JPS63196637A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in degree of matting, uniformity of mating, matting property such as prevention of formation of silver surfaces and mechanical properties, by mixing a specified thermoplastic rubber- reinforced aromatic vinyl resin with a bisoxazoline compound. CONSTITUTION:A thermoplastic rubber-reinforced aromatic vinyl resin (A) is obtained by polymerizing 0.02-10wt.% ethylenically unsaturated carboxylic acid (b) [e.g., (meth)acrylic acid], an aromatic vinyl compound (c) [e.g., (alpha- methyl)-styrene], an unsaturated nitrile (d) [e.g., (meth)acrylonitrile] and/or an unsaturated carboxylate (e) [e.g., (meth)acrylate] and, optionally, other monomers (f) copolymerizable therewith (e.g., N-phenylmaleimide) in the presence of 5-40wt.% rubbery polymer (a) such as polybutadiene or an ethylene/ propylene polymer. 100pts.wt. component A is mixed with 0.01-2.0pts.wt. bisoxazoline compound (B) [e.g., 2,2'-(1,3-phenylene)-bis(2-oxazoline)].

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a thermoplastic resin composition which has excellent mechanical properties, is free from glossy spots, and has good matte properties.

<Conventional technology> The technological progress of various thermoplastic resins has been remarkable.
Its range of use is wide-ranging.

Specifically, there are too many to list, such as light electrical appliances, automobile parts, miscellaneous goods, and OA equipment.

Some fields require high gloss, while others require low gloss. Low-gloss product (1) It has a soft and luxurious feel, and also has safety benefits such as preventing light reflection, such as in automobile interior parts.

Various methods are known for reducing the gloss of thermoplastic resins. For example, a method of blending an inorganic filler, a method of blending a rubbery polymer, a method of total copolymerization of ethylenically unsaturated carboxylic acid (JP-A-60-44517.6
O-197713).

<Problems to be Solved by the Invention> The method of blending an inorganic filler not only does not provide a sufficient matting effect, but also involves a significant decrease in cylindrical strength. In addition, in the method of blending a rubbery polymer such as a styrene-butadiene block polymer, the dispersion of the rubbery polymer particles cannot be controlled due to the crosstalk conditions with the thermoplastic resin, and the matting effect may not be sufficiently tenacious. The product value is significantly inferior due to rubber streaks and glossy spots. Furthermore, the method of total copolymerization of ethylenically unsaturated carboxylic acids and the method of adding a metal compound to the copolymer, which is also a method of crosslinking carboxylic acids to reduce gloss, Influence of history? Since the crosslinking degree of the bridge varies, not only is it not possible to obtain stable matte properties, but also gloss spots occur. In addition, since the crosslinking reaction of carboxylic acid is a neutralization reaction, water metal is generated, and the scratching also causes silver streaks (silver) to appear on the surface of the molded product during molding.

Means for Solving All Problems〉 As a result of intensive study in view of the above-mentioned problems, the present inventors have found that
A composition consisting of a rubber-reinforced aromatic vinyl thermoplastic resin copolymerized with ethylenically unsaturated carboxylic acid and a small amount of a specific compound has excellent mechanical properties and is free from gloss spots.
The inventors have discovered that the composition has good matting properties, and have arrived at the present invention.

That is, the present invention reduces ethylenically unsaturated carboxylic acid to 0.
．． Thermoplastic resin with good matting properties, consisting of 0.02 to 10 parts by weight of a copolymerized rubber-reinforced aromatic vinyl thermoplastic resin and 0.01 to 2.0 parts by weight of a bisoxazolin compound. A composition is provided.

The composition of the present invention will be explained in detail below.00 Rubber-reinforced aromatic vinyl thermoplastic resin Rubber-reinforced aromatic (mu) copolymerized with ethylenically unsaturated carboxylic acid, which is a constituent component of the composition of the present invention. The vinyl thermoplastic resin is exemplified by the following (1) to 1.

(1) In the presence of rubbery polymer (a), ethylenically unsaturated carboxylic acid (b), aromatic vinyl (Cl), unsaturated nitrile (d) and/''! or unsaturated carboxylic acid ester (e ), or (b), (cl, (dl) and/or (e), and other monomers (f) which can be copolymerized with each other.

