JP2767916B2 - Thermoplastic resin composition for low gloss molded products - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having extremely good matting properties and excellent surface appearance.

[Prior Art] Thermoplastic resins are lightweight and have good moldability and good electrical insulation. Therefore, the thermoplastic resin is used in fields such as automobile interior parts and household electric appliance parts.
However, these parts usually have a high gloss. However, in recent years, there has been an increasing demand for molded articles having a reduced surface gloss for the purpose of imparting quality and graffiti to the molded articles. In addition, a molded product with high gloss is dazzling to the user's eyes and poses a safety problem. To solve this problem, a molded product with low gloss has been demanded.

As a general matting method for a thermoplastic resin, there are a method of embossing a mold surface, a method of applying a liquid matting agent to a molded product surface, and a method of mixing an inorganic filler with the resin (Japanese Patent Publication No. 44582), a method of adding a rubbery polymer after polymerization (Japanese Patent Publication No. 48-24034, Japanese Patent Application Laid-Open No. 54-142259 and Japanese Patent Publication No. 62-59725), and adding a rubber-modified thermoplastic resin. Methods (JP-A-56-133353, JP-A-59-89346, JP-A-60-18536,
JP-A-202143 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.

However, the method based on the improvement of the mold surface has problems of expensive mold manufacturing cost and warranty management, and does not achieve a sufficient matting effect. In addition, in the method by coating, the coating process is costly, and there is a possibility that the resin surface is deteriorated by the solvent. The method of mixing the inorganic filler has a disadvantage that the mechanical drop properties of the resin, particularly the impact strength, are greatly reduced, and the appearance of the molded article is poor.

In addition, the method of adding the rubbery polymer after the polymerization causes a decrease in heat resistance and rigidity, and further causes the gloss to not disappear uniformly (glare unevenness). The method of adding a rubber-modified thermoplastic resin has a problem that the degree of matting varies depending on molding conditions. Furthermore, the method of adding a three-dimensional resin component using a crosslinkable monomer has drawbacks in that the moldability is poor and the appearance of the molded product is poor.

In addition, recently, a styrene-based resin matted by introducing an epoxy group has been proposed. For example, an ABS resin containing an epoxy group-introduced graft copolymer as a component (JP-A-61-218651), containing an epoxy group-containing copolymer
An ABS resin (Japanese Patent Application Laid-Open No. 63-63740) and a matting resin composition containing an ABS resin and an epoxy group-containing olefin copolymer have also been proposed (Japanese Patent Application Laid-Open No. 59-89346).

A matte resin composition has also been proposed by blending a metal compound with a copolymer of a rubbery polymer and an ethylenically unsaturated carboxylic acid (Japanese Patent Application Laid-Open No. 60-19771).
3).

However, such a resin composition in which an epoxy group or a carboxyl group is simply introduced not only does not have a sufficiently low gloss but also has a poor appearance of a molded article.

On the other hand, a resin composition in which polyglutarimide (hereinafter sometimes abbreviated as PGI) and an ABS resin are blended has been proposed (JP-A-58-83057). This resin composition is excellent in impact resistance and heat resistance, but has high gloss.

Further, a resin composition in which a polymer of an acrylic rubber and an acrylic ester and ABS are mixed with PGI has been proposed (U.
SP4,217,424). Although this resin composition improves the impact resistance of PGI, it still has high gloss.

Further, a resin composition comprising an imidized acrylic resin and a polyamide has been proposed (EPC94,215,
-25836, JP-A-59-117550), there is no matting effect at all.

The applicant of the present application has previously proposed a matting thermoplastic resin composition comprising a vinyl-based cross-linked copolymer containing an ABS resin, a PGI resin and a polyfunctional monomer as a copolymer component (Japanese Patent Application Laid-Open No. Sho 64-64).
48848).

The crosslinked copolymer in this composition is partially crosslinked in advance in the polymer and has no reactivity with PGI. Although it is unknown for this reason, this composition has problems in surface appearance and impact resistance.

