JP3177151B2 - Method for producing rubber-like polymer latex, method for producing graft copolymer using the same, and ABS resin composition using graft copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a rubber latex for an ABS resin having excellent moldability, surface gloss, and impact resistance at ordinary temperature and low temperature, and a graft copolymer using the rubber latex. The present invention relates to a method for manufacturing a united product.

[0002]

2. Description of the Related Art ABS resins (acrylonitrile-butadiene-styrene resins) are obtained by graft-polymerizing a monomer mixture comprising a vinyl cyanide monomer and an aromatic vinyl monomer onto a rubbery polymer. It is widely used in the world because of its many characteristics such as high impact resistance, high surface gloss, and good fluidity.

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 the graft copolymerized on the rubber-like polymer and the thickness of the graft layer. Is generally well known. In particular, excellent impact resistance, which is a characteristic of ABS resin, is a property that greatly varies depending on these factors, and it is important to appropriately set these factors in order to obtain an ABS resin having excellent impact resistance. is there. From such a viewpoint, various studies have conventionally been made on a suitable rubbery polymer used for an ABS resin, and an ABS resin developed based on these findings has been widely used as an industrial material.

However, in recent years, the variety of uses and the shape of molded products have become increasingly diversified. Extremely strict performance is required, for example, color unevenness does not occur depending on the part of the molded product. With regard to impact resistance, when applied to exterior parts such as vehicles, not only impact resistance at room temperature but also impact resistance below freezing is required.

However, in general, the impact resistance and the appearance of the resin tend to contradict each other, and the content of the rubber-like polymer is increased or the rubber-like polymer is increased in order to exhibit the impact resistance of the ABS resin. It is known that when the average dispersed particle size is increased, the glossiness and the coloring property are deteriorated.

In order to overcome these conflicting conditions and achieve both impact resistance and excellent resin appearance, attempts have been made to improve rubbery polymers and graft copolymers. For example, a method of combining two or more kinds of rubbery polymers having different particle diameters (JP-A-52-141859, JP-A-54-133588, JP-A-57-2780)
3652, JP-A-59-202211) and a method for specifying the gel content and composition of a rubber-like polymer (JP-A-53-202).
No. 572933, JP-A-59-184244 and JP-A-62-84109), all of which require the presence of a relatively large rubber-like polymer, which results in an effect of improving the appearance. Is insufficient, and the impact resistance at low temperatures is also insufficient.

[0007]

[Problems that the Invention is to Solve Thus, an object of the present invention uses a resin Appearance (surface gloss) and ABS resin having improved impact resistance at ordinary temperature and low temperature are conflicting conditions
For producing graft copolymers and rubbers used therefor
An object of the present invention is to provide a method for producing latex .

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a method for improving the same, a polymerization conversion rate of 1 to 80% by weight during the production of a rubber-like polymer has been found.
The above-mentioned problem is solved by adding a monomer (mixture) having a low aliphatic conjugated diene monomer content in the above method and further using a method of forming a rubbery polymer having a specific particle size and a specific gel content. I found that it could be solved.

That is, the gist of the present invention is that 50 to 100% by weight of an aliphatic conjugated diene monomer, an aromatic vinyl monomer, an alkyl acrylate monomer and a vinyl cyanide monomer. Emulsion polymerization of 10 to 99 parts by weight of a monomer (mixture) (total 100% by weight) (F) consisting of 0 to 50% by weight of at least one type of monomer selected from a body, and a polymerization conversion rate of 1 to 80% by weight % (Polymerization conversion of the monomer (mixture) (F)), 0 to 99% by weight of the aliphatic conjugated diene monomer and the aromatic vinyl monomer and / or the alkyl acrylate ester Monomer 1
To 100% by weight of monomer (mixture) (total 100
% By weight) (S) 1 to 90 parts by weight of a monomer (mixture)
Content of aliphatic conjugated diene monomer in (F) (% by weight)
Under a condition higher than the content of the aliphatic conjugated diene-based monomer (% by weight) in the monomer (mixture) (S) (total 100 parts by weight of (F) + (S)), Further, polymerization was carried out, and in some cases, a bloating operation was carried out, and the weight average particle diameter was 0.15 to 0.40 μm and the gel content was 5%.
A method for producing a rubber-like polymer (A) latex, characterized by obtaining a rubber-like polymer (A) latex of 0 to 90% by weight, and a rubber-like polymer (A) latex 5 to 80% by weight obtained Parts (as solid content), 10 to 40% by weight of vinyl cyanide monomer, 60 to 90% by weight of aromatic vinyl monomer and other vinyl monomers copolymerizable therewith. There is a method in which 20 to 95 parts by weight of a monomer mixture composed of 0 to 20% by weight (total 100% by weight) is polymerized to produce a graft copolymer (B) having a graft ratio of 20 to 100% by weight .

