JPH08319327A - Rubbery polymer and abs-based resin using the same - Google Patents

Abstract

PURPOSE: To obtain an ABS-based resin excellent in impact resistance, flowability, and appearance when molded. CONSTITUTION: This ABS-based resin consisting of a graft copolymer is obtained by polymerization of 95-30 pts.wt. of a monomer mixture composed of a total of 100wt.% of 10-40wt.% of a vinyl cyanide-based monomer, 60-90wt.% of an aromatic vinyl-based monomer and 0-20wt.% of at least one kind of other vinyl- based monomer copolymerizable therewith, in the presence of 5-70 pts.wt. of a rubbery polymer >=100000 in the weight-average molecular weight of the toluene solubles therein, 40wt.% in gel content and 15-50 in swelling degree. In this graft copolymer, the weight-average particle diameter and the graft rate of the rubbery polymer is 0.15-0.40μm and 15-100%, respectively.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a rubber-like polymer suitable for obtaining an ABS resin excellent in impact resistance, fluidity and molding appearance (surface gloss) and an ABS resin using the same.

[0002]

PRIOR ART AND PROBLEM TO BE SOLVED BY THE INVENTION AB
The S resin is a vinyl cyanide-based monomer and an aromatic vinyl-based monomer, and in some cases, other copolymerizable monomers such as unsaturated carboxylic acid ester-based monomers. It is a resin obtained by graft polymerization on a rubber-like polymer, and is widely used because of its many features such as high impact resistance, smooth molding appearance, and good moldability.

The mechanical properties of the ABS resin depend on the properties of the rubber-like polymer, the dispersed particle size and particle size distribution in the matrix resin, the amount of graft copolymerization on the rubber-like polymer, the thickness of the graft layer and the like. That is generally well known. In particular, the excellent impact resistance, which is a characteristic of ABS resin, is a property that varies greatly depending on these factors, and it is important to set these factors appropriately in order to obtain an ABS resin having excellent impact resistance. is there.

From this point of view, various studies have been conventionally made on suitable rubbery polymers to be used as a raw material for ABS resins, and ABS resins developed based on these findings have come to be widely used as industrial materials.

Recently, resin molded products have become larger and thinner,
Due to the complicated shape, demands on ABS resins have been increased, and various physical properties such as impact resistance, fluidity, rigidity, and appearance have been improved for these resin compositions.

However, some applications require a more strict balance, and at present, satisfactory physical properties have not been obtained yet. That is, if the content of the rubber-like polymer is increased for the purpose of improving impact resistance, the fluidity, appearance, hardness, elastic modulus, and heat resistance of the resin are lowered, and there is a limit in achieving balance. .

[0007]

In view of the above situation, the inventors of the present invention have made earnest studies in order to provide an ABS resin excellent in impact resistance, fluidity and molding appearance (surface gloss). As a result of proceeding, as one of the improvement methods, focusing on the molecular weight of the toluene-soluble component of the rubber-like polymer,
It was found that the molecular weight greatly affects the impact resistance of the ABS resin, and the present invention has been achieved.

That is, the present invention comprises 30 to 100 parts by weight of an aliphatic conjugated diene monomer, vinyl cyanide monomer, aromatic vinyl monomer and unsaturated carboxylic acid ester monomer. A rubber-like polymer obtained by polymerizing 70 to 0 parts by weight (at 100 parts by weight in total) of at least one other copolymerizable monomer selected from the group consisting of: A rubber-like polymer having a molecular weight of 100,000 or more, a gel content of 40% by weight or more, and a swelling degree of 15 to 50, and in the presence of 5 to 70 parts by weight of the rubbery polymer, Vinyl cyanide monomer 1
0 to 40% by weight, 60 to 90% by weight of an aromatic vinyl monomer, and 0 to 20% by weight (at least 100% by weight in total) of at least one other vinyl monomer copolymerizable therewith. It comprises a graft copolymer obtained by polymerizing 95 to 30 parts by weight of the monomer mixture, and the weight average particle diameter of the rubber-like polymer in the graft copolymer is 0.15 to 0.
Cyan in the presence of 5 to 70 parts by weight of an ABS resin having a diameter of 40 μm and a graft ratio of 15 to 100%, and an enlarged rubber-like polymer obtained by enlarging the above rubber-like polymer. Vinyl chloride monomer 10 to 40% by weight,
Aromatic vinyl-based monomer 60 to 90% by weight and at least one other vinyl-based monomer copolymerizable therewith 0 to
A graft copolymer obtained by polymerizing 95 to 30 parts by weight of a monomer mixture consisting of 20% by weight (total 100% by weight), and the weight average particle of the enlarged rubber-like polymer in the graft copolymer. An ABS resin having a diameter of 0.15 to 0.40 μm and a graft ratio of 15 to 100%.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
As the monomer used for producing the rubber-like polymer of the present invention, an aliphatic conjugated diene monomer alone, or the aliphatic conjugated diene monomer and a vinyl cyanide monomer,
Examples thereof include a mixture with at least one other copolymerizable monomer selected from the group consisting of aromatic vinyl-based monomers and unsaturated carboxylic acid ester-based monomers.

Examples of the aliphatic conjugated diene type monomer include
For example, 1,3-butadiene, isoprene, chloroprene and the like can be mentioned, and it is preferable to use 1,3-butadiene from the viewpoint of impact resistance.

Examples of other monomers copolymerizable with the aliphatic conjugated diene monomer include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; styrene, α-methylstyrene, p -Aromatic vinyl monomers such as chlorostyrene and p-methylstyrene; methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate,
Examples thereof include unsaturated carboxylic acid esters such as methyl methacrylate and ethyl methacrylate.