(2) Ethylenically unsaturated carboxylic acid (b), aromatic vinyl (C) and unsaturated nitrile (d) and /'! or unsaturated carboxylic acid Nisal(e) or 7'CU(b8(c)
), (d) and/or <8) and another monomer (j) copolymerizable with them, and a rubbery polymer (a). 10(3) Between the above-mentioned copolymers and in the presence of the rubbery polymer (a), aromatic vinyl (e) and unsaturated nitrile (e) and/or unsaturated carboxylic acid ester (e), or ( e), (d) and/
or other monomers copolymerizable with (e) and others (f+
(4) Between the above-mentioned copolymers, the graft polymer (6), aromatic vinyl (C), unsaturated nitrile (d) and/ or unsaturated carboxylic acid ester (el, or (C), (
A copolymer formed by polymerizing d) and/or (e) and another monomer (f) copolymerizable with them (resin consisting of ■0 (5) the above-mentioned resin stamp, Co-M association prisoner, graft polymer l
and a resin (YIO (6)) consisting of at least one kind selected from the group consisting of the above-mentioned resin stamps to polystyrene, rubber-reinforced polystyrene, polycarbonate,
A resin leaf comprising at least one member selected from the group consisting of polyamide, polyester, and polyphenylene ether.

As the rubber-reinforced aromatic vinyl thermoplastic resin, any of the above-mentioned resin stamps to [YI] may be used, but from the standpoint of commercial production, resins DI, +: tv+, and resin paste with resin [11'] are preferred. .

Rubbery polymers ((conversion) include polybutadiene, butadiene-styrene polymer, butadiene-acrylonitrile polymer, polyisoprene, polychloroprene, ethylene-propylene polymer, ethylene-propylene-nonconjugated diene polymer, polybutyl acrylate , ethylene-vinyl acetate polymer, chlorinated polyethylene, etc.
One type or two or more types can be used.

As the ethylenically unsaturated carboxylic acid (BL), one or more of acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, etc. can be used.

Aromatic vinyl (b) includes styrene, α-methylstyrene, α-chlorostyrene, pt-butylstyrene, p-methylstyrene, o-chlorostyrene, p-10
Rostyrene, 2.5-dichlorostyrene, 3.4-dichlorostyrene, p-bromostyrene, 0-bromostyrene, 2.5-Schiff"lomostyrene, 3.4-Schiff"lomostyrene, cyanostyrene, 2-isopropenylnaphthalene One or more types can be used. Particularly preferred are styrene and α-methylstyrene.

Examples of the unsaturated nitrile (C) include acrylonitrile, methacrylonitrile, maleonitrile, and fumaronitrile, and one or more of them can be used. Acrylonitrile is particularly preferred.

As the unsaturated carboxylic acid ester (e), (meth)acrylic acid ester monomers such as methyl, ethyl, propyl, butyl, lauryl, cyclohexyl, 2-hydroxyethyl, glycidyl, and dimethylaminoethyl of (meth)acrylic acid are used. mono- and dialkyl esters of unsaturated dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid, and hymic acid.

One or more types of these fLs can be used. Particularly preferred is methyl methacrylate.

Other copolymerizable monomers (fl include maleimide,
N-methylmaleimide, N-
butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-7enylmaleimide)", N
-o-chlorophenylmaleimide and the like are mentioned, and one or two of them are preferably used.

The amount of copolymerized ethylenically unsaturated carboxylic acid in the rubber-reinforced aromatic vinyl thermoplastic resin is 0.02 to 10% by weight.
It is. 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 will increase and the mechanical properties will also deteriorate, which is not preferable.

0.02~3, OM in terms of mechanical properties, matte properties, etc.
Particularly preferred is quantity.

There is no particular restriction on the ratio of each component other than the ethylenically unsaturated carboxylic acid in the rubber-reinforced aromatic vinyl thermoplastic resin, but the proportion of the rubbery polymer (a) in the resin is 5 to 5.
The content is preferably 40% by weight in terms of mechanical properties, workability, etc.

Furthermore, there are no restrictions on the method of polymerizing the rubber-reinforced aromatic vinyl thermoplastic resin, and examples include emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, and combinations thereof.