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

The aliphatic conjugated diene-based monomer which can be used for producing the rubbery polymer (A) latex includes:
Although 1,3-butadiene, isoprene, chloroprene and the like can be used, 1,3-butadiene is preferred from the viewpoint of impact resistance.

As the aromatic vinyl monomer, styrene,
α-Methylstyrene, p-chlorostyrene, p-methylstyrene and the like can be used, and styrene is particularly preferred.

Examples of the alkyl acrylate monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate,
T-butyl, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, and the like can be used, and ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and the like are particularly preferable.

As the vinyl cyanide monomer, acrylonitrile, methacrylonitrile and the like can be used, and acrylonitrile is particularly preferable.

The content of the aliphatic conjugated diene monomer in the monomer mixture (F) is from 50 to 100% by weight, and when it is more than 50% by weight, the obtained ABS resin has excellent impact resistance. It is preferable because it has properties. Aromatic vinyl monomer,
The alkyl acrylate monomer and the vinyl cyanide monomer may each be used in an amount of 0 to 50 depending on the purpose.
Wt% can be used.

The monomer mixture (F) is a rubbery polymer (A)
It is used in an amount of 10 to 99 parts by weight per 100 parts by weight. 10
When used in an amount less than parts by weight, the resulting rubber-like polymer has a very high gel content, so that the impact resistance at normal temperature of the molded product obtained from the ABS resin composition tends to decrease. .

The content of the aliphatic conjugated diene monomer in the monomer mixture (S) is from 0 to 99% by weight. If it exceeds 99% by weight, the molded article obtained from the ABS resin composition tends to have poor impact resistance.

The monomer mixture (S) is a monomer mixture (F)
Is emulsion-polymerized, and is added at a polymerization conversion rate of 1 to 80% by weight (polymerization conversion rate of the monomer mixture (F)). When the polymerization conversion of the monomer mixture (F) is in the range of 1 to 80% by weight when the monomer mixture (S) is added, the obtained ABS resin composition has excellent low temperature. Impact resistance and a molded product free from fish eyes.

The method of adding the monomer mixture (S) may be any method such as a method of adding all at once, a method of dividingly adding in several times, and a method of continuously dropping over a long time.
It is important that the timing of starting the addition and the timing of terminating the addition fall within the range of the polymerization conversion of the monomer mixture (F) from 1 to 80% by weight.

This method for producing a rubber-like polymer has a high degree of freedom for producing a high-performance ABS resin composition because of easy control of the dispersion particle size and gel content of the rubber-like polymer. Therefore, emulsion polymerization is optimal.

The gel content of the rubbery polymer (A) is in the range of 50 to 90% by weight, preferably 60 to 85%.
% By weight. If the amount is less than 50% by weight, the impact resistance and surface gloss of the resin will be reduced, and if it exceeds 90% by weight, the impact resistance will tend to be reduced again.

The particle size of the rubbery polymer (A) latex should be 0.15 to 0.4 μm as a weight average particle size in order to obtain a resin having excellent impact resistance, fluidity and surface gloss. is important. If it is less than 0.15 μm, the surface gloss is good, but the impact resistance and the moldability tend to deteriorate. If it exceeds 0.4 μm, the moldability will be good, but the impact resistance and the surface gloss will tend to deteriorate. Thus, 0.15-0.
Any method may be used to obtain the rubber-like polymer having a size of 4 μm. For example, the rubber-like polymer (A) latex in the above range may be obtained by growing particles to obtain the rubber-like polymer by emulsion polymerization. Or a similar agglomeration during polymerization, or a relatively small rubbery polymer of less than 0.15 μm is prepared in advance, and this is used as a solvent, an acid, an electrolyte, a copolymer latex having an acid group, or the like. A method called so-called hypertrophy operation can be used, such as a method of increasing the particle size by adding iron or a method of mechanically destabilizing the particles to increase the particle size.