The ratio of the aliphatic conjugated diene monomer used to obtain the rubbery polymer to the other copolymerizable monomer is 30 to 100. The amount of the other copolymerizable monomer is 70 to 0 parts by weight (total 100 parts by weight) with respect to parts by weight. When the amount of the aliphatic conjugated diene-based monomer used is less than 30 parts by weight, A obtained is
The impact resistance of the BS resin will be reduced.

The rubber-like polymer may be solution-polymerized by using a Ziegler type catalyst, homogenized with an emulsifier and water and then emulsion-dispersed, or a polymer obtained by emulsion-polymerization may be used. The method is not limited. Emulsion polymerization is most suitable because of the dispersed particle size and molecular weight of the rubber-like polymer, the gel content, the ease of controlling the degree of swelling, and the degree of freedom for producing a high-performance ABS resin.

The rubber-like polymer of the present invention needs to have a weight average molecular weight of the toluene-soluble component of 100,000 or more, more preferably 130,000 or more. When the weight average molecular weight of the toluene-soluble component is less than 100,000, the impact resistance of the obtained ABS resin is lowered.

Any method may be used to control the molecular weight of the toluene-soluble component, but the type and amount of the polymerization initiator, the polymerization temperature, the type and amount of the chain transfer agent such as mercaptans, etc. may be used. This can be achieved by changing it according to the purpose.

The weight average molecular weight of the toluene-soluble component referred to in the present invention is 100 g after 0.5 g of the dried rubber-like polymer is immersed in 60 ml of toluene at 30 ° C. for 48 hours.
The insoluble matter was removed with a mesh wire net and the toluene solution was dried to dissolve the sample in tetrahydrofuran (sample concentration: 2.
4 mg / ml), GPC (Shimadzu Corporation, LC-6)
It means a value obtained by polystyrene conversion in A).

The rubber-like polymer of the present invention has a gel content of 40% by weight or more, preferably 60% by weight or more, and a swelling degree of 15 to 50, preferably 20 to 40.
It is necessary to be. When the gel content is less than 40% by weight, impact resistance and gloss of the obtained ABS resin will be deteriorated. Further, if the degree of swelling is less than 15, the impact resistance of the obtained ABS resin will be lowered, and if it exceeds 50, the flexural modulus of the obtained ABS resin will be lowered and the gloss will be poor.

The gel content and the degree of swelling referred to in the present invention are 0.5 g of dried rubbery polymer and 60 parts of toluene.
After dipping in 30 ml at 30 ° C. for 48 hours, the mixture was filtered through a 100-mesh wire net, the insoluble content on the mesh and its weight after drying were measured, and determined by the following formulas (I) and (II). Says the value.

Gel content (%) = [M ₂ / M ₀ ] × 100 (I)

Swelling degree = [(M ₁ −M ₂ ) / M ₂ ] (II)

However, in the above formulas (I) and (II), M
₀ represents the weight of the dry rubber-like polymer, M ₁ represents the swelling weight of the insoluble matter remaining on the 100-mesh wire net, and M ₂ represents the weight of the insoluble matter after drying.

The gel content and swelling degree of the rubber-like polymer can be adjusted by known methods. For example, the use of crosslinkable monomers such as divinylbenzene, allyl methacrylate, ethylene glycol dimethacrylate, diallyl adipate. The polymerization temperature can be adjusted, the initiator concentration can be adjusted, the polymerization conversion can be adjusted, and a chain transfer agent such as mercaptans can be used.

Next, the ABS resin of the present invention is a bloated rubber obtained by polymerizing a monomer mixture with the above rubber-like polymer or expanding the above rubber-like polymer by the following method. It is composed of a graft copolymer obtained by polymerizing a monomer mixture with a rubber-like polymer. In the present invention, the weight average particle diameter of the rubber-like polymer in the graft copolymer is 0.15 to 0. It is important to be in the range of 0.40 μm, preferably 0.20 to 0.35 μm. The weight average particle diameter of the graft copolymer is 0.1
If it is less than 5 μm, the resulting ABS resin is inferior in impact resistance and moldability (fluidity). On the other hand, if it exceeds 0.40 μm, the moldability is good, but the impact resistance and molding appearance (surface) are low. (Gloss) becomes worse.

The distribution of the dispersed particle size of the rubber-like polymer is not particularly limited, and two or more rubber-like polymers having different dispersed particle sizes may be used in combination.

The particle size of the rubber-like polymer can be adjusted by polymerization, but the following method, for example, enlargement of the rubber-like polymer by agglomeration during polymerization,
A method of preliminarily producing a relatively small rubber-like polymer having a size of 0.1 μm or less, and enlarging it by shear stress due to acid, salt, stirring, etc., a copolymer latex containing an acid group into a rubber-like polymer latex A method of adding, etc. can be used.

The graft copolymer constituting the ABS resin of the present invention can be produced by known graft polymerization. As the method of graft polymerization, emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination of two or more thereof can be used, but since the rubber-like polymer is easily produced by emulsion polymerization, emulsion polymerization Is the best. For example, a monomer mixture is added to the rubbery polymer obtained by emulsion polymerization, and graft polymerization is carried out by a known method.

The monomer mixture used in the graft polymerization is 10 to 40% by weight of vinyl cyanide-based monomer, 60 to 90% by weight of aromatic vinyl-based monomer, and at least one copolymerizable with these. It is a monomer mixture consisting of 0 to 20% by weight of another vinyl monomer (total 100% by weight).

