JP2987975B2 - Low gloss 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 thermoplastic resin composition having excellent matting properties and surface appearance, and also having excellent heat resistance. It is suitable as a part.

[0002]

2. Description of the Related Art Thermoplastic resins are lightweight, moldable and processable.
Due to its characteristics such as electrical insulation, demand has been rapidly increasing in recent years, and its use in the metal replacement field has been greatly expanded. On the other hand, in the fields of automobile interior parts and household electrical equipment parts, there is a demand for safety issues such as dazzling sight and for products with reduced gloss on the surface of molded products for the purpose of giving a sense of calm. Is growing.

[0003] As a general matting method, a method of embossing a mold surface, a method of applying a liquid matting agent to a surface of a molded product, and a method of mixing an inorganic filler with a resin (Japanese Patent Publication No. Sho 4)
No. 9-44582), a method of adding a rubbery polymer after polymerization (Japanese Patent Publication No. 48-24034, Japanese Patent Application Laid-Open No.
JP-A-142259 and JP-B-62-59725), a method of adding a rubber-modified thermoplastic resin (JP-A-56-133353, JP-A-59-89346, JP-A-60-18536). JP-A-60-2
JP-A No. 02143 and JP-A-62-101616) and a method of adding a three-dimensional resin component using a crosslinkable monomer (JP-A-63-63740) are known. JP-A-1-48848 discloses a composition in which a graft copolymer, a crosslinked copolymer and polyglutarimide are blended.

[0004]

The method based on the improvement of the mold surface has problems of expensive mold manufacturing cost, compensation management, and
A sufficient matting effect is not achieved. In addition, in the method using coating, the coating process is costly, and there is a possibility that the surface of the resin may deteriorate due to the solvent. In the mixing of inorganic fillers,
There is a drawback that the mechanical properties of the resin, particularly the impact strength, are greatly reduced, and the appearance of the molded article is poor.

In the method of adding a rubbery polymer,
This causes a reduction in heat resistance and rigidity, and also causes gloss to not disappear evenly (irregularity).

The method using a rubber-modified thermoplastic resin has a problem that the degree of matting varies depending on molding conditions.

Further, the method of adding a three-dimensional resin component using a crosslinkable monomer has problems such as deterioration of the fluidity of the composition and deterioration of the appearance of the surface of a molded article. An object of the present invention is to provide a low-gloss thermoplastic resin composition in which the surface of a molded article has reduced gloss and has an excellent appearance.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention.

That is, the present invention provides (A) (a) 5 to 80 parts by weight of a rubbery polymer, (b) an aromatic vinyl monomer,
One or more vinyl monomers selected from the group consisting of vinyl cyanide monomers and unsaturated carboxylic acid alkyl ester monomers, or a monomer mixture obtained by graft polymerization of 95 to 20 parts by weight. 1 to 99 parts by weight of the graft copolymer, (B) 1 to 60 parts by weight of the polyglutarimide resin, and (C) the formula (I)

[0010]

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Wherein R ₁ , R ₂ and R ₃ may be the same or different, R ₁ is an alkyl group, an alkenyl group (having 1 to 26 carbon atoms) or a hydroquinylalkyl group, and Y is N or CON group, R ₂ and R ₃ represent H or an alkyl group, an alkenyl group (having 1 to 26 carbon atoms), a hydroxyalkenyl group and a hydroquinylalkyl group.
The present invention provides a low-gloss thermoplastic resin composition obtained by blending the compound represented by the formula (A), (B) with respect to 100 parts by weight, and 0.01 to 10 parts by weight. .

As the rubbery polymer (a) which is a constituent component of the graft copolymer (A) used in the present invention, those having a glass transition temperature of 0 ° C. or lower are preferable, and specifically, polybutadiene, Diene rubbers such as polystyrene-butadiene and polyacrylonitrile-butadiene, acrylic rubbers such as polyisoprene, polychloroprene and polybutyl acrylate, and rubbery polymers such as ethylene-propylene-diene monomer terpolymer can be used. Particularly, butadiene or butadiene copolymer is preferred.

(B) Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, op-dichlorostyrene and the like. Styrene is particularly preferred, and these are preferred. One type or two or more types can be used. As the vinyl cyanide monomer, acrylonitrile, methacrylonitrile,
Ethacrylonitrile and the like can be mentioned, and acrylonitrile is particularly preferable.

The unsaturated carboxylic acid alkyl ester monomer is preferably an acrylate ester and / or a methacrylate ester having an alkyl group having 1 to 10 carbon atoms. Can be. Examples of the acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, chloromethyl acrylate, 2-chloroethyl acrylate And the like, but methyl acrylate is particularly preferable.

Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, chloromethyl methacrylate, Examples thereof include 2-chloroethyl methacrylate and the like, and particularly preferred are methyl methacrylate and ethyl methacrylate.