As the polyfunctional monomer, for example, two or more, preferably two, copolymerizable double bonds such as a non-conjugated divinyl compound represented by divinylbenzene, diallyl maleate, and a polyacrylate compound are used. Is used.

[Problems to be Solved by the Invention] An object of the present invention is to provide a low-gloss thermoplastic resin composition having excellent matting properties and surface appearance, and also having good impact resistance.

Another object of the present invention is to provide a low-gloss thermoplastic resin composition having excellent rigidity and moldability.

Still another object of the present invention is to provide a low gloss thermoplastic resin composition having excellent heat resistance.

[Means for Solving the Problem] The present invention has the following configuration to achieve the above object.

(A) (a) 5 to 80% by weight of a rubbery polymer, (b) 40 to 90% by weight of an aromatic vinyl monomer, 60 to 10% by weight of a cyanic vinyl monomer, and copolymerizable Other vinyl monomers 0 to 50% by weight mixed monomer 95 to
Graft copolymer 1 to 98 parts by weight of 20 _{wt%, (B) (B 1} ). (A) 40 to 90% by weight of an aromatic vinyl monomer, (b) 60 to 10% by weight of a cyanic vinyl monomer,
(C) 0.01 to 10% by weight of a monomer having a functional group selected from an epoxy group, a carboxyl group and an amino group in the molecule, and (d) another vinyl monomer 0 copolymerizable therewith.
Modified vinyl copolymer obtained by copolymerizing 40% by weight, or (B ₂₎ (e) at least one monomer selected from ethylene and propylene from 50 to 95 wt%, (f) in the molecule 0.1 to 20% by weight of a monomer having a group selected from an epoxy group, a carboxyl group and an amino group, and (g) 0 to 40% by weight of another copolymerizable vinyl monomer. 1 to 40 parts by weight of a modified olefin copolymer, (C) 1 to 60 parts by weight of an imidized acrylic resin, and (D) 40 to 90% by weight of an aromatic vinyl monomer, and a vinyl cyanide monomer 60 And 10 to 90% by weight of a vinyl copolymer obtained by copolymerizing 0 to 40% by weight of another copolymerizable vinyl monomer. A thermoplastic resin composition for a low-gloss molded article, comprising 5 to 40% by weight of a coalescence.

As the rubbery polymer (a) which is a component of the graft copolymer (A) used in the present invention, those having a glass transition temperature of 0 ° C. or lower are suitable, and specifically, polybutadiene and polystyrene-butadiene Diene rubbers such as polyacrylonitrile-butadiene, polyisoprene,
Acrylic rubbers such as 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) As the aromatic vinyl monomer in the monomer mixture, styrene, α-methylstyrene, vinyltoluene,
Examples thereof include o-ethylstyrene and o-chlorostyrene, and particularly preferred are styrene and α-methylstyrene, and one or more of these can be used in combination.

Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is particularly preferable.

Other copolymerizable vinyl monomers are not particularly limited, but are preferably unsaturated carboxylic acid alkyl ester monomers such as acrylates and methacrylates having an alkyl group having 1 to 10 carbon atoms, One or two
More than one species can be used.

Examples of the acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, and the like. preferable.

Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, and the like. Particularly, methyl methacrylate and ethyl methacrylate are preferred.

Further, as other copolymerizable vinyl monomers,
(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.

Further, the graft copolymer (A) is prepared by adding (a) 5 to 80 parts by weight, preferably 7 to 75 parts by weight, more preferably 10 to 70 parts by weight of an aromatic vinyl monomer 40 -90% by weight, preferably 45-85% by weight, more preferably 50-80% by weight, vinyl cyanide monomer 60-10% by weight, preferably 55-12% by weight, more preferably 50-15% by weight %, And if necessary, 95 to 20 parts by weight, preferably 93 to 30 parts by weight, more preferably 90 to 40 parts by weight of a monomer mixture comprising 0 to 50 parts by weight of another vinyl monomer. Obtained by polymerization.

