JPH0328258A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition which has a good balance between the impact resistance and the flowability and gives a molding with a uniform matte surface by mixing a rubber-toughened styrene resin with a specified modified copolymer at a specified ratio. CONSTITUTION:The subject composition is obtained by mixing 100 pts.wt. rubber-toughened styrene resin, about 0.1-30 pts.wt. oxazoline-modified copolymer prepared from 0.1-20wt.% vinyl oxazoline, 50-89.9wt.% aromatic vinyl monomer, and 49.9-10wt.% other copolymerizable monomer, and about 0-30 pts.wt. copolymer prepared from 0.1-20wt.% monomer having a functional group reactive with an oxazoline group, 50-89.9wt.% aromatic vinyl monomer, and 49.9-10wt.% other copolymerizable vinyl monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a thermoplastic resin composition that has excellent impact resistance and flowability, and provides a uniform matte surface of a molded product during molding.

<Conventional technology> Rubber-reinforced styrene resins, typified by ABS resins, have excellent mechanical properties such as impact resistance and rigidity, workability, and the appearance of molded products such as gloss, and are used for automobile parts, office machine parts, It is used for a wide range of purposes such as miscellaneous goods. However, in recent years, there has been an increasing demand for low-gloss matte materials mainly for automobile interior parts from the viewpoint of safety or to obtain a calm matte texture. Conventionally, it has been proposed to introduce a rubber-reinforced styrenic tree-based unsaturated carboxylic acid by copolymerization, and (v) to add an olefin copolymer containing an epoxy group.

(11) Addition of rubbery polymers causes defects such as flow marks on the surface of the molded product, resulting in a uniform matte finish. There is a problem that a surface cannot be obtained, and the addition of (l) ethylenically unsaturated carboxylic acid and (Iv) epoxy group-containing olefin copolymer has the problem of (+) and (II) mentioned above.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that by mixing a specific modified copolymer with a rubber-reinforced styrenic resin in a specific ratio, The present invention was achieved by discovering that a thermoplastic resin composition having a good balance between impact strength and flowability and giving a uniform matte molded product surface can be obtained.

That is, the present invention comprises (A) a rubber-reinforced styrenic resin, 0.1 to 20% by weight of vinyloxazoline, 50 to 89.9% by weight of an aromatic vinyl monomer, and other copolymerizable vinyl monomers. Oxazoline modified copolymer consisting of 49.9 to 10% by weight, 0 Monomer having a functional group reactive with an oxazoline group 0
．． 1 to 20% by weight, aromatic vinyl monomer hakama W50 to
(B) 0.89.9% by weight and a copolymer consisting of 49.9-10% by weight of other copolymerizable vinyl monomers per 0.100 parts by weight. The present invention provides a thermoplastic resin composition characterized in that it is blended in a proportion of 1 to 30 parts by weight and 0 to 30 parts by weight.

The present invention will be explained in detail below.

The rubber-reinforced styrenic resin (A) in the present invention is obtained by polymerizing an aromatic vinyl monomer and, if necessary, another copolymerizable vinyl monomer in the presence of a rubbery polymer. a graft copolymer or the graft copolymer;
It is a mixture of an aromatic vinyl monomer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl monomer and, if necessary, another copolymerizable vinyl monomer.

Rubbery polymers used in graft copolymers include:
Diene rubber polymers such as polyptadiene, butadiene-sterene copolymer, butadiene-acrylic nitrile copolymer, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, acrylic rubber polymer Examples include non-diene rubber-like polymers such as coalescent and chlorinated polyethylene, which can be used alone or in a mixture of two or more. These rubbery polymers are produced by emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, and the like.

Regarding the particle size and gel content of the rubbery polymer when produced by emulsion polymerization, the aromatic vinyl monomers include styrene, a-methylstyrene, 0-
Examples include methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, d-methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, promstyrene, dibromstyrene, etc.
They can be used alone or in a mixture of two or more.

Other vinyl monomers that can be copolymerized with aromatic vinyl monomers include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethyl. Unsaturated carboxylic acid alkyl esters such as xyl acrylate, methyl methacrylate, ethyl methacrylate, probyl methacrylate, and 2-ethylhexyl methacrylate; maleimides such as maleimide, N-phenylmaleimide, N-methylmaleimide, and N-cyclohexylmaleimide; Monomers are exemplified and can be used alone or in a mixture of two or more.

As the graft polymerization method, known methods such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination thereof are used.

The aromatic vinyl monomer constituting the aromatic vinyl polymer to be mixed with the graft copolymer and other copolymerizable vinyl monomers include those used in the graft copolymer. Any one or more types can be selected and used from the same group as . Further, as a method for polymerizing the polymer, known methods such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination thereof are used.