The graft copolymer (A) comprises (a) 5 to 80 parts by weight, preferably 7 to 75 parts by weight of a rubbery polymer,
More preferably 10 to 70 parts by weight of the monomer mixture 95 to
20 parts by weight, preferably 93 to 25 parts by weight, more preferably 90 to 30 parts by weight of a monomer mixture and a polymerization initiator in the above-described ratio in the presence of a known polymerization method such as a rubbery polymer latex. It can be obtained by, for example, a method of emulsifying graft polymerization by supplying the same.

If the proportion of the rubbery polymer (a) in the graft copolymer is less than 5 parts by weight, the resulting resin will have poor impact resistance, and if it exceeds 80 parts by weight, the rubbery polymer will be poorly dispersed and will not be molded. It is not practical because it impairs the appearance of the product.

The ratio of the aromatic vinyl monomer, vinyl cyanide monomer and unsaturated carboxylic acid alkyl ester monomer in the monomer mixture (b) is not particularly limited. The content is preferably from 40 to 90% by weight of an aromatic vinyl monomer, and from 60 to 10% by weight of a vinyl cyanide monomer and / or an unsaturated carboxylic acid alkyl ester monomer.

The polyglutarimide resin (B) used in the present invention is represented by the formula (II)

[0020]

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(Wherein R ₄ , R ₅ and R ₆ in the formula each represent hydrogen or a substituted or unsubstituted alkyl or aryl group having 1 to 20 carbon atoms). It is a polymer or a copolymer.

[0022] If containing formula (II) cyclic imide units, can be applied to even present invention a polyglutarimide any chemical structure, typically R ₄ in formula (II) cyclic imide units And R ₅ is hydrogen or a methyl group, and R ₆ is hydrogen, a methyl group, an ethyl group, a propyl group,
Those which are butyl or phenyl are commonly used. The method for producing polyglutarimide is not particularly limited. For example, polymethyl methacrylate described in JP-A-52-16389 is reacted with ammonia or a primary amine such as methylamine or ethylamine in an extruder. A method of forming a glutarimide ring is useful.

The compound (C) used in the present invention is represented by the formula (I)

[0024]

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(Wherein R ₁ , R ₂ and R ₃ may be the same or different, R ₁ is an alkyl group, an alkenyl group (having 1 to 26 carbon atoms) or a hydroquinylalkyl group, and Y is N or CON group, R ₂ and R ₃ represent H or an alkyl group, an alkenyl group (having 1 to 26 carbon atoms), a hydroxyalkenyl group and a hydroquinylalkyl group.
It is a compound represented by these.

Specific examples include N, N-di (2-hydroxypropyl) dodecylamine, N, N-dihydroxyethylstearylamine, N, N-di (2-hydroxypropyl) dodecaneamide and diethanolamide laurate. And diethanolamides of alkyl monocarboxylic acids such as undecanoic acid diethanolamide, and N, N-dihydroxyethylstearylamine and N, N-di (2-hydroxypropyl) dodecaneamide are particularly preferable. These can be used alone or in combination of two or more.

The resin composition of the present invention further comprises an aromatic vinyl monomer, a vinyl cyanide monomer, a maleimide monomer and, if necessary, another copolymerizable vinyl monomer. It is preferable to incorporate a copolymer (D) obtained by polymerizing the added monomer mixture, since heat resistance is improved.

The aromatic vinyl monomer and vinyl cyanide monomer constituting the copolymer (D) are the same as the graft copolymer.
Aromatic vinyl monomers and vinyl cyanide monomers usable in (A) can be used.

The maleimide-based monomers include maleimide, N-methylmaleimide, N-ethylmaleimide,
-Isopropylmaleimide, Nt-butylmaleimide, N-phenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, N-
p-methylphenylmaleimide, N-cyclohexylmaleimide, No-hydroxyphenylmaleimide, N
-M-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, N-
p-methoxyphenylmaleimide, No-chlorophenylmaleimide, Nm-chlorophenylmaleimide,
N-p-chlorophenylmaleimide, N-naphthylmaleimide and the like are mentioned, and especially N-phenylmaleimide, N-cyclohexylmaleimide, Nt-butylmaleimide, N-isopropylmaleimide and Nm-
Methylphenylmaleimide is preferred. These can be used alone or in combination of two or more.

Other copolymerizable vinyl monomers added as needed include unsaturated carboxylic acid alkyl ester monomers usable in the graft copolymer (A).
(Meth) acrylamide monomers such as acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, dicarboxylic anhydrides such as maleic anhydride and itaconic anhydride, vinyl acetate, vinyl propionate, and vinyl butyrate And carboxylic acid vinyl ester monomers.