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,
If the amount exceeds the weight part, the rubbery polymer becomes poorly dispersed,
It is not practical because it impairs the appearance of the molded article.

If the proportion of the aromatic vinyl monomer is less than 40% by weight, the molding processability is poor, and if it exceeds 90% by weight, the resulting resin has poor impact resistance and chemical resistance.

On the other hand, if the proportion of the vinyl cyanide monomer is less than 10% by weight, the resulting resin has poor impact resistance, which is not preferred. On the other hand, when the content exceeds 60% by weight, the thermal stability of the graft copolymer is remarkably reduced, and a molded article having a poor color tone is not preferred.

As a method of the graft polymerization, a known polymerization method, for example, a method of continuously supplying a monomer mixture and a polymerization initiator at the above-described ratio in the presence of a rubbery polymer latex to perform emulsion graft polymerization, or the like may be employed. Can be.

Next, the aromatic vinyl-based monomer (a) and vinyl cyanide-based monomer (b) constituting the copolymer (B) can be used in the graft copolymerization (A). And those similar to vinyl cyanide monomers can be used.

The monomer having an epoxy group in the molecule constituting (c) is a compound which shares both a radically polymerizable vinyl group and an epoxy group. For example, the following general formulas (I), (II) and ( And unsaturated carboxylic acid glycidyl esters, unsaturated glycidyl ethers, and epoxy group-containing alkenes represented by III).

(R is an aliphatic or aromatic hydrocarbon radical of C ₂ -C ₁₀ having an ethylenically unsaturated bond.) (R is an aliphatic or aromatic hydrocarbon radical of C ₂ -C ₁₀ having an ethylenically unsaturated bond.) (R ¹ is a C _{2 to} C ₁₀ aliphatic or aromatic hydrocarbon group having an ethylenically unsaturated bond, and R ² is a hydrogen or methyl group.) Specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl ethate Acrylate, glycidyl itaconate, allyl glycidyl ether, 2-methylallyl glycidyl ether, 4-vinylphenyl glycidyl ether, 4,5-epoxy-1-pentene, 5,6-epoxy-1-hexene, p-glycidyl styrene, etc. Is mentioned. These can be used alone or in combination of two or more.

Monomers having a carboxyl group in the molecule constituting (c) include monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid and crotonic acid, itaconic acid,
Examples thereof include dicarboxylic acids such as maleic acid and fumaric acid. Among them, acrylic acid and methacrylic acid can be preferably used. These can be used alone or in combination of two or more.

Examples of the monomer having an amino group in the molecule include aliphatic amines such as 2-aminoethyl acrylate, 2-aminoethyl acrylate, 2-aminoethyl vinyl ether, and 3-aminopropyl vinyl ether; p-aminostyrene; Aminostyrene, p-allylaniline,
and aromatic amines such as m-allylaniline.

The copolymerization amount of the aromatic vinyl monomer (a) in the copolymer (B ₁ ) is 40 to 90% by weight, preferably 45 to 85% by weight, and the vinyl cyanide monomer (b) Copolymer of 60 to 10
%, Preferably 55 to 15% by weight.

If the copolymerization amount of the aromatic vinyl monomer (a) and the vinyl cyanide monomer (b) in the copolymer (b ₁ ) is out of the above range, mechanical properties such as impact resistance may be reduced. Is not practical due to insufficient mechanical properties and insufficient thermal stability.

In the present invention, at least one selected from an epoxy group, a carboxyl group and an amino group in the molecule of (c).
The copolymerization amount of the monomer having the seed is 0.01% in the copolymer (B ₁ ).
To 10% by weight, preferably 0.01 to 5% by weight. If the amount is less than 0.01% by weight, the matting effect cannot be obtained. Also,
If the amount is more than 10% by weight, the surface appearance of the molded article is deteriorated.