In the present invention, the graft copolymer (B)
Are 10 to 40% by weight of a vinyl cyanide monomer and 60 to 9 of an aromatic vinyl monomer in the presence of 5 to 80 parts by weight of the rubbery polymer (A) latex obtained by the above method.
It is obtained by graft polymerization of 20 to 95 parts by weight of a monomer mixture (total 100% by weight) consisting of 0% by weight and 0 to 20% by weight of another vinyl monomer copolymerizable therewith.

As the vinyl cyanide monomer used for the graft copolymer (B), acrylonitrile, methacrylonitrile, vinylidene cyanide and the like can be used, and acrylonitrile is preferred.

Examples of the aromatic vinyl monomer include vinyl toluenes such as styrene, α-methylstyrene and p-methylstyrene, halogenated styrenes such as p-chlorostyrene, pt-butylstyrene, dimethyl Styrene, vinylnaphthalenes and the like can be used, and styrene or α-methylstyrene is preferred. These aromatic vinyl monomers can be used alone or as a mixture of two or more.

Other vinyl monomers copolymerizable with the vinyl cyanide monomer or the aromatic vinyl monomer include, for example, methyl acrylate, ethyl acrylate, and n-acrylic acid. Alkyl acrylates such as butyl, 2-ethylhexyl acrylate, and n-hexyl acrylate; alkyl methacrylates such as methyl methacrylate and ethyl methacrylate; and similar alkyl crotonates and alkyl itaconates. Can be used. These vinyl monomers can be used alone or as a mixture of two or more.

The method for producing the graft copolymer (B) is not particularly limited, and emulsion polymerization, emulsion suspension polymerization, emulsion bulk polymerization,
Bulk polymerization and the like can be used, and among them, emulsion polymerization is optimal because of easy control of the structure.

At the time of the graft polymerization, known emulsifiers, catalysts and initiators are usually used, and the kind, amount and method of addition are completely arbitrary.

The amount of the vinyl cyanide monomer to be used is 10 to 100% by weight of the monomer mixture to be graft-polymerized.
It is 40% by weight, preferably 15 to 35% by weight. 10
When the amount is less than 40% by weight, the impact resistance of the resin is low, and when it exceeds 40% by weight, the surface gloss of the resin tends to decrease.

Further, the amount of the aromatic vinyl monomer used is limited by the amount of vinyl cyanide and other vinyl monomers to be copolymerized.

The other vinyl monomer is used in a range of 0 to 20% by weight in the monomer mixture. 20% by weight
It is not preferable that the ratio exceeds the range, since the impact resistance of the resin decreases.

The ratio of the rubbery polymer (A) latex and the monomer mixture to be graft-copolymerized with the rubbery polymer (A) latex is 5 to 80% by weight (as solid content), preferably 10 to 10% by weight. It is used so as to be about 70% by weight. If the amount is less than 5% by weight, the proportion of the rubbery polymer (A) in the resin is inevitably small, and the impact resistance of the resin is low, which is of no practical value. On the other hand, if it exceeds 80% by weight, the graft ratio is inevitably low, and the dispersion of the rubber-like polymer does not work well, and the fluidity and impact resistance of the resin deteriorate.

When graft-polymerizing the rubbery polymer (A) latex, the monomer mixture to be polymerized may be added all at once, or may be added dropwise or continuously, and the method of addition is particularly limited. There is no.

The graft copolymer (B) thus obtained needs to be adjusted so that the graft ratio is 20 to 100% by weight, preferably 25 to 80% by weight. Here, the graft ratio is a value expressed as a percentage of [(weight of monomer mixture graft-polymerized on rubber-like polymer (A)) / (weight of rubber-like polymer (A)) × 100]. In general, it can be calculated from the acetone-insoluble content of the graft polymer obtained after the graft polymerization.

When the graft ratio is less than 20% by weight, the impact resistance, surface gloss and fish eye of the resin are deteriorated,
If it exceeds 0% by weight, the fluidity of the resin will be greatly reduced.

The thus-obtained graft copolymer (B) can be recovered as a powdery solid by a coagulation with an acid or a salt, which is a usual method for recovering a polymer from a latex, and a drying step.

In the present invention, the following copolymer (C) is further added to the graft copolymer (B) to give ABS
It can be used as a system resin composition.

The copolymer (C) comprises 10 to 40% by weight of a vinyl cyanide monomer unit and 6 of an aromatic vinyl monomer unit.
0 to 90% by weight and 0 to 20% by weight of other vinyl monomer units copolymerizable therewith (total 100% by weight). Obtained by polymerizing a monomer mixture of a monomer and at least one other vinyl monomer copolymerizable therewith, a vinyl cyanide monomer, an aromatic vinyl monomer and As the other vinyl monomer copolymerizable with the above, the same vinyl monomers as those used for the graft copolymer (B) can be used.

