JPH0623293B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a thermoplastic resin composition which is excellent in mechanical properties, has no gloss, and has good matting properties.

<Prior art> The resinous progress of various thermoplastic resins is remarkable,
The range of use is also wide. Specifically, there are many appliances such as light electrical appliances, automobile parts, miscellaneous goods, and office automation equipment.

Some of these fields require high gloss and some require low gloss. The low-gloss products have advantages in terms of softness and luxury, and also in terms of safety such as preventing reflection of light as in automobile interior parts.

Various methods are known to reduce the gloss of the thermoplastic resin (gloss digestion). For example, a method of blending an inorganic filler, a method of blending a rubbery polymer, a method of copolymerizing an ethylenically unsaturated carboxylic acid (JP-A-60-44517,
60-197713) and the like.

<Problems to be Solved by the Invention> The method of blending the inorganic filler not only has an insufficient matting effect, but also causes a marked decrease in impact strength. Further, the method of blending a rubbery polymer such as styrene-butadiene block polymer cannot control the dispersed particles of the rubbery polymer due to the kneading conditions with the thermoplastic resin, and the matting effect is insufficient, or the rubber The product value is significantly inferior because streaks and gloss are generated. Furthermore, the method of copolymerizing ethylenically unsaturated carboxylic acid and the method of adding a metal compound to these are both methods of cross-linking carboxylic acids to reduce gloss, but the thermal history such as granulation temperature and molding temperature Since the degree of cross-linking fluctuates under the influence of, not only stable matte property cannot be obtained, but also glossiness occurs. Also, since the crosslinking reaction of the carboxylic acid is a neutralization reaction, water is produced, which is
It can also cause silver streaks (silver) on the surface of molded products.

<Means for Solving Problems> As a result of intensive investigations by the present inventors in view of the above problems,
A composition comprising a rubber-reinforced aromatic vinyl-based thermoplastic resin copolymerized with an ethylenically unsaturated carboxylic acid and a small amount of a specific compound has excellent mechanical properties, has no luster, and has good matting properties. Found to be a composition,
The present invention has been reached.

That is, the present invention, the ethylenically unsaturated carboxylic acid.
02-10 wt% copolymerized rubber-reinforced aromatic vinyl-based thermoplastic resin 100 parts by weight and bisoxazoline compound 0.01-
It is intended to provide a thermoplastic resin composition having 2.0 parts by weight and having a good matting property.

Hereinafter, the composition of the present invention will be described in detail.

Rubber-reinforced aromatic vinyl-based thermoplastic resin is a rubber-reinforced aromatic vinyl-based thermoplastic resin copolymerized ethylenically unsaturated carboxylic acid is a constituent of the composition of the present invention, the following (1) ~ (6) It is an exemplified resin.

(1) In the presence of the rubbery polymer (a), an ethylenically unsaturated carboxylic acid (b), an aromatic vinyl (c) and an unsaturated nitrile (d) and / or an unsaturated carboxylic acid ester (e), Or (b),
A resin [I] obtained by polymerizing (c), (d) and / or (e) with another monomer (f) copolymerizable therewith.

(2) ethylenically unsaturated carboxylic acid (b), aromatic vinyl (c)
And unsaturated nitrile (d) and / or unsaturated carboxylic acid ester (e), or (b), (c), (d) and / or (e)
A resin [I] composed of a copolymer [A] obtained by polymerizing the above monomer and another monomer (f) copolymerizable therewith and a rubbery polymer (a) [I]
I].

(3) In the presence of the above-mentioned copolymer [A] and rubbery polymer (a), aromatic vinyl (c) and unsaturated nitrile (d) and / or unsaturated carboxylic acid ester (e), Alternatively, a resin [I] comprising (c), (d) and / or (e) and a graft polymer [B] obtained by polymerizing another monomer (f) copolymerizable therewith
II].

(4) The above-mentioned copolymer [A], graft polymer [B], aromatic vinyl (c), unsaturated nitrile (d) and / or unsaturated carboxylic acid ester (e), or (c), A resin [IV] comprising a copolymer [C] obtained by polymerizing (d) and / or (e) and another monomer (f) copolymerizable therewith.

