JP3306205B2 - Matte thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a matte thermoplastic resin composition having excellent impact resistance and flowability.

[0002]

2. Description of the Related Art Rubber-reinforced styrene resins represented by ABS resin are excellent in mechanical properties such as impact resistance and rigidity and workability, and are excellent in appearance of molded articles such as gloss, and are used in automobile parts and office work. It is used in a wide range of applications such as equipment parts and miscellaneous goods.

[0003] However, recently, there has been an increasing demand for matte materials of low gloss, mainly for automobile interior parts, from the viewpoint of safety and to obtain a matte and soft texture.

[0004] Conventional general matting methods include:
There are (i) a method of subjecting a mold surface to graining, (ii) a method of adding an inorganic filler such as calcium carbonate, (iii) a method of adding a rubbery polymer, and (iv) an epoxy group-containing olefin. A method of adding a copolymer (JP-A-59-89)
346) has been proposed.

[0005] Among the above matting methods, in the method (i) in which the mold surface is subjected to graining, the mold surface needs to be repaired frequently because the mold surface is worn. The state depends. Also, (ii) the method of adding an inorganic filler such as calcium carbonate has a drawback that the impact resistance characteristic of the rubber-reinforced styrene resin is significantly reduced. (Iii) The method of adding a rubbery polymer has a problem that defects such as flow marks occur on the surface of a molded product, and a uniform matte surface cannot be obtained. Further, (iv) a method of adding an epoxy group-containing olefin copolymer comprises the steps of (i)
Although a uniform matte surface can be obtained as compared with the methods (i) and (iii), there is a problem that the flowability of the resin decreases as the amount of addition increases.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies on the above-mentioned problems and found that, by mixing a specific graft copolymer in a specific ratio with a rubber-reinforced styrene resin, the problems were solved. The inventors have found that the point can be solved, and have reached the present invention.

That is, the present invention provides the following general formula (1) in the presence of 50 to 99.8 parts by weight of a rubber-reinforced styrene resin (A) and a rubbery polymer (b-1). Wherein R ₁ is H or CH ₃ , R ₂ is a hydroxyalkyl group having 1 to 4 carbon atoms, and a hydroxyalkyl group-containing monomer (b-2) and an aromatic vinyl monomer; Graft obtained by polymerizing a monomer (b-3) consisting of a vinyl cyanide monomer and / or an unsaturated carboxylic acid alkyl ester monomer or another vinyl monomer copolymerizable therewith. A composition comprising the copolymer (B) in an amount of from 0.2 to 50 parts by weight, and wherein the hydroxyalkyl group-containing monomer accounts for 0.05% of the composition comprising the components (A) and (B).
The present invention provides a matte thermoplastic resin composition excellent in impact resistance and flowability, characterized by being mixed at a ratio of up to 5% by weight.

Hereinafter, the present invention will be described in detail.

The rubber-reinforced styrenic resin (A) is defined as a rubbery polymer (a-1) and an aromatic vinyl monomer, a vinyl cyanide monomer and / or an unsaturated carboxylic acid alkyl ester monomer. And a resin obtained by polymerizing a monomer (a-2) composed of a monomer or another vinyl monomer copolymerizable therewith, in the presence of the rubbery polymer (a-1) described above. And a mixture of a graft polymer obtained by polymerizing the monomer (a-2) and a copolymer obtained by polymerizing the graft polymer and the monomer (a-2).

Examples of the rubbery polymer (a-1) include diene polymers having a glass transition temperature of 0 ° C. or lower, such as polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, and ethylene-propylene copolymer. Examples thereof include an ethylene-propylene-based copolymer such as a copolymer, an ethylene-propylene-non-conjugated diene-based copolymer, an acrylate ester-based copolymer, and chlorinated polyethylene, and one or more kinds thereof can be used.

These rubbery polymers are produced by emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization and the like. The gel content of the rubbery polymer in the case of production by emulsion polymerization is not particularly limited, but is preferably from 0 to 95%.

As the aromatic vinyl monomer, styrene,
α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene,
Examples thereof include α-methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, vinylnaphthalene, and the like, and one or more kinds can be used. Particularly, styrene is preferred.

Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, fumaronitrile and the like, and one or more kinds thereof can be used. Acrylonitrile is particularly preferred.

The unsaturated carboxylic acid alkyl ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
-Ethylhexyl (meth) acrylate and the like,
One or two or more can be used. Particularly, methyl methacrylate is preferred.

Other copolymerizable vinyl monomers which can constitute the rubber-reinforced styrene resin (A) together with the above-mentioned monomers include maleimide, methylmaleimide,
Maleimide monomers such as ethylmaleimide, N-phenylmaleimide, O-chloro-N-phenylmaleimide, and unsaturated amide monomers such as acrylamide and methacrylamide are exemplified. it can.

Aromatic vinyl monomer (i), vinyl cyanide monomer and / or unsaturated carboxylic acid alkyl ester monomer (ii) in monomer (a-2) and copolymerizable The composition ratio of the other vinyl monomer (iii) is not particularly limited, but (i) 50 to 90% by weight, (ii)
It is preferably 50 to 10% by weight and (iii) 0 to 40% by weight, more preferably (i) 50 to 80% by weight, (ii) 50 to 20% by weight and (iii) 0 to 30% by weight. It is particularly preferable to use a vinyl cyanide monomer as (ii).

The composition ratio of the rubbery polymer (a-1) to the monomer (a-2) is not particularly limited, but is preferably 5 to 80% by weight of the rubbery polymer (a-1). Monomer (a-2) 9
It is preferably from 5 to 20% by weight.

In particular, a resin comprising a graft polymer having a graft ratio of 20 to 100% and a weight average particle diameter of 0.05 to 5 μm and a copolymer is preferred.

The method for producing the rubber-reinforced styrenic resin (A) (graft polymer and copolymer) is not particularly limited, and may be a known emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, or a combination thereof. Is used.

The graft copolymer (B) in the present invention is represented by the following general formula (1) in the presence of the rubbery polymer (b-1). Wherein R ₁ is H or CH ₃ , R ₂ is a hydroxyalkyl group having 1 to 4 carbon atoms, and a hydroxyalkyl group-containing monomer (b-2) and an aromatic vinyl monomer; Graft obtained by polymerizing a monomer (b-3) consisting of a vinyl cyanide monomer and / or an unsaturated carboxylic acid alkyl ester monomer or another vinyl monomer copolymerizable therewith. It is a copolymer.

As the rubber-like polymer (b-1), those similar to those described in the section of the rubber-reinforced styrene-based resin (A) are exemplified, and one kind or two or more kinds can be used.
The weight-average particle size of the rubber-like polymer (b-1) is not particularly limited. However, from the viewpoint of mattability and balance of physical properties, it is preferable to use a rubber-like polymer of 0.15 μm or less. preferable.

The monomer (b) represented by the above general formula (1)
-2) is a compound having both a radically polymerizable vinyl group and a hydroxyl group, and specific examples thereof include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxymethylbenzyl acrylate, and hydroxymethylbenzyl. Methacrylate, 1
-Hydroxymethyl-4-vinylbenzene, 1- (2-
Hydroxyethyl) -4-vinylbenzene and the like are exemplified, and one kind or two or more kinds can be used.

Further, an aromatic vinyl monomer, a vinyl cyanide monomer, an unsaturated carboxylic acid alkyl ester monomer and other copolymerizable monomers used as the monomer (b-3) Examples of the vinyl-based monomer include the same ones as described in the section of the rubber-reinforced styrene-based resin (A), and one or more kinds thereof can be used.

Aromatic vinyl monomer (i), vinyl cyanide monomer and / or unsaturated carboxylic acid alkyl ester monomer (ii) in monomer (b-3) and copolymerizable The composition ratio of the other vinyl monomer (iii) is not particularly limited, but (i) 50 to 90% by weight, (ii)
It is preferably 50 to 10% by weight and (iii) 0 to 40% by weight, more preferably (i) 50 to 80% by weight, (ii) 50 to 20% by weight and (iii) 0 to 30% by weight. It is particularly preferable to use a vinyl cyanide monomer as (ii).