As the copolymer (C), those obtained separately by the following method can be used, and those obtained when producing the above graft copolymer (B) can also be used. it can.

The method for producing the copolymer (C) includes the following:
Methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization can be used.

The proportion of the graft copolymer (B) and the copolymer (C) in the ABS resin composition of the present invention is as follows:
The amount of the copolymer (C) is in the range of 0 to 95 parts by weight (total 100 parts by weight) with respect to 5 to 100 parts by weight of the graft copolymer (B), and the blending amount of the copolymer (C) is 95 parts by weight. When the amount exceeds the part, the rubbery polymer (A) in the resin composition is inevitably contained.
, The impact resistance of the resulting resin composition is reduced, and is not of practical value.

In the ABS resin composition comprising the graft copolymer (B) and the copolymer (C) of the present invention,
If necessary, thermoplastic resins such as polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and polyamide, various known stabilizers and plasticizers, lubricants, metal soaps, antistatic agents, dyes, inorganic or organic particles, powders, or fibers Fillers, foaming agents, etc. can be added, and these devices are mixed using devices such as Banbury mixers, extruders, heating rolls, and various molding methods such as injection molding, extrusion molding, and blow molding. Thus, a useful molded article can be obtained.

[0043]

The present invention will be specifically described below with reference to examples. However, the following Examples and Comparative Examples are for more specifically explaining the present invention, and the present invention is not limited to the following examples unless it exceeds the gist thereof.

In the following examples,% and parts are by weight unless otherwise specified.

In the following examples and comparative examples,
Various physical properties were measured by the following methods.

(1) Average particle size of rubbery polymer: The size of 300 to 400 rubbery polymer particles was counted using a transmission electron microscope, and the weight average particle size was determined.

(2) Gel content: After the rubbery polymer was dried, 0.5 g of the rubbery polymer was added to 60 ml of toluene at 30 ° C.
After immersion for 8 hours, the mixture was filtered through a 100-mesh wire gauze, the insoluble matter was dried, and the insoluble matter weight% was measured.

(3) Graft ratio: 2.5 g of the dried powdery graft copolymer was dispersed in 60 ml of acetone.
After heating at 5 ° C. for 3 hours, insolubles were separated by centrifugation.
This was weighed after drying, the insoluble content weight% was measured, and the amount of the rubbery polymer in the insoluble content was determined and calculated by the above-mentioned formula.

(4) Izod impact strength; ASTM D
Measured in an atmosphere at 23 ° C. and −20 ° C. according to 256.

(5) Melt flow rate; JIS K7
The measurement was performed under the conditions of a temperature of 200 ° C. and a load of 5 kg in accordance with No. 210, and the result was indicated by the number of grams of outflow per 10 minutes.

(6) Surface gloss: measured in accordance with ASTM D523.

(Example 1) (1) Production of rubbery polymer (A-1) latex In a 10-liter SUS autoclave, distilled water (hereinafter abbreviated as water) 2,400 parts potassium oleate 12.8 parts tert -Dodecyl mercaptan 3.2 parts Sodium hydroxide 1.6 parts Potassium persulfate 5.6 parts are added, and after nitrogen substitution, as a monomer mixture (F), styrene 40.0 parts 1,3-butadiene 760.0 parts , And the temperature was raised to 60 ° C., and the polymerization was continued for 6 hours. From the point of the polymerization conversion rate of 35% by weight, as a monomer mixture (S), 680.0 parts of 1,3-butadiene and 120.0 parts of styrene were added over 6 hours, and after the addition was completed, the temperature was raised to 70 ° C. The polymerization was further continued for 12 hours to obtain a rubbery polymer (A-1) latex having a solid content of 39.5%, a polymerization conversion of 97%, a weight average particle diameter of 0.26 μm, and a gel content of 83%. .