Acrylonitrile, methacrylonitrile, vinylidene cyanide, and the like can be used as the vinyl cyanide-based monomer used in the graft polymerization, and acrylonitrile is preferable as the raw material of the ABS resin.

The amount of the vinyl cyanide-based monomer used is 10 to 40% by weight, preferably 15 to 35% by weight in the graft-polymerized monomer mixture. If it is less than 10% by weight, the impact resistance of the obtained ABS resin is low, and if it exceeds 40% by weight, the fluidity of the obtained ABS resin is lowered.

Examples of the aromatic vinyl monomer used in the graft polymerization include vinyltoluenes such as styrene, α-methylstyrene and p-methylstyrene, halogenated styrenes such as p-chlorostyrene and p-. t-Butylstyrene, dimethylstyrene, vinylnaphthalene, etc. can be used, and styrene or α-methylstyrene is preferable as a raw material for the ABS resin. These aromatic vinyl monomers can be used alone or in combination of two or more.

The amount of the aromatic vinyl monomer used is 60 to 90% by weight, preferably 65 to 85% by weight in the grafted monomer mixture. If it is less than 60% by weight, the fluidity of the resin is lowered, and if it exceeds 90% by weight, the impact resistance of the resin is lowered.

Other copolymerizable vinyl-based monomers used for graft polymerization include unsaturated carboxylic acid ester-based monomers, unsaturated dicarboxylic acid anhydrides and unsaturated dicarboxylic acid imide compounds. These are one kind,
Alternatively, two or more kinds can be used in combination.

Examples of the unsaturated carboxylic acid ester-based monomer which can be used in the graft polymerization include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, Examples thereof include methyl methacrylate and ethyl methacrylate. These unsaturated carboxylic acid ester monomers can be used alone or in combination of two or more.

Examples of unsaturated dicarboxylic acid anhydrides that can be used in the graft polymerization include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. Maleic anhydride is preferred.

Further, examples of the imide compound of unsaturated dicarboxylic acid that can be used in the graft polymerization include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like. Preferred is N-phenylmaleimide.

The amount of these other copolymerizable monomers used is 0 to 2 in the monomer mixture used for graft polymerization.
It is in the range of 0% by weight, and if the amount used exceeds 20% by weight, the impact resistance of the resin will be reduced.

In the present invention, if necessary, 20% by weight or less of other monomers such as glycidyl methacrylate, methacrylic acid, acrylic acid, methacrylamide, 2-hydroxyethyl methacrylate, polyethylene glycol monomethacrylate, It is also possible to use an amount of preferably 15% by weight or less in the monomer mixture.

The proportion of the monomer mixture grafted to the rubber-like polymer is 95 to 30 parts by weight, preferably 10 to 70 parts by weight of the rubber-like polymer, relative to 5 to 70 parts by weight of the rubber-like polymer. It is in the range of 90 to 30 parts by weight (total 100 parts by weight) with respect to parts by weight. If the amount of the rubber-like polymer is less than 5 parts by weight, the impact resistance of the obtained ABS resin will be deteriorated, and if it exceeds 70 parts by weight, the graft ratio to the rubber-like polymer will be low. Even if the amount of the rubber-like polymer in the obtained ABS resin is increased, the impact resistance and the gloss are deteriorated.

When the monomer mixture is graft-polymerized to the rubber-like polymer, the monomer mixture may be added all at once, or may be added in portions or continuously, and the addition method is not particularly limited. Absent.

In the emulsion graft polymerization, generally known emulsifiers, catalysts and initiators are used, and the kind, addition amount and addition method thereof are not particularly limited.

The graft copolymer thus obtained is recovered as a powdery solid by the steps of coagulation and drying with an acid or salt, which is a usual method for recovering a polymer from latex.

It is important that the graft ratio in the graft copolymer of the present invention is in the range of 15 to 100%,
It is preferably 20 to 80%. If the graft ratio is less than 15%, the resulting ABS resin will have poor impact resistance and appearance, while if the graft ratio exceeds 100%, the ABS resin will have poor fluidity.

The graft ratio as used in the present invention means that 2.5 g of the dry powdery graft copolymer is added to 60 m of acetone.
After heating for 3 hours at 55 ° C., the insoluble matter was separated by a centrifuge, dried to measure the weight of the insoluble matter,
It means the value calculated by the following formula (III).

Graft ratio (%) = [(S ₂ −S ₁ ) / S ₁ ] × 100 (III)

However, in the above formula (III), S ₁ represents the weight of the rubber-like polymer in the graft copolymer, and S ₂ represents the weight of the acetone-insoluble component.

The graft copolymer obtained according to the present invention can be used alone as the ABS resin, but can also be used in combination with other thermoplastic resins depending on the purpose. Examples of the other thermoplastic resin include polystyrene, acrylonitrile-styrene copolymer, styrene-maleic anhydride copolymer, acrylonitrile-styrene-maleimide compound terpolymer, acrylonitrile-α-methylstyrene copolymer. , Polymethylmethacrylate, polyvinyl chloride, polycarbonate, polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyamides.

The mixing ratio of the ABS resin and the above-mentioned thermoplastic resin is not particularly limited, but the ABS resin 5-10.
0 to 0 parts by weight of thermoplastic resin 95 to 0 parts by weight (total 1
00 parts by weight) and the blending amount of the thermoplastic resin is 9
If it exceeds 5 parts by weight, the content of the rubber-like polymer in the resin composition will decrease, and the impact resistance of the resulting resin will decrease.