(5) A resin [V] comprising the above resin [I] and at least one selected from the group consisting of a copolymer [A], a graft polymer [B] and a copolymer [C].

(6) At least one of the above resins [I] to [V], polystyrene, rubber-reinforced polystyrene, polycarbonate,
A resin [VI] comprising at least one selected from the group consisting of polyamide, polyester and polyphenylene ether.

The rubber-reinforced aromatic vinyl-based thermoplastic resin may be any of the above-mentioned resins [I] to [VI], but from the viewpoint of commercial production, resins [III], [IV] and resins based on the resin [III] are used. [VI] is preferred.

Examples of the rubbery polymer (a) include polybutadiene, butadiene-styrene polymer, butadiene-acrylonitrile polymer, polyisoprene, polychloroprene, ethylene-
Propylene polymer, ethylene-propylene-non-conjugated diene polymer, polybutyl acrylate, ethylene-vinyl acetate polymer, chlorinated polyethylene and the like can be mentioned, and one kind or two or more kinds can be used.

Examples of the ethylenically unsaturated carboxylic acid (b) include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid and the like, and one or more kinds can be used.

As the aromatic vinyl (C), styrene, α-methylstyrene, α-chlorostyrene, pt-butylstyrene,
p-methylstyrene, o-chlorostyrene, p-chlorostyrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, p-bromostyrene, o-bromostyrene, 2,5-dibromostyrene, 3,4- Dibromostyrene, cyanostyrene, 2-isopropenyl naphthalene, etc. are mentioned, and 1 type (s) or 2 or more types can be used. Particularly preferred are styrene and α-methylstyrene.

Examples of the unsaturated nitrile (d) include acrylonitrile, methacrylonitrile, maleonitrile, fumaronitrile and the like, and one kind or two or more kinds can be used.
Acrylonitrile is particularly preferable.

Examples of the unsaturated carboxylic acid ester (e) include (meth) acrylic acid ester-based monomers such as methyl, ethyl, propyl, butyl, lauryl, cyclohexyl, 2-hydroxyethyl, glycidyl and dimethylaminoethyl of (meth) acrylic acid. And mono- and dialkyl esters of unsaturated dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid and hymic acid. These may be used alone or in combination of two or more.
Methyl methacrylate is particularly preferable.

Other copolymerizable monomers (f) include maleimide, N
-Methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-o-
Chlorophenylmaleimide and the like can be mentioned, and one kind or two or more kinds can be used. Particularly, N-phenylmaleimide, N-cyclohexylmaleimide and N-o-chlorophenylmaleimide are preferably used.

The copolymerized ethylenically unsaturated carboxylic acid in the rubber-reinforced aromatic vinyl-based thermoplastic resin is 0.02 to 10% by weight. If it is less than 0.02% by weight, sufficient matting properties cannot be obtained. On the other hand, if it exceeds 10% by weight, the gloss is rather increased and the mechanical properties are deteriorated, which is not preferable.

From the viewpoints of mechanical properties and matting properties, it is particularly preferable that the content is 0.02 to 3.0% by weight.

The ratio of each component other than the ethylenically unsaturated carboxylic acid in the rubber-reinforced aromatic vinyl-based thermoplastic resin is not particularly limited, but the ratio of the rubber-like polymer (a) in the resin is 5 to 4
It is preferably 0% by weight from the viewpoint of mechanical properties, workability and the like.

The method for polymerizing the rubber-reinforced aromatic vinyl-based thermoplastic resin is not particularly limited, and examples thereof include emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method and combinations thereof.