The composition ratio of the rubbery polymer (b-1) to the monomer (b-2) and the monomer (b-3) is not particularly limited. -1) 5 to 80% by weight, monomer (b-2) 1 to 50% by weight and monomer (b)
-3) preferably 10 to 94% by weight, more preferably (b-1) 10 to 60% by weight, and (b-2) 5
-30% by weight and (b-3) 20-85% by weight.

The method for producing the graft copolymer (B) is also not particularly limited, and may be any of known emulsion polymerization, suspension polymerization, bulk polymerization,
Solution polymerization or a method combining these is used.

The resin composition of the present invention comprises 50 to 99.8 parts by weight of the rubber-reinforced styrene resin (A) and 0.2 to 50 parts by weight of the graft copolymer (B).
If the rubber-reinforced styrene resin (A) is less than 50 parts by weight,
The balance between the impact resistance and the flowability is poor, and if it exceeds 99.8 parts by weight, the matting effect is insufficient, which is not preferable. Preferably it is 75 to 99.5 parts by weight.

The content of the hydroxyalkyl group-containing monomer in the composition comprising the rubber-reinforced styrene resin (A) and the graft copolymer (B) is 0.05 to 5%.
% By weight. If the content is less than 0.05% by weight, the matting effect is insufficient, and if it exceeds 5% by weight, the flowability decreases, which is not preferable. Preferably it is 0.5 to 3% by weight.

The method of mixing the rubber-reinforced styrenic resin (A) and the graft copolymer (B) is not particularly limited, and they can be mixed in a latex state or in a state of powder, beads, pellets or the like. In addition, as a melt kneading method, a known method such as a Banbury mixer, a roll, and an extruder can be adopted.

At the time of mixing, additives such as an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a dye, a pigment, a plasticizer, a flame retardant, and a release agent can be blended, if necessary. In addition, thermoplastic resins such as polyacetal, polycarbonate, polybutylene terephthalate, polyphenylene oxide, polymethyl methacrylate, and polyvinyl chloride can be appropriately blended.

[Embodiments] Next, the present invention will be described based on embodiments, but the present invention is not limited to only these embodiments. All parts and percentages in the composition are based on weight.

-Production of rubber-reinforced styrenic resin (A)-A-1: In a reactor purged with nitrogen, an average particle diameter of 0.5 μm was prepared.
100 parts of polybutadiene latex having a gel content of 85% and a solid content of 50%, 0.3 parts of potassium persulfate and 1 part of pure water
After charging 00 parts, the temperature was raised to 65 ° C. with stirring. Thereafter, 15 parts of acrylonitrile, 35 parts of styrene and t
-A mixed monomer solution consisting of 0.2 parts of dodecyl mercaptan and 30 parts of an aqueous solution of an emulsifier containing 2 parts of sodium dodecylbenzenesulfonate are each added continuously over 4 hours, and thereafter the temperature of the polymerization system is raised to 70 ° C and 3 hours. After aging, the polymerization was completed to obtain a graft copolymer A-1.

A-2: Ethylene-propylene-ethylidene norbornene polymer (propylene content: 40, iodine value: 8, Mooney viscosity: 75) based on a known suspension polymerization method
50%, 34% styrene and 16% acrylonitrile
Was obtained.

A-3: A graft copolymer (average particle diameter of rubber) comprising 50% of a crosslinked butyl acrylate-acrylonitrile rubber (acrylonitrile content: 5%), 35% of styrene and 15% of acrylonitrile based on a known emulsion polymerization method. , 0.25μ) A-3 was obtained.

AI: 0.3 parts of potassium persulfate and 120 parts of pure water were charged into a reactor purged with nitrogen, and then heated to 65 ° C. with stirring. Then acrylonitrile 30
Parts, a mixed monomer solution consisting of 70 parts of styrene and 0.3 part of t-dodecyl mercaptan and 30 parts of an aqueous emulsifier solution containing 2 parts of sodium dodecylbenzenesulfonate were continuously added over 4 hours.
And the mixture was aged for 3 hours to complete the polymerization to obtain an acrylonitrile-styrene copolymer.