The ABS resin of the present invention may be added with various stabilizers, plasticizers, lubricants, metal soaps, antistatic agents and the like which are usually used. For the mixing of these, a Henschel mixer or a Banbury mixer is used. A device such as an extruder, a heating roll, or the like is used, and a useful molded product can be obtained by various molding methods such as injection molding and extrusion molding.

[0049]

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition,% and parts in the following examples are based on parts by weight unless otherwise specified. In addition, various physical properties in the following Examples and Comparative Examples were measured by the following methods.

(1) Weight average particle diameter of rubber-like polymer The weight average particle diameter was determined using a transmission electron microscope.

(2) Weight average molecular weight of toluene-soluble component It was measured by the above-mentioned method.

(3) Gel content It was measured by the method described above.

(4) Swelling degree It was measured by the method described above.

(5) Graft ratio Measured by the method described above.

(6) Izod impact strength; ASTM D
It measured based on 256.

(7) Melt flow rate; JIS K7
According to No. 210, measurement was carried out under the conditions of a temperature of 200 ° C. and a load of 5 kg, and the outflow rate per 10 minutes was expressed in g.

(8) Flexural modulus; measured according to ASTM D790.

(9) Surface gloss; measured according to ASTM D523.

Example 1 (1) Production of Rubbery Polymer Latex (A-1) 2300 parts of deionized water (hereinafter simply referred to as water) and potassium rosinate were placed in a 10-liter stainless steel autoclave. 16.0 parts, potassium oleate 16.0
Parts, sodium hydroxide 1.0 part, mirabilite 8.0 parts and t
After charging 4.8 parts of dodecyl mercaptan and substituting with nitrogen, 2000 parts of 1,3-butadiene were charged and the temperature was 60 ° C.
The temperature was raised to. Then, 4.8 parts of potassium persulfate was added to 10 parts of water.
Polymerization was initiated by pressing in an aqueous solution dissolved in 0 part. During the polymerization, the polymerization temperature was controlled at 65 ° C., and after the polymerization for 12 hours, the unreacted butadiene was recovered when the internal pressure reached 4.5 kg / cm ² (gauge pressure). After that, the internal temperature was kept at 80 ° C. and kept for 1 hour to obtain a rubber-like polymer latex (A-1). The weight average particle diameter was 0.08 μm, the solid content was 41.0%, and the polymerization conversion rate was 81.2%.
The weight average molecular weight of the toluene-soluble component was 157,000
The gel content was 0, the gel content was 75%, and the swelling degree was 41.

(2) Acid group-containing copolymer latex (B-
Preparation of 1) A 5 liter glass reactor was charged with 3000 parts of water, 30 parts of potassium oleate, 15 parts of sodium dioctylsulfosuccinate and 4.5 parts of sodium formaldehyde sulfoxylate and heated to 60 ° C. From that point, after a mixture consisting of 1275 parts of n-butyl acrylate, 225 parts of methacrylic acid and 6.0 parts of cumene hydroperoxide was continuously added dropwise over 120 minutes,
After further aging for 2 hours, an acid group-containing copolymer latex (B-1) having a polymerization conversion rate of 98% and a weight average particle diameter of 0.08 μm was obtained.

(3) Rubber-like polymer latex (A-2)
Manufacture of the above rubber-like polymer latex (A-1) 2489 parts (as rubber-like polymer 1
000 parts), and then, with stirring, 61 parts of the above acid group-containing copolymer latex (B-1) (20 parts as solid content).
Part) and subsequently stirred for 30 minutes to obtain an enlarged rubber-like polymer latex (A-2) having a weight average particle diameter of 0.28 μm and a solid content of 40.7%.

(4) Production of Graft Copolymer (C-1) In a 5 liter glass reactor, 1500 parts of water and 2500 parts of the above rubber-like polymer latex (A-2) (as a rubber-like polymer) 1000 parts), 6.0 parts of Dextrose,
1.0 part of sodium pyrophosphate and 0.1 part of ferrous sulfate heptahydrate were charged, and after nitrogen substitution, the temperature was raised to 60 ° C., 300 parts of acrylonitrile, 700 parts of styrene, 12.0 parts of t-dodecyl mercaptan and A monomer mixture consisting of 3.0 parts of cumene hydroperoxide was added dropwise over 200 minutes, during which the internal temperature was controlled so as to be 65 ° C.

After the completion of the dropping, 1.2 parts of cumene hydroperoxide was added, and the mixture was further maintained at 70 ° C. for 1 hour to prepare an antioxidant (Antage W-40 manufactured by Kawaguchi Chemical Industry Co., Ltd.).
0) 10 parts were added and then cooled. This graft copolymer latex (C-1) is coagulated with a 5% sulfuric acid aqueous solution,
It is washed and dried to obtain a milky white powder graft copolymer (C-
1) 1930 parts were obtained. The polymerization conversion rate was 97% and the graft rate was 46%.

Then, the graft copolymer (C-1)
37 parts and AS resin (acrylonitrile (AN) -styrene (ST) copolymer, AN / ST weight ratio = 30/7
0, melt flow rate (3.6 g / 10 min) 63 parts at 200 ° C. by using a twin-screw extruder, and after pelletizing, each test piece was prepared by injection molding to evaluate physical properties. did. The results obtained are shown in Table 1.