(2) Production of graft copolymer (B-1) In a 5 liter glass reactor, 1,468 parts of water, 2,532 parts of rubbery polymer (A-1) latex, 2,532 parts (as a rubbery polymer) 1,000 parts) Dextrose 6.0 parts Sodium pyrophosphate decahydrate 1.0 part Ferrous sulfate heptahydrate 0.1 part was charged, and after purging with nitrogen, the temperature was raised to 60 ° C, acrylonitrile 300 parts Styrene 700 A mixture of 12.0 parts of tert-dodecyl mercaptan and 3.0 parts of cumene hydroperoxide was added dropwise over 200 minutes. At that time, the internal temperature was controlled to 65 ° C. After the addition, 1.2 parts of cumene hydroperoxide was added,
The mixture was kept at 0 ° C. for 1 hour, cooled after adding 10 parts of an antioxidant (Kawaguchi Chemical Industry Antage W-400). This latex was coagulated with a 0.5% aqueous sulfuric acid solution, washed and dried to obtain a milky white powder graft copolymer (B-1). The polymerization conversion was 96%, and the graft ratio of the graft copolymer (B-1) was 46%.

(3) Evaluation of ABS resin composition Graft copolymer (B-1) 3 thus obtained
7 parts and acrylonitrile (AN) produced by bulk polymerization
-Styrene (St) copolymer (E) (AN / ST weight ratio = 30/70, melt flow rate 3.6 [200 ° C,
10 kgf]) was compounded at 200 ° C. using a twin-screw extruder to form pellets, and then each test piece was prepared by injection molding and provided for each evaluation.

The results are as shown in Table 1.

[0056]

[Table 1]

Example 2 (1) Production of Small Particle Rubbery Polymer (D) Latex In a 10-liter SUS autoclave, deionized water (hereinafter simply referred to as water) 2,640 parts potassium rosinate 16. 0 parts Potassium oleate 16.0 parts Sodium hydroxide 3.2 parts Glucose 3.2 parts Anhydrous sodium sulfate 4.8 parts tert-Dodecyl mercaptan 4.8 parts Diisopropylbenzene hydroperoxide
After charging 3.2 parts, and after nitrogen substitution, 320 parts of 1,3-butadiene were charged as a monomer (F), and the temperature was raised to 50 ° C.

An aqueous solution consisting of 0.048 parts of ferrous sulfate heptahydrate, 1.6 parts of sodium pyrophosphate decahydrate, 8 parts of water, and 80.0 parts of water was injected into the kettle to initiate polymerization. 30 minutes after the start of polymerization, the temperature in the kettle was raised to 55 ° C.,
At 55 ° C. (at a polymerization conversion of 22% at this time), as a monomer mixture (S), 160 parts of styrene and 1,120 parts of butadiene were added simultaneously over 3 hours, and after 7 hours, the internal pressure was reduced to 0%. When the pressure reached 0.5 kg / cm ² (gauge pressure), unreacted butadiene was removed by steam distillation to obtain a rubbery polymer latex (D). Solid content 37.0%, polymerization conversion rate 97.5
%, An average particle diameter of 0.068 μm, and a gel content of 81%.

(2) Acid group-containing copolymer latex (E)
In a 5 liter glass reactor, water 3,000 parts Potassium oleate 30.0 parts Sodium dioctyl sulfosuccinate 35.0 parts Sodium formaldehyde sulfoxylate
4.5 parts were charged and the temperature was raised to 60 ° C. From that point, a mixture consisting of 1,275 parts of n-butyl acrylate, 225 parts of methacrylic acid and 6.0 parts of cumene hydroperoxide was continuously taken over 120 minutes. Was dropped. Further aging was carried out for 2 hours to obtain an acid group-containing copolymer latex (E) having a polymerization conversion of 98% and an average particle diameter of 0.08 μm.

(3) Preparation of rubbery polymer (A-2) latex In a 5 liter glass reactor, 2703 parts (1000 parts as solid content) of the above small particle rubbery polymer latex (D)
After adding 61 parts of an acid group-containing copolymer latex (E) (20 parts as a solid content) under stirring, the mixture was continuously stirred for 30 minutes to obtain an average particle diameter of 0.32 μm, a gel content of 81%, and a solid content of 36.9% of a rubbery polymer latex (A-2) was obtained.

(4) Production of Graft Copolymer (B-2) In the example described in Example 1 (2), the rubber latex used was changed to (A-2), and the amount of water was converted to a solid content. Polymerization was carried out in the same manner except for the adjustment, to obtain a graft copolymer (B-2). The polymerization conversion was 96%, and the graft ratio was 44%.

(5) Evaluation of ABS resin composition Evaluation was made in the same manner as in Example 1 (5) except that the graft copolymer used was changed to (B-2). The results were as shown in Table 1.