The copolymerization amount of the aromatic vinyl monomer and the vinyl cyanide monomer in the copolymer (D) is not particularly limited, but is preferably 30 to 90% by weight of the aromatic vinyl monomer. %, Preferably 10 to 60% by weight of a vinyl cyanide monomer. Further, the copolymerization amount of the maleimide-based monomer is 2 to 60.
% By weight, particularly preferably 5 to 55% by weight.

When the copolymerization amount of the aromatic vinyl monomer, vinyl cyanide monomer and maleimide monomer satisfies the above range, mechanical properties such as impact resistance and thermal stability. However, a particularly excellent composition can be obtained.

The method for producing the copolymer (D) is not particularly limited, and a generally known method such as solution polymerization, bulk-suspension polymerization, suspension polymerization, and emulsion polymerization can be used. There is also no particular limitation on the method of charging the copolymer component, and batch charging may be initially performed, and a part or all of the charged monomers may be continuously charged to prevent generation of a composition distribution of the copolymer, Alternatively, the polymerization may be carried out while being charged separately.

The resin composition of the present invention comprises (A) 1 to 99 parts by weight of a graft copolymer, and (B) 1 to 99 parts by weight of a polyglutarimide resin.
60 parts by weight, preferably 1 to 55 parts by weight, and more preferably 1 to 50 parts by weight. If necessary, the copolymer (D) may further contain 0 to 90 parts by weight, preferably 0 to 70 parts by weight.
You may mix | blend a weight part, More preferably, 1-65 weight part may be mix | blended. Further, the compound (C) is used in a total amount of (A), (B) and (D) of 0.01 to 10 parts by weight, preferably 0.02 to 9 parts by weight, more preferably 0 to 9 parts by weight, per 100 parts by weight. .03
-8 parts by weight.

If the proportion of (A) is less than 1 part by weight, the impact resistance of the molded article is low, while if it exceeds 99 parts by weight, a sufficiently low gloss resin cannot be obtained. If the proportion of (B) is less than 1 part by weight, uniform low gloss of the molded article cannot be achieved, and if it exceeds 60 parts by weight, the moldability is remarkably deteriorated. If the proportion of (C) is less than 0.01 part by weight, a sufficiently low gloss resin cannot be obtained, while if it exceeds 10 parts by weight, the appearance of the molded article is impaired. Further, the heat resistance is improved by adding (D), but if it exceeds 90 parts by weight, the moldability is poor and the impact resistance is poor, which is not preferable.

The amount of the rubbery polymer in the resin composition of the present invention is suitably from 1 to 40% by weight, and particularly preferably from 2 to 35% by weight. Outside the above range, it is difficult to obtain a composition having a good balance of impact resistance, rigidity and thermal stability, which is not preferable. There is no particular limitation on the method for producing the resin composition of the present invention, for example, a graft copolymer (A), a polyglutarimide resin (B), a compound
After uniformly mixing (C) and the copolymer (D) in the form of pellets, powders, pieces, etc. using a high-speed stirrer, melt-kneading with a single-screw or multi-screw extruder with sufficient kneading capacity For example, various methods can be adopted. Two or three components out of the four components, such as the graft copolymer (A) and the polyglutarimide resin (B), and the graft copolymer (A) and the compound (C) and the copolymer (D). May be preliminarily kneaded, and then kneaded while adjusting to a predetermined mixing ratio.

The resin composition of the present invention may be optionally mixed with a thermoplastic resin such as polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polyamide and polymethyl methacrylate, or mixed with polyethylene, polypropylene or ethylene / propylene copolymer. Copolymer, ethylene / butene-1 copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene 2-norbornene copolymer, ethylene / propylene / 1,4-hexadiene copolymer,
By appropriately mixing a polyolefin-based rubber such as an ethylene / vinyl acetate copolymer and an ethylene / butyl acrylate copolymer, it is possible to adjust more desirable physical properties and characteristics.

Depending on the purpose, pigments and dyes, reinforcing agents and fillers such as glass fibers, metal fibers, metal flakes and carbon fibers, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, A plasticizer, an antistatic agent, a fire retardant and the like can be added.

[0039]

EXAMPLES The present invention will now be described more specifically with reference to examples and comparative examples, but these examples do not limit the present invention. Here, “parts” means “parts by weight” and “%” means “% by weight” unless otherwise specified. In addition, after the resin composition finally obtained was molded by an injection molding method, various physical properties were measured by the following test methods.

Izod impact strength: ASTM D-25
6 1/2 inch, notched, 23 ° C (J / m) Deflection temperature under load: ASTM D-648 1/2 inch, 1.82 MPa load (° C) Surface gloss: Suga Test Instruments Co., Ltd., digital bending Using a gloss meter UGV-5D, the surface reflectance (%) of the mirror surface of the molded article at an incident angle of 60 degrees was measured.

Surface appearance: The molded product was visually evaluated.