[Example 2] (1) Production of rubber-like polymer latex (A-3) A 10-liter stainless steel autoclave was charged with water 23.
00 parts, 40 parts of potassium oleate, 8.0 parts of sodium hydrogencarbonate and 3.2 parts of sodium formaldehyde sulfoxylate (Rongalit) were charged and, after nitrogen substitution, 1440 parts of 1,3-butadiene and 1 part of styrene.
60 parts, t-dodecyl mercaptan 2.4 parts and diisopropylbenzene hydroperoxide 3.2 parts were charged. Then, an aqueous solution prepared by dissolving 0.072 part of disodium ethylenediaminetetraacetate and 0.025 part of ferrous sulfate heptahydrate in 100 parts of water was added at an internal temperature of 5 ° C to initiate polymerization. After the polymerization for 18 hours, when the pressure in the reactor became 0.5 kg / cm ² or less (gauge pressure),
Unreacted butadiene was removed to obtain a rubber-like polymer latex (A-3). The weight average particle diameter was 0.07 μm, the solid content was 39.2%, and the polymerization conversion rate was 94.6%.
The weight average molecular weight of the toluene-soluble component is 593,00.
0, the gel content was 82%, and the swelling degree was 28.

(2) Rubber-like polymer latex (A-4)
Production of rubber-like polymer latex (A-
In the production of 2), the rubber-like polymer latex (A-1) used is the above-mentioned rubber-like polymer latex (A-3).
In the same manner as in Example 1 (3), except that the above was changed to, an enlarged rubber-like polymer latex (A-4) having a weight average particle diameter of 0.27 μm and a solid content of 39.0% was obtained. It was

(3) Production of Graft Copolymer (C-2) The rubbery polymer latex (A- used in the production of the graft copolymer (C-1) described in Example 1 (4).
A graft copolymer (C-2) was obtained in the same manner as in Example 1 (4) except that 2) was changed to the above rubbery polymer latex (A-4). The polymerization conversion rate was 96% and the graft rate was 48%.

Then, the graft copolymer (C-2)
After 37 parts and 63 parts of the AS resin of Example 1 were blended using an extruder in the same manner as in Example 1 to form pellets, each test piece was prepared with an injection molding machine to evaluate the physical properties. Table 1 shows the results.

[Example 3] (1) Production of rubber-like polymer latex (A-5) In a 10-liter stainless steel autoclave, water 39 was added.
00 parts, sodium hydroxide 0.2 parts, higher fatty acid sodium 40 parts, dextrose 4.0 parts and anhydrous sodium sulfate 4.0 parts were charged, and after nitrogen substitution, 1,3-
2000 parts of butadiene, t-dodecyl mercaptan 2.
Of the monomer mixture consisting of 0 part and 4.0 parts of diisopropylbenzene hydroperoxide, first 6
After charging 70 parts, the temperature was raised, and an aqueous solution in which 6.0 parts of sodium pyrophosphate and 0.04 part of ferrous sulfate heptahydrate were dissolved in 100 parts of water at an internal temperature of 35 ° C. was injected to initiate polymerization. . After 1 hour from the start of the reaction, the remaining 1336 parts of the monomer mixture was added dropwise over about 6 hours, while controlling the internal temperature of the reactor to 40 ° C. After polymerization for 16 hours, when the internal pressure became 0.5 kg / cm ² (gauge pressure) or less, unreacted butadiene was removed to obtain a rubber-like polymer latex (A-5). The weight average particle diameter is 0.
10 μm, solid content 33.5%, polymerization conversion 98.6.
%Met. The weight average molecular weight of the toluene-soluble component was 272,000, the gel content was 92%, and the swelling degree was 19.

(2) Rubber-like polymer latex (A-6)
Production of 3100 parts of the above rubber-like polymer latex (A-5) in a 5 liter glass reactor (1 as rubber-like polymer)
000 parts) and 3.0 g parts of sodium dodecylbenzenesulfonate are charged, and a 5% phosphoric acid aqueous solution 800 is added thereto.
Parts were added dropwise over 3 minutes, and 200 parts of 10% aqueous sodium hydroxide solution was added immediately after the completion of the addition to obtain a solid content of 26.4.
%, The enlarged rubber-like polymer latex (A-6) having a weight average particle diameter of 0.26 μm was obtained.

(3) Production of Graft Copolymer (C-3) The rubbery polymer latex (A- used in the production of the graft copolymer (C-1) described in Example 1 (4).
A graft copolymer (C-3) was obtained in the same manner as in Example 1 (4) except that 2) was changed to the above rubbery polymer latex (A-6). The polymerization conversion rate was 95% and the graft rate was 42%.

Then, the graft copolymer (C-3)
After 37 parts and 63 parts of the AS resin of Example 1 were blended using an extruder in the same manner as in Example 1 to form pellets, each test piece was prepared with an injection molding machine to evaluate the physical properties. Table 1 shows the results.

Example 4 (1) Production of rubber-like polymer (A-7) The rubber-like polymer latex (A-) described in Example 3 (1).
In the production of 5), the amount of 1,3-butadiene used is 20
Example 3 (1) except that the amount of 00 parts was changed to 1000 parts of 1,3-butadiene and 1000 parts of n-butyl acrylate.
Polymerization was performed in the same manner as above (however, the polymerization time was 14 hours) to obtain a rubber-like polymer latex (A-7). The weight average particle diameter was 0.08 μm, the solid content was 33.1%, and the polymerization conversion rate was 96.9%. The weight average molecular weight of the toluene-soluble component is 298,000, the gel content is 92%,
The swelling degree was 19.

(2) Rubber-like polymer latex (A-8)
Production of rubber-like polymer latex (A-
2) Rubber-like polymer latex (A) used in the production of
-1) 2489 parts were changed to the above rubber-like polymer latex (A-7) 3050 parts, and the solid content was 33.0% and the weight average particle diameter was 0 in the same manner as in Example 1 (3). ．
An enlarged rubber-like polymer latex (A-8) having a size of 27 μm was obtained.