(Example 3) (1) Preparation of rubbery polymer (A-3) latex In the example described in Example 1 (1), styrene used in the monomer mixture (F) was replaced with acrylic acid. Polymerization was carried out in the same manner except that the amount was changed to n-butyl [the polymerization conversion rate at the start of the addition of the monomer mixture (S) was 33%], and the solid content was 3%.
A rubbery polymer (A-3) having 9.4% and a weight average particle diameter of 0.25 μm was obtained. The polymerization conversion was 97% and the gel content was 78%.

(2) Production of Graft Copolymer (B-3) In the example described in Example 1 (2), the rubber latex used was changed to (A-3), and the amount of water in terms of solid content was reduced. Polymerization was carried out in the same manner except for the adjustment, to obtain a graft copolymer (B-3). The polymerization conversion rate was 95% and the graft rate was 45%.

(3) Evaluation of ABS Resin Composition The evaluation was performed in the same manner as in Example 1 (5) except that the graft copolymer used was changed to (B-3). The results were as shown in Table 1.

(Example 4) (1) Production of rubbery polymer latex (A-4) In the example described in Example 1 (1), the monomer mixture (S) was polymerized for 8 hours after the start of polymerization. Polymerization conversion at the time of 64
%], A rubber having a solid content of 39.4%, a polymerization conversion of 97%, a weight average particle diameter of 0.25 μm, and a gel content of 84% was obtained. A polymer (A-4) latex was obtained.

(2) Production of Graft Copolymer (B-4) In the example described in Example 1 (2), the rubber latex used was changed to (A-4), and the amount of water in terms of solid content was changed. Polymerization was carried out in the same manner except for the adjustment, to obtain a graft copolymer (B-4). The polymerization conversion was 96% and the graft ratio was 42%.

(3) Evaluation of ABS Resin Composition Evaluation was performed in the same manner as in Example 1 (3) except that the graft copolymer used was changed to (B-4). The results were as shown in Table 1.

Example 5 (1) Production of Rubbery Polymer Latex (A-5) A small particle rubbery polymer latex (D) 2 was placed in a 5-liter glass reactor.
703 parts (1,000 parts as solid content) 3.0 parts of sodium dodecylbenzenesulfonate was charged, and 100 parts of a 5% aqueous solution of phosphoric acid was added dropwise over 3 minutes. 61 parts by weight, an average particle diameter of 0.22 μm, and a gel content of 81 parts.
%, And a rubbery polymer (A-5) latex having a solid content of 35.4%.

(2) Production of Graft Copolymer (B-5) In the example described in Example 1 (2), the enlarged rubber latex used was changed to (A-5), and the amount of water in terms of solid content was changed. The polymerization was carried out in the same manner except that was adjusted, to obtain a graft copolymer (D-5). Polymerization conversion rate 94%, graft rate 5
1%. (3) Evaluation of ABS resin composition Evaluation was performed in the same manner as in Example 1 (3) except that the graft copolymer used was changed to (B-5). The results were as shown in Table 1.

Comparative Example 1 (1) Production of Rubbery Polymer Latex (A-6) In the example described in Example 1 (1), the monomer mixture (F) used was 1,3-butadiene 640. Part, styrene 16
Polymerization was carried out in the same manner except that the monomer mixture (S) was changed to 800 parts (polymerization conversion rate at the start of addition: 39%) to 0 parts, and the solid content was 39.3% and the polymerization conversion rate was 96.
%, A weight average particle diameter of 0.24 μm, and a gel content of 94%, thereby obtaining a rubbery polymer (A-1) latex.

(2) Production of Graft Copolymer (B-6) In the example described in Example 1 (2), the rubber latex used was changed to (A-6), and the amount of water was converted to a solid content. Polymerization was carried out in the same manner except for the adjustment, to obtain a graft copolymer (B-6). The polymerization conversion was 97% and the graft ratio was 42%.

(3) Evaluation of ABS Resin Composition The evaluation was performed in the same manner as in Example 1 (3) except that the graft copolymer used was changed to (B-6). The results were as shown in Table 1.

(Comparative Example 2) (1) Production of rubber-like polymer latex (A-7) In the example described in Example 1 (1), the monomer mixture (S)
The polymerization was carried out in the same manner except that the time of adding was changed to 14 hours from the start of the polymerization (the polymerization conversion rate at this time was 89%),
Rubber-like polymer (A) having a solid content of 38.9%, a polymerization conversion of 95%, a weight average particle diameter of 0.3 μm, and a gel content of 96%.
-7) A latex was obtained.