Bisoxazoline Compounds Examples of the bisoxazoline compound constituting the composition of the present invention include 2,2 ′ (1,2phenylene) -bis (2-oxazoline) and 2,2 ′-(1,3phenylene) -bis (2 -Oxazoline), 2,2 '-(1,4phenylene) -bis (2-oxazoline), 2,2'-(1,2
Cyclohexane) -bis (2-oxazoline), 2,
2 '-(1,3 cyclohexane) -bis (2-oxazoline), 2,2'-(1,4 cyclohexane) -bis (2-oxazoline), 2,2 '-(1,1 methylene)
-Bis (2-oxazoline), 2,2 '-(1,2 ethylene) -bis (2-oxazoline), 2,2'-(1,
3 propane) -bis (2-oxazoline), 2,2'-
Examples include (1,4 butane) -bis (2-oxazoline) and alkyl-substituted products thereof, and one or more kinds can be used. Especially easy to obtain 2,
2 '-(1,3phenylene) -bis (2-oxazoline) is commercially preferred.

The bisoxazoline compound is used in an amount of 0.01 to 2.0 parts by weight based on 100 parts by weight of the rubber-reinforced aromatic vinyl-based thermoplastic resin. If it is less than 0.01 part by weight, sufficient mattness cannot be obtained,
Also, silver is easily generated. On the other hand, even if the amount exceeds 2.0 parts by weight, the gloss does not become lower, and the cost is rather increased.

The composition of the present invention can be produced by any method depending on the production method of the rubber-reinforced aromatic vinyl-based thermoplastic resin. For example, they can be blended in the form of powder, beads, pellets and the like. Generally, they are mixed with a Banbury mixer, a kneader, or a melt-kneader such as a single-screw or twin-screw extruder,
A uniform resin composition can be obtained.

Further, for the composition of the present invention, if necessary, an antioxidant,
A heat stabilizer, a light stabilizer, a lubricant, a plasticizer, an antistatic agent, an inorganic and organic colorant, a foaming agent, an inorganic and organic filler and the like can be added.

Hereinafter, the composition of the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Examples and Comparative Examples Copolymer [A] To a reactor substituted with nitrogen, 1.5 parts by weight of sodium alkylbenzenesulfonate (emulsifier), 0.3 parts by weight of potassium persulfate (initiator), and 150 parts by weight of water were added, and the mixture was heated to 65 ° C. After the temperature was raised, the monomer mixture shown in Table 1 was continuously added and reacted for 4 hours while maintaining the temperature at 65 ° C, followed by aging for 2 hours to complete the polymerization.

The obtained latex was salted out with sulfuric acid and magnesium sulfate and then dried to obtain a powder.

Graft polymer [B] Each substance shown in Table 2 was added to a reactor substituted with nitrogen.
Polymerization was carried out at 5 ° C. for 6 hours.

Sumitomo Chemical Co., Ltd. antioxidant Sumilizer (registered trademark) BBM and Sumilizer TPL were each added to the obtained latex.
After adding 0.5 parts by weight, the product was salted out with sulfuric acid and magnesium sulfate and dried.

Copolymer [C] Copolymer C-1 (3 containing 75% by weight of styrene and 25% by weight of acrylonitrile according to the method for producing copolymer [A]
0 ℃, dimethylformamide, intrinsic viscosity 0.62), α
A copolymer C-2 (inherent viscosity 0.58) containing 75% by weight of methylstyrene and 25% by weight of acrylonitrile was obtained.

The above-mentioned copolymer [A], graft polymer [B], copolymer [C] and commercially available polycarbonate Teijin Kasei Panlite (registered trademark) L-1250W were added in the weight ratios shown in Tables 3 to 4. Blended and kneaded at 275 ° C using an extruder,
After granulating, use an injection molding machine to create a flat plate (length 150 mm × width 70 mm × thickness 3 mm (one gate in the horizontal center) and the gloss of the gate and anti-gate (reflected light at an incident angle of 60 ° C)) Was measured. In addition, the silver generation state was visually evaluated.

The results are shown in Tables 3 to 4.

<Effects of the Invention> The composition of the present invention is superior in the degree of matting, the uniformity of matting, and the suppression of silver as compared with the conventionally known matting compositions.

Claims (1)

[Claims] 1. An ethylenically unsaturated carboxylic acid containing 0.02 to 10
A thermoplastic resin composition having good matting properties, which comprises 100 parts by weight of a rubber-reinforced aromatic vinyl-based thermoplastic resin copolymerized by weight% and 0.01 to 2.0 parts by weight of a bisoxazoline compound.