(3) Preparation of Graft Copolymer (C-4) The rubber-like polymer latex (C-) used in the preparation of the graft copolymer (C-1) described in Example 1 (4).
A graft copolymer (C-4) was obtained in the same manner as in Example 1 (4) except that 2) was changed to the above rubbery polymer latex (A-8). The polymerization conversion rate was 98% and the graft rate was 39%.

Then, the graft copolymer (C-4)
After 37 parts and 63 parts of the AS resin of Example 1 were blended using an extruder in the same manner as in Example 1 to form pellets, each test piece was prepared with an injection molding machine to evaluate the physical properties. Table 1 shows the results.

Example 5 (1) Production of acid group-containing copolymer latex (B-2) In a 5 liter glass reactor, 3000 parts of water, 25 parts of potassium oleate, 38 parts of sodium dioctylsulfosuccinate were added. And 4.5 parts of sodium formaldehyde sulfoxylate were charged and the temperature was raised to 60 ° C., and from that point, a mixture of 1328 parts of n-butyl acrylate, 173 parts of methacrylic acid and 8.0 parts of cumene hydroperoxide was added. After dripping continuously for 120 minutes,
After further aging for 2 hours, an acid group-containing copolymer latex (B-2) having a polymerization conversion rate of 99% and a weight average particle diameter of 0.05 μm was obtained.

(2) Acid group-containing copolymer latex (B-
Preparation of 3) A 5 liter glass reactor was charged with 3000 parts of water, 35 parts of potassium oleate, 38 parts of sodium dioctylsulfosuccinate and 4.5 parts of sodium formaldehyde sulfoxylate and heated to 60 ° C. From that point, a mixture of 1260 parts of n-butyl acrylate, 240 parts of methacrylic acid and 8.0 parts of cumene hydroperoxide was continuously added dropwise over 120 minutes,
After further aging for 2 hours, an acid group-containing copolymer latex (B-3) having a polymerization conversion rate of 98% and a weight average particle diameter of 0.10 μm was obtained.

(3) Rubber-like polymer latex (A-9)
Production of rubber-like polymer latex (A-
In the production of 2), an acid group-containing copolymer latex (B
The amount of 61-1 used was changed to 40.6 parts of the acid group-containing copolymer latex (B-2) and 20.4 parts of the acid group-containing copolymer latex (B-3). Otherwise in the same manner as in Example 1 (3), an enlarged rubber-like polymer latex (A-9) having a solid content of 40% and a weight-average particle diameter of 0.35 μm and 0.21 μm of two dispersants. Got

(4) Production of Graft Copolymer (C-5) The rubbery polymer latex (A- used in the production of the graft copolymer (C-1) described in Example 1 (4).
A graft copolymer (C-5) was obtained in the same manner as in Example 1 (4) except that 2) was changed to the above rubbery polymer latex (A-9). The polymerization conversion rate was 98% and the graft rate was 48%.

Then, the graft copolymer (C-5)
After 37 parts and 63 parts of the AS resin of Example 1 were blended using an extruder in the same manner as in Example 1 to form pellets, each test piece was prepared with an injection molding machine to evaluate the physical properties. Table 1 shows the results.

Example 6 (1) Production of Rubber Copolymer Latex (A-10) In a 10-liter stainless steel autoclave, 30 parts of water was added.
00 parts, potassium rosinate 40 parts, potassium hydroxide 2.
0 parts, Glauber's salt 6.0 parts, t-dodecyl mercaptan 4.0
Parts, 6.0 parts of potassium persulfate and 2000 parts of 1,3-butadiene were charged and polymerization was initiated at 50 ° C. Furthermore, the reaction temperature is raised according to the polymerization conversion rate, and finally 70 ° C.
Polymerization was carried out for 75 hours to remove unreacted butadiene to obtain a rubber-like polymer latex (A-10). The solid content was 37.5%, the polymerization conversion rate was 87.9%, and the weight average particle diameter was 0.28 μm. In addition, the molecular weight of the toluene-soluble component is 218,000, the gel content is 82%, and the swelling degree is 2.
It was 3.

(2) Production of Graft Copolymer (C-6) The rubbery polymer latex (A- used in the production of the graft copolymer (C-1) described in Example 1 (4).
A graft copolymer (C-6) was obtained in the same manner as in Example 1 (4) except that 2) was changed to the above rubbery polymer latex (A-10). The polymerization conversion rate was 97% and the graft rate was 41%.

Then, the graft copolymer (C-6)
After 37 parts and 63 parts of the AS resin of Example 1 were blended using an extruder in the same manner as in Example 1 to form pellets, each test piece was prepared with an injection molding machine to evaluate the physical properties. Table 1 shows the results.

Comparative Example 1 (1) Production of Rubber-like Polymer Latex (A-11) The rubber-like polymer latex (A-) described in Example 1 (1).
In the production of 1), polymerization was performed in the same manner as in Example 1 (1) except that the amount of t-dodecyl mercaptan was changed from 4.8 parts to 9.6 parts (however, the polymerization time was 14 hours), and the rubber was obtained. Polymer latex (A-11) was obtained. The weight average particle diameter was 0.08 μm, the solid content was 40.7%, and the polymerization conversion rate was 80.3. The molecular weight of the toluene-soluble component was 87,000, the gel content was 70%, and the degree of swelling was 4
It was 1.