-Production of graft copolymer (B)-B-1: In a reactor purged with nitrogen, an average particle diameter of 0.1 μm was prepared.
After charging 100 parts of polybutadiene latex having a gel content of 85% and a solid content of 50%, 100 parts of pure water and 0.3 part of potassium persulfate, the temperature was raised to 65 ° C. with stirring. Thereafter, 30 parts of an emulsifier aqueous solution containing 15 parts of acrylonitrile, 30 parts of styrene, 5 parts of hydroxyethyl acrylate and 0.3 part of t-dodecylmercaptan and 2 parts of sodium dodecylbenzenesulfonate were each added for 4 hours. After continuous addition, the polymerization system was heated to 70 ° C. and aged for 3 hours to complete the polymerization to obtain a graft copolymer B-1.

B-2: Hydroxyethyl acrylate 5
A graft copolymer B-2 was obtained in the same manner as in B-1 except that 12 parts of hydroxypropyl acrylate was substituted.

B-3: Graft copolymer B-3 in the same manner as B-1 except that polybutadiene latex having an average particle diameter of 0.4 μm, a gel content of 85%, and a solid content of 50% was substituted.
I got

BI: Pure water 12 was placed in a reactor purged with nitrogen.
After charging 0 part and potassium persulfate 0.3 part, the temperature was raised to 68 ° C. with stirring. Then acrylonitrile 30
Parts, styrene 65 parts, hydroxyethyl acrylate 5
Parts and a mixed monomer solution consisting of 0.3 parts of t-dodecyl mercaptan and 30 parts of an emulsifier aqueous solution containing 2 parts of sodium dodecylbenzenesulfonate were added continuously over 4 hours, and then the polymerization system was heated to 70 ° C. After aging for 3 hours, the polymerization was completed.

Production of Epoxy Group-Containing Olefin Copolymer Ethylene-glycidyl methacrylate-vinyl acetate copolymer (composition ratio: 90) using an autoclave-type polyethylene production apparatus according to the polymerization conditions of high-pressure polyethylene.
-7-3) was produced by a bulk polymerization method.

The rubber-reinforced styrene resin (A), the graft copolymer (B), the olefin copolymer containing an epoxy group, the SB block ("Tuffrene A" manufactured by Asahi Kasei Corporation) and various organic carboxylic acid compounds are shown in Table 1. After mixing with the composition shown in 1 and melt-kneading using a 40 mm single screw extruder,
Pelletized. The properties of the obtained composition were measured by the following methods. Table 1 shows the results.

Izod with impact notch, conforming to ASTM D-256. 1/4 inch thick, 23 ° C

Heat deformation temperature According to ASTM D-648. 1/2 inch, 18.6 Kg / cm ² load.

The flowability Koka type flow tester, 210 ℃, 30 Kg / cm 2

Surface gloss : 60 mm × 60 mm × 3 mm using a 3.5 oz injection molding machine.
Of the test plate, and the gloss at the center of the test plate was measured at an incident angle of 60 ° using a digital variable-angle gloss meter UGV-4D manufactured by Suga Test Instruments Co., Ltd.

[0046]

[Table 1]

[0047]

As described above, the resin composition of the present invention comprises:
Compared with conventional ones, it has a better balance of impact resistance, matting and flowability, and can be suitably used in applications requiring matting.

Claims (1)

(57) [Claims] 1. A rubber-reinforced styrene resin (A) 50 to 9
In the presence of 9.8 parts by weight and the rubber-like polymer (b-1), the following general formula (1) Wherein R ₁ is H or CH ₃ , R ₂ is a hydroxyalkyl group having 1 to 4 carbon atoms, and a hydroxyalkyl group-containing monomer (b-2) and an aromatic vinyl monomer; Graft obtained by polymerizing a monomer (b-3) consisting of a vinyl cyanide monomer and / or an unsaturated carboxylic acid alkyl ester monomer or another vinyl monomer copolymerizable therewith. A composition comprising the copolymer (B) in an amount of from 0.2 to 50 parts by weight, and wherein the hydroxyalkyl group-containing monomer accounts for 0.05% of the composition comprising the components (A) and (B).
A matte thermoplastic resin composition which is mixed at a ratio of up to 5% by weight.