It is a copolymer consisting of 50 to 89.9% by weight of an aromatic vinyl monomer and 49.9 to 10% by weight of other copolymerizable vinyl monomers.

Examples of vinyloxazoline include 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline,
4.4-dimethyl-2-vinyl-2-oxazoline, 4
．． 4-dimethyl-2-vinyl-5,6-dihydro-4H
-1.3-oxazine, 4.4.6-trimethyl-2-
Vinyl-5,6-dihydro-4H-1,8-oxazine, 2-isobropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline, etc. are exemplified, and one or more of them may be used.

Particularly preferred is 2-vinyl-2-oxazoline.

If the amount of vinyloxazoline is less than 0.1% by weight, sufficient matting properties cannot be obtained, and if it exceeds 20% by weight, the flowability is poor, which is not preferable.

As the aromatic vinyl monomer and other copolymerizable vinyl monomers, the same ones as those exemplified in the section of the graft copolymer are exemplified, and each can be used alone or in combination of two or more. It is preferable.

There is no particular restriction on the molecular weight of Copolymer 0, but preferably the weight average molecular weight is 10.000 to 1,000.0.
It is 00.

The copolymer 0 used in the present invention refers to a monomer 0.1 having a functional group that is reactive with an oxazoline group, that is, a functional group that is reactive with an oxazoline group in the oxazoline-modified copolymer (b). -20% by weight, 50-89.9% by weight of an aromatic vinyl monomer, and 49.9-10% by weight of other copolymerizable vinyl monomers. Examples of functional groups reactive with oxazoline include amino groups, carboxyl groups, acid anhydride groups, epoxy groups, mercapto groups, isocyanate groups, halogen groups, and hydroxyl groups.

The above monomer having an amino group includes acrylamide,
Monomers with carboxyl groups, such as methacrylamide, dimethylaminoethyl acrylate, and dimethylaminoethyl methacrylate, include monomers with acid anhydride groups, such as acrylic acid, methacrylic acid, maleic acid, phthalic acid, fumaric acid, and itaconic acid. Examples of monomers having an epoxy group include glycidyl acrylate-11 glycidyl methacrylate and glycidyl itaconate; examples of monomers having an isocyanate group include vinyl isocyanate, etc. Examples of monomers having a halogen group include thyl acrylate, hydroxyethyl methacrylate, o-, m- or p-hydroxystyrene, and examples of monomers having a mercapto group include vinyl mercabutane. It can be used above.

Among these, monomers having a carboxyl group, an acid anhydride group, and an epoxy group are particularly preferred.

The amount of monomers with functional groups reactive with oxazoline is 0.
．． If it is less than 1% by weight, the reactivity with the oxazoline group is unfavorable, and if it exceeds 20% by weight, the flowability of the final composition will be unfavorable.

Examples of the aromatic vinyl monomer and other copolymerizable vinyl monomers are the same as those exemplified in the graft copolymer section, and each may be used alone or in combination of two or more. Can be done.

There is no particular restriction on the molecular weight of copolymer O, but preferably the weight average molecular weight is 10.000 to 1,000.0.
It is 00.

Further, as the polymerization method for the above-mentioned copolymers ◎ and 0, known emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination thereof can be used.

The thermoplastic resin composition of the present invention consists of the aforementioned rubber-reinforced styrenic resin (6), oxazoline-modified copolymer ◎, and copolymer ◎, and the composition ratio thereof is (f) per 100 parts by weight, (Bl O. 1 to 30 parts by weight and (Q O
-80 parts by weight; outside this range, the balance between impact strength, fluidity and matte level is poor and is not preferred.

Preferably, per 100 parts by weight (A), 00.5 to 25
parts by weight and 00 to 25 parts by weight.

There are no particular restrictions on the method of mixing the rubber-reinforced styrene resin (A), oxazoline-modified copolymer 0, and copolymer (C), and they may be mixed in a latex state, powder, beads,
It can be mixed in the form of pellets, etc. There is also no particular restriction on the order of mixing the three components, including simultaneous mixing of the three components,
Any method of premixing two components and then mixing the remaining component may be used.

The melt mixing method includes Banbury mixer roll,
Any known method such as an extruder can be used.

In addition, when mixing, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, dyes, pigments, plasticizers, flame retardants,
Additives such as a mold release agent can be added. Further, thermoplastic resins such as polyacetal, polycarbonate, polybutylene terephthalate, polyphenylene oxide, polymethyl methacrylate, and polyvinyl chloride can also be appropriately blended.