In the composition of the present invention, the epoxy group, carboxyl group or amino group of the monomer (c) coexists with the polyglutarimide (C) and is important for the matting effect and the surface appearance of the molded article. Play a role.

The amount of the monomer having an epoxy group, a carboxyl group and an amino group in the (B ₁ ) modified vinyl copolymer in the composition of the present invention is, in the case of a monomer having an epoxy group in the molecule, 0.001 to 0.2% by weight, preferably 0.005 to 0.2
% By weight, in the case of a monomer having a carboxyl group in the molecule, 0.01 to 0.3% by weight, preferably 0.02 to 0.3% by weight, and in the case of a monomer having an amino group in the molecule, 0.01 to 0.8% by weight, preferably Is preferably 0.02 to 0.8% by weight.

(B ₁ ) constituting the modified vinyl copolymer (a),
The (b), (c) and (d) other copolymerizable vinyl monomers are not particularly limited, but (A) other copolymerizable vinyl monomers constituting the graft copolymer. The same as the body is applicable.

In particular, it is preferable that a monomer having a hydroxyl group in the molecule is contained in (d) because the matting effect of the composition is further improved.

The monomer having a hydroxyl group in the molecule is a compound that shares both a radically polymerizable vinyl group and a hydroxyl group, and specific examples thereof include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and acrylic acid. 4
(Meth) acrylates such as -hydroxymethylbenzyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxymethylbenzyl methacrylate, 1-hydroxymethyl-4
-Vinylbenzene, 1- (2-hydroxyethyl) -4
-A vinyl aromatic compound such as vinyl benzene is exemplified as a compound having a relatively small molecular weight. On the other hand, as the compound having a relatively large molecular weight, a compound having a polyalkylene oxide group or a derivative thereof, for example, compounds of the following formulas (IV) and (V) are preferable.

(Wherein, R ³ represents hydrogen or an alkyl group having 1 to ⁴ carbon atoms, R ⁴ represents an alkylene group having 2 to 6 carbon atoms, and n represents 2 to 2)
Indicates 20. As specific examples, polyethylene glycol acrylate, polyethylene glycol methacrylate, poly (propylene oxide) glycol acrylate, poly (propylene oxide) methacrylate, poly (tetramethylene oxide) glycol acrylate, poly (tetramethylene oxide) glycol methacrylate, poly (propylene) (Hexamethylene oxide) remethol methacrylate, polyethylene glycol acrylamide, polyethylene glycol methacrylamide, poly (propylene oxide) glycol acrylamide, poly (propylene oxide) glycol acrylamide, poly (propylene oxide) glycol methacrylamide, poly (tetramethylene oxide) glycol acrylamide , Poly (tetramethylene (Oxide) glycol methacrylamide, and polyethylene glycol methacrylate and polyethylene glycol methacrylamide are particularly preferably used. These can be used alone or in combination of two or more.

Monomers containing a hydroxyl group, (B ₁₎ modified vinyl copolymer 0.1 to 10% by weight, in particular is 0.1 to 5 wt%, preferably for matting effect of the composition is significantly better.

There are no particular restrictions on the method for producing the modified vinyl copolymer (B ₁ ), and bulk polymerization, solution polymerization, bulk-suspension polymerization,
Conventionally known methods such as suspension polymerization and emulsion polymerization are used.
There is no particular limitation on the method of charging the copolymer components, and batch charging may be performed at an initial stage.Also, in order to prevent generation of a composition distribution of the copolymer, a part or all of the charged monomers are continuously added. The polymerization may be carried out while charging or dividing.

The epoxy group-, carboxyl group- or amino group-containing olefin copolymer (B ₂ ) used in the present invention refers to a monomer having an epoxy group in the molecule, a monomer having a carboxyl group in the molecule, or an amino acid in the molecule. It is a copolymer of a monomer having a group and an olefin, or a copolymer of these and an ethylenically unsaturated compound.

