as S, SEBS, and thermoplastic polyurethane; at least one selected from the group consisting of the above-mentioned aromatic vinyl compounds, vinyl cyanide compounds, and other copolymerizable vinyl monomers (co) A (co) polymer having an intrinsic viscosity of 0.2 to 1.0 dl / g, preferably a styrene-acrylonitrile copolymer, a polymethyl methacrylate, a styrene-methyl methacrylate copolymer,
Styrene-N-phenylmaleimide copolymer and the like can be mentioned.

The other thermoplastic polymer is selected from the group consisting of the above-mentioned aromatic vinyl compound, vinyl cyanide compound and other copolymerizable vinyl monomers in the presence of the above-mentioned rubbery polymer. Rubber-modified thermoplastic resin obtained by graft polymerization of at least one type of monomer, preferably ABS resin, MBS resin, acrylic rubber-based graft copolymer, silicone rubber-based graft copolymer, AES resin, hydrogenated rubber-based Examples include a graft copolymer. Further, other thermoplastic polymers include nylon 12, nylon 6,
Polyamides such as nylon 6,6 and nylon 4,6, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polyethylene and polypropylene, polytetrafluoroethylene (PTFE), polycarbonate, polyphenylene sulfide resin, polyoxymethylene (POM) , Polyphenylene oxide (PPO), vinyl chloride resin, polyamide elastomer, polyester elastomer and the like. These other thermoplastic polymers can be used singly or as a mixture of two or more.

The thermoplastic resin of the present invention and the composition using the same are obtained by kneading the (each) component using various extruders, Banbury mixers, kneaders, rolls, ribbon blenders, Henschel mixers and the like. Can be A preferred production method is a method using a twin screw extruder or a Banbury mixer. When kneading the components, the components may be kneaded at once, or may be kneaded by a multi-stage addition method.

The thermoplastic resin of the present invention or a composition using the same may contain a known stabilizer, plasticizer,
Lubricants, colorants, wood powder, paper, inorganic fillers, antioxidants, weathering (light) agents, metal powders, antibacterial agents, antifungal agents, silicone oils, capron agents, and the like can be added together.

The composition using the thermoplastic resin of the present invention comprises:
Since it has excellent workability, a good molded product can be obtained by various processing methods. In particular, processing methods in which the composition using the thermoplastic resin of the present invention is effective include (foaming) extrusion molding, blow molding, injection molding, calendering, vacuum molding, and inflation molding.

Here, in the (foaming) extrusion molding, sheets such as pipes, hoses, sheets for building materials, sheets for vacuum forming, laminated sheets, and irregularly shaped articles can be obtained.
In the blow molding, various molded products can be obtained by an extrusion blow molding method, an injection blow method, a sheet blow method, a cold parison method, or the like.

In the injection molding, in addition to a normal molding machine, various molding methods such as gas assist molding, in-mold molding, two-color molding, thermo-ejection molding, and sandwich molding are used.
A molded article can be obtained. In the calendering process, it is possible to obtain surface-decorated molded products by various thicknesses of films, sheets, and embossing. In vacuum forming, straight forming, drape forming, plug assist forming, plug assist reverse draw forming, air slip forming, snapback forming, reverse draw forming, air cushion forming, plug assist air slip forming, free forming,
There are matched mold molding, plug ring molding, slip molding, contact heating molding, and the like, and various molded products can be obtained using various sheets, films or embossed sheets and films. In inflation molding, molded articles such as tubes, general films, stretchable films, and multilayer films can be obtained. The various molded products obtained by the above-mentioned molding method can be used for various parts such as OA / home electric appliances, automobile parts, building material products, daily necessities, etc. by utilizing their excellent properties.

[0031]

EXAMPLES The present invention will now be described more specifically with reference to examples. Parts and% in Examples are parts by weight and% by weight unless otherwise specified. During the implementation, various measurement items were as described below.