(2) Production of Graft Copolymer (B-7) In the example described in Example 1 (2), the rubber latex used was changed to (A-7), and the amount of water was converted to a solid content. Polymerization was carried out in the same manner except for the adjustment, to obtain a graft copolymer (B-7). The polymerization conversion was 97% and the graft ratio was 39%.

(3) Evaluation of ABS resin composition Evaluation was performed in the same manner as in Example 1 (3) except that the graft copolymer used was changed to (B-7). The results were as shown in Table 1.

(Comparative Example 3) (1) Production of rubber-like polymer latex (A-8) In the example described in Example 1 (1), the monomer mixture (S)
Was added in the same manner as above before the start of polymerization, and a rubber-like polymer (A) having a solid content of 39.6%, a polymerization conversion of 98%, a weight average particle diameter of 0.27 μm, and a gel content of 87% was prepared. -8) A latex was obtained.

(2) Production of Graft Copolymer (B-8) In the example described in Example 1 (2), the rubber latex used was changed to (A-8), and the amount of water was converted to a solid content. Polymerization was carried out in the same manner except for the adjustment, to obtain a graft copolymer (B-8). The polymerization conversion was 97% and the graft ratio was 41%.

(3) Evaluation of ABS resin composition Evaluation was performed in the same manner as in Example 1 (3) except that the graft copolymer used was changed to (B-8). The results were as shown in Table 1.

Comparative Example 4 (1) Production of Rubbery Polymer (A-9) Latex Same as in Example 1 (1) except that potassium oleate used was changed to 24.0 parts. After 4 hours (at a conversion of 43% at this time), the monomer mixture (S) was added over 4 hours to continue the polymerization, and the solid content was 39.7%. A rubbery polymer (A-9) latex having a conversion of 97%, a weight average particle diameter of 0.12 μm, and a gel content of 84% was obtained.

(2) Production of Graft Copolymer (B-9) In the example described in Example 1 (2), the rubber latex used was changed to (A-9), and the amount of water was converted to a solid content. Polymerization was carried out in the same manner except for the adjustment, to obtain a graft copolymer (B-9). The polymerization conversion was 98% and the graft ratio was 52%.

(3) Evaluation of ABS resin composition Evaluation was performed in the same manner as in Example 1 (3) except that the graft copolymer used was changed to (B-9). The results were as shown in Table 1.

(Comparative Example 5) (1) Production of rubber-like polymer (A-10) latex In a 5-liter glass reactor, a small-particle rubber-like polymer latex (D) 2,
703 parts (1,000 parts as a solid content) 3.0 parts of sodium dodecylbenzenesulfonate was charged, and 500 parts of a 5% aqueous solution of phosphoric acid was added dropwise over 5 minutes. After completion of the addition, a 10% aqueous solution of sodium hydroxide 305 was added. And an average particle diameter of 0.43 μm and a solid content of 30.0%
Was obtained as a rubber-like polymer (A-10) latex.

(2) Production of Graft Copolymer (B-10) In the example described in Example 1 (2), the rubber latex used was changed to (A-10), and the amount of water was converted to a solid content. Polymerization was carried out in the same manner except for the adjustment, to obtain a graft copolymer (B-10). The polymerization conversion rate was 95% and the graft rate was 39%.

(3) Evaluation of ABS resin composition Evaluation was performed in the same manner as in Example 1 (3) except that the graft copolymer used was changed to (B-10). The results were as shown in Table 1.

Comparative Example 6 (1) Production of Graft Copolymer (B-11) In a 5 liter glass reactor, 549 parts of water, 4,051 parts of rubbery polymer (A-1) latex, 1,600 parts) Dextrose 3.0 parts Sodium pyrophosphate decahydrate 0.5 part Ferrous sulfate heptahydrate 0.05 part was charged, the temperature was raised to 60 ° C. after nitrogen replacement, and acrylonitrile 120 parts styrene A mixture consisting of 280 parts tert-dodecyl mercaptan 4.8 parts cumene hydroperoxide 1.2 parts was added dropwise over 200 minutes, and at that time, the internal temperature was controlled to 65 ° C. After dropping, 0.6 parts of cumene hydroperoxide was added,
The mixture was kept at 0 ° C. for 1 hour, cooled after adding 10 parts of an antioxidant (Kawaguchi Chemical Industry Antage W-400). This graft copolymer latex is coagulated with a 0.5% aqueous sulfuric acid solution, washed and dried to obtain a milky white powder of the graft copolymer (B
-11) was obtained. Polymerization conversion rate 93%, graft rate 14%
Met.