◎: very good ：: good ×: poor Reference Example 1 (Production of Graft Copolymer (A)) A-1: 35 parts of polybutadiene latex (rubber particle diameter 0.25 μm, gel content 80%) In the presence of (solid content), 65 parts of a monomer mixture composed of 70% styrene and 30% acrylonitrile was emulsion-polymerized. The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to prepare a powdery graft copolymer (A-1).

A-2: Styrene 65 in the presence of 35 parts (in terms of solid content) of the polybutadiene latex used in A-1
%, Acrylonitrile 30%, methyl methacrylate 5
% Of a monomer mixture comprising 100% by weight of emulsion, and the same treatment as in A-1 was carried out to obtain a powdery graft copolymer (A
-2) was prepared.

Reference Example 2 (Production of polyglutarimide resin (B))
1: Pellets of polymethyl methacrylate were charged into an extruder together with ammonia, and extruded at a resin temperature of 270 ° C. while degassing an evolved gas from an exhaust port attached to the extruder. Was manufactured.

B-2: A polyglutarimide resin (B-2) was produced in the same manner as in B-1 except that methylamine was used instead of ammonia as the imidizing agent.

Reference Example 3 (Production of copolymer (D)) D-1:
Styrene 50%, acrylonitrile 20%, N-phenylmaleimide 30% were subjected to suspension polymerization to obtain a copolymer (D-1)
Was prepared.

D-2: 30% of styrene, 20% of α-methylstyrene, 20% of acrylonitrile and 30% of N-cyclohexylmaleimide are subjected to suspension polymerization to obtain a copolymer (D-
2) was prepared.

Reference Example 4 (Production of crosslinked copolymer (E)) A monomer mixture comprising 65% of styrene, 30% of acrylonitrile, and 5% of diethylene glycol dimethacrylate was emulsion-polymerized and subjected to the same treatment as in A-1. Then, a powdery crosslinked copolymer (E) was prepared.

Examples 1 to 6, Comparative Examples 1 to 4 Graft copolymers produced in Reference Examples 1, 2, 3, and 4
(A), polyglutarimide resin (B), copolymer (D), crosslinked polymer (E) and compound (C) as N, N-dihydroxyethylstearylamine (C-1) or N, N
-Di (2-hydroxypropyl) dodecaneamide was mixed with a Henschel mixer in the proportions shown in Table 1 and then extruded at a temperature of 270 with a 40 mmφ extruder.
After extruding at ℃ and pelletizing each, each pellet was subjected to injection molding under the conditions of a molding temperature of 270 ° C and a mold temperature of 80 ° C to prepare each test piece and evaluate its physical properties. Table 1 shows the results.

[0050]

[Table 1]

The following is clear from the examples and comparative examples. That is, the thermoplastic resin composition obtained by the present invention, the gloss of the surface of the molded product is uniformly reduced,
High quality matte, good balance of impact resistance and heat resistance. On the other hand, those without the compound (C) (Comparative Example 1), those without the polyglutarimide resin (B) and the compound (C) (Comparative Example 2), and those with a composition outside the scope of the present invention ( In Comparative Example 3), the reduction in surface gloss was insufficient. In addition, a cross-linked copolymer (E) is blended,
In the case where the compound (C) was not added (Comparative Example 4), the surface gloss and the surface appearance were insufficient.

[0052]

Industrial Applicability The thermoplastic resin composition obtained by the present invention has a remarkable improvement in surface glossiness without impairing the mechanical properties of a molded article, and is used for exterior parts of automobile interior parts and electric appliances for home appliances. It is suitable as a molding material for parts and the like.

This effect is exhibited only when the graft copolymer (A), the polyglutarimide resin (B), and the compound (C) are mixed at a predetermined ratio.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C08L 51/04 33:24) (C08L 55/02 33:24)

Claims (1)

(57) [Claims] (A) In the presence of (a) 5 to 80 parts by weight of a rubbery polymer, (b) an aromatic vinyl monomer, a vinyl cyanide monomer and an unsaturated carboxylic acid alkyl ester One or more vinyl monomers selected from the group consisting of monomers, or 1 to 99 parts by weight of a graft copolymer obtained by graft polymerization of 95 to 20 parts by weight of a monomer mixture, (B) polyglutar 1 to 60 parts by weight of an imide resin, and (C) a compound of the formula (I) (Wherein R ₁ , R ₂ and R ₃ may be the same or different, R ₁ is an alkyl group, an alkenyl group (having 1 to 26 carbon atoms) or a hydroquinylalkyl group, and Y is N
Or a compound represented by CON or R ₂ or R ₃ representing H or an alkyl group, an alkenyl group (having 1 to 26 carbon atoms), a hydroxyalkenyl group, or a hydroquinylalkyl group) by converting (A), (B) For a total amount of 100 parts by weight,
A low-gloss thermoplastic resin composition containing 0.01 to 10 parts by weight.