(2) Rubber-like polymer latex (A-1
2) Production The rubber-like polymer latex (A- described in Example 1 (3).
In the production of 2), a rubber-like polymer latex (A-
1) was changed to the above rubbery polymer latex (A-11), and the solid content was 40.
An enlarged rubbery polymer latex (A-12) having 5% and a weight average particle diameter of 0.29 μm was obtained.

(3) Production of Graft Copolymer (C-7) In the production of graft copolymer (C-1) described in Example 1 (4), rubber-like polymer latex (A-2) was used. The procedure of Example 1 (4) was repeated except that the above rubber-like polymer latex (A-12) was used.
-7) was obtained. Polymerization conversion rate is 96%, graft rate is 4
5%.

Then, the graft copolymer (C-7)
After 37 parts and 63 parts of the AS resin of Example 1 were blended using an extruder in the same manner as in Example 1 to form pellets, each test piece was prepared with an injection molding machine to evaluate the physical properties. The results are shown in Table 2.

Comparative Example 2 (1) Production of Rubber-like Polymer Latex (A-13) The rubber-like polymer latex (A-) described in Example 1 (1).
In the production of 1), polymerization was carried out in the same manner as in Example 1 (1) except that the polymerization end time was changed to 10 hours to obtain a rubber-like polymer latex (A-13). 35.5 solids
%, The polymerization conversion rate is 63.9%, the weight average particle size is 0.0
It was 7 μm. The weight average molecular weight of the toluene-soluble component was 159,000, the gel content was 35%, and the swelling degree was 6%.
It was 4.

(2) Rubber-like polymer latex (A-1
4) Production of rubbery polymer latex (A-) described in Example 1 (3)
In the production of 2), a rubber-like polymer latex (A-
Polymerization was performed in the same manner as in Example 1 (3) except that 1) was changed to the above rubbery polymer latex (A-13), the solid content was 63.7%, and the weight average particle diameter was 0.29 μm. The enlarged rubbery polymer latex (A-14) was obtained.

(3) Production of Graft Copolymer (C-8) In the production of the graft copolymer (C-1) described in Example 1 (4), the rubber-like polymer latex (A-2) was used. The graft copolymer (C) was prepared in the same manner as in Example 1 (4) except that the above rubbery polymer latex (A-14) was used.
-8) was obtained. Polymerization conversion rate is 97%, graft rate is 4
7%.

Then, the graft copolymer (C-8)
After 37 parts and 63 parts of the AS resin of Example 1 were blended using an extruder in the same manner as in Example 1 to form pellets, each test piece was prepared with an injection molding machine to evaluate the physical properties. The results are shown in Table 2.

Comparative Example 3 (1) Production of Rubber-like Polymer Latex (A-15) The rubber-like polymer latex (A-) described in Example 1 (1).
In the production of 1), the amount of 1,3-butadiene used was 2
Changed from 000 parts to 1600 parts and set polymerization end time to 18
Polymerization was performed in the same manner as in Example 1 (1) except that the time was used to obtain a rubber-like polymer latex (A-15). The solid content was 40.1%, the polymerization conversion rate was 98.3%, and the weight average particle diameter was 0.08 μm. Further, the weight average molecular weight of the toluene-soluble component was 159,000, and the gel content was 94.
%, And the swelling degree was 12.

(2) Rubber-like polymer latex (A-1
Production of 6) The rubber-like polymer latex (A- described in Example 1 (3).
In the production of 2), a rubber-like polymer latex (A-
The solid content was 3 in the same manner as in Example 1 (3) except that 1) was changed to the above rubbery polymer latex (A-15).
An enlarged rubbery polymer latex (A-16) having a weight average particle diameter of 9.9% and a weight average particle diameter of 0.29 μm was obtained.

(3) Production of Graft Copolymer (C-9) In the production of graft copolymer (C-1) described in Example 1 (4), rubber-like polymer latex (A-2) was used. The procedure of Example 1 (4) was repeated except that the rubber-like polymer latex (A-16) was changed to the graft copolymer (C).
-9) was obtained. Polymerization conversion rate is 97%, graft rate is 4
It was 1%.

Then, the graft copolymer (C-9)
After 37 parts and 63 parts of the AS resin of Example 1 were blended using an extruder in the same manner as in Example 1 to form pellets, each test piece was prepared with an injection molding machine to evaluate the physical properties. The results are shown in Table 2.

Comparative Example 4 (1) Production of Rubber-like Polymer Latex (A-17) The rubber-like polymer latex (A-) described in Example 1 (1).
In the production of 1), polymerization was carried out in the same manner as in Example 1 (1) except that the amount of t-dodecyl mercaptan used was changed to no addition (polymerization time: 12 hours) to give a rubber-like polymer latex (A-17). ) Got. Weight average particle diameter is 0.07μ
m, the solid content was 41.0%, and the polymerization conversion rate was 81.3%. The weight average molecular weight of the toluene-soluble component is 12
The gel content was 3,000, the gel content was 98%, and the swelling degree was 10.

(2) Rubber-like polymer latex (A-1
8) Production of rubber-like polymer latex (A-) described in Example 1 (3)
In the production of 2), a rubber-like polymer latex (A-
The solid content was 4 in the same manner as in Example 1 (3) except that 1) was changed to the above rubbery polymer latex (A-17).
An enlarged rubber-like polymer latex (A-18) having a weight average particle diameter of 0.8% and 0.25 μm was obtained.

(3) Production of Graft Copolymer (C-10) In the production of graft copolymer (C-1) described in Example 1 (4), rubber-like polymer latex (A-2) was used. The graft copolymer (C) was prepared in the same manner as in Example 1 (4) except that the above rubber-like polymer latex (A-18) was used.
-10) was obtained. The polymerization conversion rate was 96% and the graft rate was 38%.