(2) Evaluation of ABS resin composition In the example described in Example 1 (3), the graft copolymer used to adjust the content of the rubbery polymer in the ABS resin composition was used. Was changed to (B-11) 21 parts and the copolymer (C) 79 parts, and the same evaluation was performed. The results were as shown in Table 1.

As shown in Table 1, the graft copolymer which does not satisfy the conditions specified in the present invention is unsatisfactory in any of the properties, particularly the impact resistance and the appearance of the molded article. It can be seen that the graft copolymer according to the present invention is particularly excellent in the balance of impact resistance, flowability, and surface gloss of the molded product at ordinary temperature and low temperature.

[0089]

The graph obtained by the manufacturing method of the present invention.
The ABS resin composition using the copolymer is excellent in glossiness, fluidity and impact resistance, and has an excellent balance of physical properties. In particular, the impact resistance in a wide temperature range is remarkably improved.

Continuation of the front page (56) References JP-A-58-187411 (JP, A) JP-A-8-41143 (JP, A) JP-A-57-23652 (JP, A) JP-A-54-133588 (JP) , A) JP-A-59-202211 (JP, A) European Patent Application Publication 9407923 (EP, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 279/02 C08F 236/04 C08F 236/10 C08L 51/04 C08L 55/02

Claims (3)

(57) [Claims] 1. An aliphatic conjugated diene monomer 50 to 100.
Monomer (mixture) consisting of 0% to 50% by weight and at least one monomer selected from aromatic vinyl monomers, alkyl acrylate monomers and vinyl cyanide monomers (Total 100% by weight) (F) 10
Emulsion polymerization of 99 parts by weight, polymerization conversion rate 1-80% by weight
At the time of (polymerization conversion of the monomer (mixture) (F)), 0 to 99% by weight of the aliphatic conjugated diene monomer and the aromatic vinyl monomer and / or alkyl acrylate monomer (S) 1 to 90 parts by weight of a monomer (mixture) consisting of 1 to 100% by weight of the monomer (total 100% by weight), and an aliphatic conjugated diene monomer in the monomer (mixture) (F) Under conditions that the content (% by weight) is higher than the aliphatic conjugated diene-based monomer content (% by weight) in the monomer (mixture) (S),
(Total of 100 parts by weight of (F) + (S)), and further polymerized to obtain a weight average particle diameter of 0.15 to 0.40 μm.
And producing a rubbery polymer (A) latex having a gel content of 50 to 90% by weight. 2. An aliphatic conjugated diene monomer 50 to 100.
% By weight and a monomer (mixture) comprising from 0 to 50% by weight of at least one selected from aromatic vinyl monomers, alkyl acrylate monomers and vinyl cyanide monomers (Total 100% by weight) (F) 10-9
Emulsion polymerization of 9 parts by weight, polymerization conversion rate 1-80% by weight
At the time of (polymerization conversion of the monomer (mixture) (F)), 0 to 99% by weight of the aliphatic conjugated diene monomer and the aromatic vinyl monomer and / or alkyl acrylate monomer (S) 1 to 90 parts by weight of a monomer (mixture) consisting of 1 to 100% by weight of the monomer (total 100% by weight), and an aliphatic conjugated diene monomer in the monomer (mixture) (F) Under conditions that the content (% by weight) is higher than the aliphatic conjugated diene-based monomer content (% by weight) in the monomer (mixture) (S),
(Total of 100 parts by weight of (F) + (S)), followed by further polymerization, followed by further enlargement operation to obtain a weight average particle diameter of 0.15 to 0.40 μm and a gel content of 50.
A method for producing a rubber-like polymer (A) latex, which comprises obtaining a rubber-like polymer (A) latex of about 90% by weight. 3. A rubber-like polymer (A) latex 5 to 8 obtained by the production method according to claim 1 or 2.
In the presence of 0 parts by weight (as solid content), 10 to 40% by weight of a vinyl cyanide monomer and 60 of an aromatic vinyl monomer
Graft polymerization of 20 to 95 parts by weight of a monomer mixture composed of 0 to 90% by weight and 0 to 20% by weight (total 100% by weight) of other vinyl monomers copolymerizable therewith results in a graft ratio of 20 to 90%. A method for producing a graft copolymer (B), wherein 100% by weight of the graft copolymer (B) is obtained.