The limiting viscosity copolymer is completely dissolved in dimethylformamide,
Five points with different concentrations were made, and using an Ubbelohde viscosity tube,
From the result of measuring the reduced viscosity at each concentration of 0 ° C., the intrinsic viscosity [η] was determined. Weight average molecular weight (Mw), number average molecular weight (Mn) and
Molecular weight distribution (Mw / Mn) manufactured by Waters, Gel Permeation Chromatograph (GPC-
244), TSK-ge manufactured by Tosoh Corporation as a column
1-GMH × 1 (2), dimethylformamide as a solvent, flow rate 0.8 ml / min, measured at a temperature of 23 ° C., and calibrated based on polystyrene.

Drawdown properties The ingredients were mixed according to the following formulation and kneaded at 220 ° C. with a twin-screw extruder to obtain pellets. ABS resin 45 parts AS resin 55 parts Any one of the following thermoplastic resins (I) to (VIII) 5 parts The drawdown time of this pellet was measured at 250 ° C by the method described below. That is, 2 g of the obtained pellets were weighed, packed in a cylinder of an elevated flow tester, heated for 10 minutes, and then loaded with 50 kg.
It was applied, 0.5 cc was extruded, the load was removed, and the start time was set. While measuring the diameter of the resin rod extruded from the lower part of the flow test, the temperature was kept constant, and the time required to reach 80% of the diameter of the resin rod at the start time was measured.

Preparation of thermoplastic resins (I) to (VIII) Potassium stearate as an emulsifier, potassium persulfate as a polymerization initiator, styrene and acrylonitrile as monomer components and, if necessary, methyl methacrylate or n Using -butyl acrylate, thermoplastic resins (I) to (VIII) having compositions, intrinsic viscosity [η], and a weight average molecular weight / number average molecular weight ratio (Mw / Mn) were obtained by an emulsion polymerization method. [Η] and Mw / Mn are:
The desired amount was obtained by changing the amount of the emulsifier and the polymerization initiator and the method of adding the monomer.

[0035]

[Table 1]

Preparation of ABS Resin An emulsion resin was obtained by emulsion graft polymerization of 36.5 parts of styrene and 13.5 parts of acrylonitrile in the presence of 40 parts (in terms of solid content) of polybutadiene latex having an average rubber particle diameter of 2,600 angstroms. ABS resin (graft rate 55
%). Here, the graft ratio (Gf) is a value calculated from the following formula from the acetone-insoluble component [gel component (g)] and the rubber content (b). Gf = [(g−b) / b] × 100 (%) Preparation of AS resin Intrinsic viscosity [η] (in dimethylformamide at 30 ° C.) =
An acrylonitrile-styrene copolymer having an acrylonitrile content of 0.7 and an acrylonitrile content of 29% was used.

Examples 1 to 6 and Comparative Examples 1 and 2 The above components were mixed at the mixing ratio shown in Table 2 with a Henschel mixer, kneaded with a Banbury mixer and pelletized. went.

[0038]

[Table 2]

As is clear from Table 2, the compositions using the thermoplastic resin of the present invention (Examples 1 to 6) are all excellent in drawdown resistance. On the other hand, in Comparative Example 1, since the molecular weight distribution (Mw / Mn) was out of the range of the present invention, good drawdown resistance was not obtained. In Comparative Example 2, since the intrinsic viscosity of the thermoplastic resin was out of the range of the present invention, good drawdown resistance was not obtained.

[0040]

Industrial Applicability The thermoplastic resin of the present invention has a high intrinsic viscosity, a wide molecular weight distribution, excellent dispersibility in other thermoplastic polymers, and is suitable as a modifier for other thermoplastic polymers. It is.

Claims (1)

[Claims] 1. An aromatic vinyl compound, a vinyl cyanide compound and at least one selected from the group consisting of other vinyl monomers copolymerizable therewith, obtained by (co) polymerizing an intrinsic viscosity. 1.5 dl / g or more, weight average molecular weight /
A thermoplastic resin having a number average molecular weight ratio exceeding 3.0.