Bisoxazoline compounds constituting the composition of the present invention include 2.2' (1,2phenylene)-bis(2-
oxazoline), 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',3cyclohexane)-bis(2-oxazoline), 2,2'-(1,4cyclohegythane)-bis(2-oxazoline), 2,2'-(1,1methylene)-bis( 2-oxazoline), 2.2-(1,2ethylene)-bis(2-oxazoline), 2.2'-(1
,3propane)-bis(2-oxazoline),2.2-
Examples include (1,4-butane)-bis(2-oxazoline) and alkyl-substituted products thereof, and one or more types thereof can be used. Particularly easy to obtain2,2
'-(1,3phenylene)-bis(2-oxazoline)
is commercially preferred.

The bisoxazolinated additive is used in an amount of 1 to 2.0 parts by weight per 100 M parts of the rubber-reinforced aromatic vinyl thermoplastic resin. If it is less than 0.01 part by weight, sufficient matting properties cannot be obtained, and silver tends to occur. On the other hand, 2.
Even if an amount exceeding 0 parts by weight is used, the gloss will not become even lower;
On the contrary, it only increases the cost.

The composition of the present invention can be produced by any method that corresponds to the production method of the rubber-reinforced aromatic vinyl thermoplastic resin. For example, it can be blended in the form of powder, beads, pellets, etc.

Generally, a uniform resin composition can be obtained by mixing in a melt kneading machine such as a Banbury mixer, a kneader, or a single-screw or twin-screw extrusion machine.

Furthermore, the composition of the present invention may optionally contain an antioxidant,
Heat stabilizers, light stabilizers, lubricants, plasticizers, antistatic agents, inorganic and organic colorants, blowing agents, inorganic and organic fillers, and the like can be added.

The composition of the present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto in any way.

Examples and Comparative Examples 0 Copolymer Threshold Into a reactor purged with nitrogen, 1.5 parts by weight of sodium alkylbenzenesulfonate (emulsifier) and potassium persulfate (
Add 3 parts by weight of initiator) and 150 M parts of water, raise the temperature to 65°C, then continuously add the monomer mixture shown in Table 1 for 4 hours while maintaining 65°C to react. Thereafter, the mixture was further aged for 2 hours to complete the polymerization.

The resulting refined latex was salted out using sulfuric acid and magnesium sulfate, and then dried to obtain a powder.

0 Graft Heavy Body (6) Add each substance shown in Table 2 to a reactor purged with nitrogen, and
It was placed at 5°C for 6 hours.

After adding 0.5 parts by weight each of Sumilizer (registered trademark) BBM and Sumilizer TPL, which are antioxidants manufactured by Sumitomo Chemical Co., Ltd., to the obtained refined latex, the mixture was salted out using sulfuric acid and magnesium sulfate, and then dried.

Table 2 (Parts by weight) Copolymer C-1 (30°C,
Dimethylformamide, intrinsic viscosity 0.62),
A copolymer C-2 (intrinsic viscosity: 0.58) containing 75% by weight of methylstyrene and 25% by weight of acrylonitrile was obtained.

The above-mentioned copolymer diagram, graft polymer (5), copolymer group, and commercially available polycarbonate Teijin Kasei Co., Ltd. Sakipanlite (registered trademark) L-1250W were combined in the weight ratios shown in Tables 3 and 4. After kneading and granulating at 275°C using an extruder, it was molded using an injection molding machine to a size of 150 f + on x 70 mm wide.
A flat plate (with one gate in the horizontal center) having a thickness of 3× was prepared, and the gloss (reflected light at an incident angle of 60 degrees) of the gate part and the anti-gate part was measured. In addition, the state of silver generation was visually evaluated.

○No Nijiru bar occurrence X； ＃ ＃ ＃　　　　　　 Tsuta: #I is significant.

The results are shown in Tables 3 and 4.

<Effects of the Invention> The composition of the present invention has
Excellent in matte degree, matte uniformity, and silver suppression.

Claims (1)

[Claims] It is characterized by consisting of 100 parts by weight of a rubber-reinforced aromatic vinyl thermoplastic resin copolymerized with 0.02 to 10% by weight of ethylenically unsaturated carboxylic acid and 0.01 to 2.0 parts by weight of a bisoxazoline compound. A thermoplastic resin composition with good matte properties.