JPH0456044B2 - - Google Patents

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to a method for producing a thermoplastic resin that has a matte appearance and is excellent in impact resistance, rigidity, heat deformation resistance, moldability, and surface appearance. . (Prior Art and Problems) ABS resins have excellent impact resistance, heat deformation resistance, moldability, and good surface gloss, and are used for various purposes. On the other hand, in the fields of automobile interior parts, light electrical parts, etc., there is a growing demand for products with reduced gloss (reflectance) on the surface of parts to ensure a sense of calm, luxury, and safety by suppressing light reflection. ing. Methods to suppress gloss and obtain matte parts include improving the mold surface, using matte coating,
For heat treatment, methods such as blending inorganic substances or rubber components have been used. However, the current situation is that these methods do not have sufficient effects. That is,
It is difficult to repair and manage the mold when improving from the mold side, and the gloss condition changes depending on the molding conditions.
It is difficult to obtain a molded product with a constant gloss. Inorganic formulations significantly reduce impact resistance, while rubber formulations reduce heat deformation resistance and rigidity, tend to cause flow marks and welt lines, and make it difficult to obtain molded products with excellent appearance. (Means and Effects for Solving the Problems) As a result of intensive studies to improve these drawbacks, the inventors of the present invention polymerized a monomer mixture containing specific components in the presence of a rubbery polymer. Later, it was discovered that a polymerized vinyl monomer mixture has a matte appearance and excellent thermal and mechanical properties and moldability, leading to the present invention. That is, in the present invention, when 95 to 65 parts by weight of a vinyl monomer is polymerized in the presence of 5 to 35 parts by weight of a rubbery polymer, 0.1 to 40 parts by weight of a glycidyl ester compound of an α,β-unsaturated acid is added. %, a monomer mixture consisting of 10-35% by weight of a vinyl cyanide compound, 50-89.9% by weight of an aromatic vinyl compound, and 0-30% by weight of other copolymerizable vinyl compounds (total 100% by weight)
After polymerizing 2-40 parts by weight of (A), 10-40% by weight of vinyl cyanide compound and 60-40% by weight of vinyl aromatic compound.
90% by weight and 0 to other copolymerizable vinyl compounds
The subject matter is a method for producing a matte thermoplastic resin by polymerizing 25 to 93 parts by weight of a monomer mixture (total 100% by weight) (B) consisting of 30% by weight. In the present invention, the monomer mixture (A) and the monomer mixture (B) are added in this order in the presence of the rubbery polymer. At this time, the method of adding monomer mixtures (A) and (B) is not particularly limited;
It is preferable to add the monomer mixture (B) after most of the monomer mixture (B) has been polymerized. Of course, monomer mixtures (A) and (B) can also be added in portions. Here, the number of rubbery polymer parts, monomer mixture (A) and
The number and composition of (B) have an optimal point depending on the desired physical properties of the resin, but the amount of rubbery polymer is preferably 5 to 35 parts by weight. Unfavorable in terms of erasability, moldability, etc. The rubbery polymer used in the present invention includes:
Diene rubbers such as polybutadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile, butadiene rubber (NBR), butyl acrylate-butadiene rubber; acrylic rubbers such as polybutyl acrylate; ethylene-propylene-nonconjugated diene rubber (EPDM), etc. Polyolefin rubber and the like are used. The monomer mixture (A) contains 2 to 40 parts by weight, preferably 2 parts by weight.
~30 parts by weight, and its composition is α, β-
Glycidyl ester compounds of unsaturated acids 0.1-40% by weight, preferably 0.5-30% by weight, vinyl cyanide compounds 10-35% by weight, aromatic vinyl compounds 50-40% by weight
89.9% by weight, 0 to other copolymerizable vinyl compounds
It is 30% by weight. Examples of glycidyl ester compounds of α,β-unsaturated acids include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Examples of vinyl cyanide compounds include acrylonitrile and methacrylnitrile, and examples of aromatic vinyl compounds include styrene, methylstyrene, chlorostyrene, and α-methylstyrene. Examples of other copolymerizable vinyl compounds include methyl methacrylate, ethyl methacrylate, ethyl acrylate, butyl acrylate, acrylic acid, methacrylic acid, phenylmaleimide, and hydroxyacrylate. If the amount of the monomer mixture (A) is outside the range of 2 to 40 parts by weight, impact resistance, moldability, matting properties, etc. will deteriorate, which is not preferable. In the monomer mixture (A),
Glycidyl ester compounds of α,β-unsaturated acids are
The content is preferably 0.1 to 40% by weight; if it is less than 0.1% by weight, the matting effect will be insufficient, and if it is more than 40% by weight, moldability and impact resistance will deteriorate, which is not preferable. The vinyl cyanide compound is preferably 10 to 35% by weight,
Outside this range, impact resistance may deteriorate or thermal coloring may occur during molding, which is not preferable. The amount of the aromatic vinyl compound is preferably 50 to 89.9% by weight, and if it is outside this range, the impact resistance may deteriorate, which is not preferable. The monomer mixture (B) is 25 to 93 parts by weight, and the vinyl cyanide compound is preferably 10 to 40 parts by weight. Outside this range, impact resistance may decrease or thermal discoloration may occur during molding. This is not desirable.
The aromatic vinyl compound is preferably 60 to 90% by weight,
Outside this range, impact resistance and moldability may deteriorate, which is undesirable. monomer mixture
The vinyl cyanide compound, aromatic vinyl compound, and copolymerizable vinyl compound used in (B) can be the same as those used in monomer mixture (A). In order to improve heat resistance, it is preferable to use α-methylstyrene as the aromatic vinyl compound. The intrinsic viscosity (dl/g, 30 DEG C., N,N'-dimethylformamide solution) of the resulting polymer soluble in methyl ethyl ketone is preferably in the range of 0.25 to 1.5. Outside this range, impact resistance and rigidity may be reduced, and moldability may be reduced, which is not preferable. The method for producing the resin of the present invention preferably involves emulsion polymerization, but is not limited to emulsion polymerization. Examples include suspension polymerization, solution polymerization, bulk polymerization, emulsion-bulk polymerization, and emulsion-suspension polymerization. Emulsion polymerization can be carried out by conventional methods. For example, the monomer mixture may be polymerized using a radical initiator in an aqueous dispersion medium in the presence of a rubbery polymer. Examples of the radical initiator include peroxides such as potassium persulfate, ammonium persulfate, and kyumene hydroperoxide. others,
Polymerization accelerators, polymerization degree regulators, emulsifiers, etc. can also be selected and used as appropriate. The polymerization temperature is preferably 30 to 90°C. A known method may be used to obtain the resin from the obtained latex. For example, it is obtained by coagulating with inorganic salts such as calcium chloride, magnesium chloride, and aluminum sulfate, and acids such as hydrochloric acid, sulfuric acid, acetic acid, and phosphoric acid. Further, stabilizers, lubricants, plasticizers, pigments, fillers, etc. may be added as necessary.
In addition, polycarbonate resin, polyvinyl chloride resin, ABS resin, AS resin, PET resin, PBT
It is also possible to use it by blending it with a resin or the like. The thermoplastic resin composition of the present invention has a matte appearance and is excellent in impact resistance, rigidity, heat deformation resistance, moldability, and surface appearance. (Example) The present invention will be specifically described below with reference to Examples, but the present invention is not limited to the Examples. In addition, "parts" below refer to "parts by weight" unless otherwise specified.
and "%" is % by weight. Examples and Comparative Examples Water 250 parts Sodium laurate 0.5 parts Sodium formaldehyde sulfoxylate
0.4 parts Disodium ethylenediaminetetraacetate
0.01 part Ferrous sulfate 0.0025 part These substances were charged into a reactor equipped with a stirrer, deoxidized, heated to 60°C in a nitrogen stream and stirred, Table 1
Rubber latex and monomer mixtures (A) and (B) were sequentially charged. Monomer mixtures (A) and (B) at 10 per hour
1 hour after the dripping is finished.
Stirring was continued at 60°C to complete polymerization. Incidentally, 1 part of sodium laurate was added each 1 hour and 4 hours after the start of dropping the monomer mixture (A). In addition, in Example 7, the monomer mixture (B) was divided into (B-1) and (B-2).
After the completion of dropping (B-1), (B-2) was added dropwise. Furthermore, in Example 8, the monomer mixture (B) was
-1) and (B-2), (B-1) was charged all at once, and (B-2) was continuously added dropwise over 6 hours. The latex was sampled during the polymerization and at the end of the polymerization and was subjected to analysis. A phenolic antioxidant was added to the obtained polymer latex, which was salted out with calcium chloride and coagulated, washed with water, dried, pelletized using a vented extruder, and subjected to measurement of physical properties. .