Next, the graft copolymer (C-10)
After 37 parts and 63 parts of the AS resin of Example 1 were blended using an extruder in the same manner as in Example 1 to form pellets, each test piece was prepared with an injection molding machine to evaluate the physical properties. The results are shown in Table 2.

Comparative Example 5 (1) Production of Graft Copolymer (C-11) In the production of the graft copolymer (C-1) described in Example 1 (4), a rubber-like polymer latex ( Graft copolymer (C-) was obtained in the same manner as in Example 1 (4) except that the rubber polymer latex (A-1) was used instead of A-2).
11) was obtained. Polymerization conversion rate is 98%, graft rate is 5
4%.

Next, the graft copolymer (C-11)
After 37 parts and 63 parts of the AS resin of Example 1 were blended using an extruder in the same manner as in Example 1 to form pellets, each test piece was prepared with an injection molding machine to evaluate the physical properties. The results are shown in Table 2.

Comparative Example 6 (1) Production of Acid Group-Containing Copolymer Latex (B-4) In a 5 liter glass reactor, 3000 parts of water, 33 parts of potassium oleate and 32 parts of sodium dioctylsulfosuccinate were added. And 4.5 parts of sodium formaldehyde sulfoxylate were charged and the temperature was raised to 60 ° C., from which point a mixture of 1150 parts of n-butyl acrylate, 350 parts of methacrylic acid and 6.0 parts of cumene hydroperoxide was added. After dripping continuously for 120 minutes,
After further aging for 2 hours, an acid group-containing copolymer latex (B-4) having a polymerization conversion rate of 98% and a weight average particle diameter of 0.15 μm was obtained.

(2) Rubber-like polymer latex (A-1
9) Production of rubber-like polymer latex (A-) described in Example 1 (3)
In the production of 2), the acid group-containing polymer latex (B-1) used is the above acid group-containing copolymer latex (B-
The same procedure as in Example 1 (3) except that the procedure was changed to 4), and the enlarged rubber-like polymer latex (A-19) had a solid content of 40.7% and a weight average particle diameter of 0.52 μm. Got

(3) Production of Graft Copolymer (C-12) In the production of graft copolymer (C-1) described in Example 1 (4), rubbery polymer latex (A-2) was used. The graft copolymer (C) was prepared in the same manner as in Example 1 (4) except that the rubber polymer latex (A-19) was used.
-12) was obtained. The polymerization conversion rate was 96% and the graft rate was 37%.

Next, the graft copolymer (C-12)
After 37 parts and 63 parts of the AS resin of Example 1 were blended using an extruder in the same manner as in Example 1 to form pellets, each test piece was prepared with an injection molding machine to evaluate the physical properties. The results are shown in Table 2.

[Comparative Example 7] 50 parts of the graft copolymer (C-7) of Comparative Example 1 and 50 parts of the AS resin of Example 1 were blended using an extruder in the same manner as in Example 1, and pelletized. After that, each test piece was prepared with an injection molding machine to evaluate the physical properties. The results are shown in Table 2.

[0108]

[Table 1]

[0109]

[Table 2]

As is clear from the results shown in Tables 1 and 2, the ABS which does not satisfy the constituent requirements defined by the present invention.
Resins are inferior in some properties, especially in impact resistance of molded products. On the other hand, it can be seen that the ABS resin according to the present invention is particularly excellent in the impact resistance, surface gloss and fluidity of the molded product.

[0111]

The ABS resin composition of the present invention can be molded into various shapes by molding methods such as injection molding and extrusion molding, and has impact resistance, fluidity and molding appearance (surface gloss). Since they are both excellent, they are useful as electric, electronic parts, automobiles, household products, and other industrial materials.

Claims (3)

[Claims] 1. An aliphatic conjugated diene-based monomer 30 to 100
70 parts by weight of at least one other copolymerizable monomer selected from the group consisting of vinyl cyanide-based monomers, aromatic vinyl-based monomers and unsaturated carboxylic acid ester-based monomers. A rubber-like polymer obtained by polymerizing 0 parts by weight (total 100 parts by weight), wherein the weight average molecular weight of the toluene-soluble component is 100,000 or more, and the gel content is 40% by weight.
As described above, the rubber-like polymer having a swelling degree of 15 to 50. 2. In the presence of 5 to 70 parts by weight of the rubber-like polymer according to claim 1, 10 to 40% by weight of vinyl cyanide monomer, 60 to 90% by weight of aromatic vinyl monomer, and At least one other vinyl-based monomer copolymerizable with these
It comprises a graft copolymer obtained by polymerizing 95 to 30 parts by weight of a monomer mixture consisting of 0 to 20% by weight of seed (total 100% by weight), and the weight average of the rubber-like polymer in the graft copolymer. An ABS resin having a particle diameter of 0.15 to 0.40 μm and a graft ratio of 15 to 100%. 3. In the presence of 5 to 70 parts by weight of the enlarged rubber-like polymer obtained by enlarging the rubber-like polymer according to claim 1, 10 to 40% by weight of a vinyl cyanide monomer and an aromatic vinyl are used. 95 to 30 parts by weight of a monomer mixture consisting of 60 to 90% by weight of the system monomers and at least one to 20% by weight (total 100% by weight) of at least one other vinyl monomer copolymerizable therewith. It is composed of a graft copolymer obtained by polymerization, and the weight average particle diameter of the enlarged rubber-like polymer in the graft copolymer is 0.15 to 0.40 μm, and the graft ratio is 15 to 100%. ABS resin characterized by the following.