Next, the present invention will be specifically explained using Examples and Comparative Examples. Note that all parts and percentages are expressed on a weight basis.

Reference example l. Production B- of oxazoline modified copolymer f3)
1: A copolymer having an intrinsic viscosity of 0.56 and consisting of 1 part of 2-vinyl-2oxazoline, 28 parts of acrylonitrile, and 71 parts of styrene was produced by a known solution polymerization method. still,
Intrinsic viscosity was measured in dimethylformamide at 30°C. (Unit 1001/2) B-2: Produce a copolymer with an intrinsic viscosity of 0.55 consisting of 5 parts of 2-vinyl-2-oxazoline, 30 parts of acrylonitrile, and 65 parts of styrene in the same manner as B-1. did.

B-8: In the same manner as B-1, a copolymer having an intrinsic viscosity of 0.53 and consisting of 15 parts of 2-vinyl-2/-oxazoli, 26 parts of acrylonitrile, and 59 parts of styrene was produced.

B-4: Same as B-1, 25 parts of 2-vinyl-2-oxazoline, 23 parts of acrylonitrile, 52 parts of styrene.
A copolymer having an intrinsic viscosity of 0.54 was prepared.

Reference example 2. Production C-1 of Copolymer 0: A copolymer having an intrinsic viscosity of 0.56 and consisting of 5 parts of methacrylic acid, 30 parts of acrylonitrile, and 65 parts of styrene was produced by a known emulsion polymerization method.

C-2: In the same manner as C-1, a copolymer having an intrinsic viscosity of 0.5 fy and consisting of 15 parts of methacrylic acid, 26 parts of acrylonitrile, and 59 parts of styrene was produced.

C-3: 5 parts of glycidyl methacrylate, 30 parts of acrylonitrile, 6 parts of styrene by a known solution polymerization method.
A copolymer having an intrinsic viscosity of 0.55 and consisting of 5 parts was produced.

B-1 to B-4 and c-B were separated and recovered after precipitation in methanol. C-1-C-2 was recovered by salting out with calcium chloride, dehydration and drying. In addition, as the rubber reinforced styrene resin (A), A-1:
“ABS resin” Clarastic @) KU-600 manufactured by Sumitomo Naugatuck ■ A-2 = “AES resin” Uniprite ■ UB-500 manufactured by Sumitomo Naugatack ■ was used.

Example Rubber-reinforced styrenic resin (A), oxazoline-modified copolymer ◎, and copolymer 0 were mixed in the composition shown in Table 1, and melt-mixed and granulated using a 401 m twin-screw extruder. Note that the granulation temperature was set at 280°C.

The physical properties of the obtained resin composition were measured by the following method, and the results are shown in Table 1.

O impact strength (notched Izod): ASTM D-25
6 0 Flowability: Koka type flow tester 0 Surface gloss and gloss unevenness: A 60m x 60+ma, 3rIn thick test piece was molded, and the gloss at the center of the test piece was measured using a Suga Test Instruments Digital Variable Gloss Meter UGV-Tile 4D. It was measured at an incident angle of 602:. The unevenness of gloss on the surface of the test piece was evaluated by visual judgment.

The above test pieces for quality evaluation were molded using a 3.5 ounce injection molding machine with the cylinder temperature set at 260°C.

Examples 1 to 6 and Comparative Examples 1 to 2> The effects of copolymer 0 will be shown.

Examples 7 to 1O1 Comparative Examples 3 to 8> The influence of the amount of oxazoline-modified copolymer 0 is shown.

<Examples 11-12, Comparative Examples 9-10> The influence of the type of rubber-reinforced styrene resin (A) will be shown.

<Effect of the Invention> Compared to conventional matte resin compositions, the resin composition of the present invention has an excellent balance between impact strength, flowability, and matte level of molded products, and has a uniform gloss with no uneven gloss. It has the characteristic that an erased surface can be obtained.

Claims (1)

Scope of Claims: (A) Rubber-reinforced styrenic resin, (B) 0.1 to 20% by weight of vinyl oxazoline, 50 to 89.9% by weight of aromatic vinyl monomer, and other copolymerizable vinyl. Oxazoline-modified copolymer consisting of 49.9 to 10% by weight of a monomer, (C) 0.1 to 20% by weight of a monomer having a functional group reactive with an oxazoline group, and an aromatic vinyl monomer. 50-89
．． 9% by weight and other copolymerizable vinyl monomers 49.
A copolymer consisting of 9 to 10% by weight, per 100 parts by weight of (A), 0.1 to 30 parts by weight of (B) and 0 to 30 parts by weight of (C). thermoplastic resin composition