【table】

【table】

【table】

[Table] In addition, as Reference Example 1, a product with the same composition as Example 2 was prepared by polymerizing the monomer mixture (A) into a rubbery polymer by ordinary emulsion polymerization, and then powdered. One was prepared by polymerizing only the monomer mixture (B), the other was made into powder, and the other was obtained by blending both. As Reference Example 2, a product with the same composition as Example 2 was prepared by polymerizing monomer mixture (B) into a rubber-like polymer by ordinary emulsion polymerization, and was made into powder, and a monomer mixture ( One was obtained by polymerizing only A), the other was made into a powder, and the other was obtained by blending both.

【table】

[Table] From Tables 1, 2, and 3, those within the scope of the present invention have a matte appearance and are excellent in impact resistance, rigidity, heat deformation resistance, moldability, and surface appearance. It can be seen that it is.

Claims (1)

[Scope of Claims] 1. When 95 to 65 parts by weight of a vinyl monomer is polymerized in the presence of 5 to 35 parts by weight of a rubbery polymer, α, β
- Glycidyl ester compounds of unsaturated fatty acids 0.1
Monomer mixture (A) 2 to 40% by weight, vinyl cyanide compound 10 to 35%, aromatic vinyl compound 50 to 89.9% by weight, and other copolymerizable vinyl compounds 0 to 30% by weight After polymerizing 40 parts by weight, vinyl cyanide compound 10-40% by weight, aromatic vinyl compound 60%
A method for producing a matte thermoplastic resin, comprising polymerizing 25 to 93 parts by weight of a monomer mixture (B) comprising ~90% by weight and 0 to 30% by weight of other copolymerizable vinyl compounds. .