As the monomer having an epoxy group, a carboxyl group or an amino group (hereinafter also referred to as an epoxy group, etc.) in the molecule, the same monomers as those of (c) constituting (B ₁ ) can be applied. .

Examples of the olefin include ethylene, propylene, 1-butene, and a copolymer thereof.

Examples of the ethylenically unsaturated compound include unsaturated carboxylic acid unsaturated alkyl esters such as vinyl acetate and vinyl propionate, (meth) acrylic acid saturated alkyl esters such as methyl methacrylate and propyl methacrylate, and vinyl halides. And alkyl vinyl ethers such as ethyl vinyl ether.

The proportion of the olefin in the olefin copolymer (B ₂ ) resin containing an epoxy group, a carboxyl group or an amino group is preferably 50 to 99.9% by weight, particularly preferably 80% by weight or more.

The copolymerization amount of a monomer containing an epoxy group or the like in the molecule is 0.1 to 20% by weight, preferably 0.1 to 15% by weight, particularly preferably 0.1 to 10% by weight.

The copolymerization amount of a monomer having an epoxy group etc. in the molecule is
If the amount is less than 0.1% by weight, the effect of lowering the gloss by copolymerization of this monomer will not be exhibited. On the other hand, if it exceeds 20% by weight, gelation occurs at the time of extrusion, so that the surface appearance of the molded article is deteriorated and the molding processability is unpreferably decreased.

The copolymerization amount of the ethylenically unsaturated compound is 0 to 40.
%, Preferably 0 to 30% by weight.

When the copolymerization amount of the ethylenically unsaturated compound exceeds 40% by weight, it is not preferable because the thermal stability of the final composition is lowered depending on the case.

Further, the amount of the monomer having an epoxy group in the molecule in the resin composition of the present invention is preferably 0.001 to 0.5% by weight, more preferably 0.005 to 0.5% by weight. Further, the amount of the monomer having a carboxyl group in the molecule is preferably 0.01 to 0.5% by weight, more preferably 0.05 to 0.5% by weight. Furthermore, the amount of the monomer having an amino group in the molecule is 0.01 to 0.
8% by weight is preferable, and 0.05 to 0.8% by weight is more preferable.
If it is out of this range, it is not preferable because the glossiness and the surface appearance cannot be simultaneously satisfied.

The epoxy group, carboxyl group or amino group-containing olefin copolymer (B ₂ ) can be produced by various methods. For example, a mixture of an unsaturated glycidyl ether compound or an unsaturated carboxylic acid, an unsaturated amine and an olefin, and, if necessary, an ethylenically unsaturated compound is added at a high temperature and a high pressure (100 to 3000 atm) in the presence of a radical generator. , 100-400 ° C.).

In the composition of the present invention, the presence of the (B ₁ ) modified vinyl copolymer or the (B ₂ ) modified olefin copolymer
The reactivity and compatibility between the ABS resin and the imidized acrylic resin are improved.

The imidized acrylic resin (C) constituting the composition of the present invention is a polymer containing a cyclic imide unit represented by the following formula (VI).

(However, R ⁵ , R ⁶ and R ⁷ in the formula each represent hydrogen or a substituted or unsubstituted alkyl group or aryl group having 1 to 20 carbon atoms.) If the cyclic imide unit is contained, any chemical Although the imidized acrylic resin having the structure can be applied to the present invention, usually, R ⁵ and R ⁶ in the cyclic imide unit are hydrogen or a methyl group, and R ⁷ is hydrogen, a methyl group, or ethyl. Those which are groups, propyl groups, butyl groups or phenyl groups are generally used. The method for producing the imidized acrylic resin is not particularly limited.
A method of forming a glutarimide ring by reacting polymethyl methacrylate with a primary amine such as ammonia or methylamine or ethylamine in an extruder described in JP-A-63989 is useful.

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

As the monomer copolymerizable with the aromatic vinyl monomer and the vinyl cyanide monomer, the same monomer as the copolymerizable monomer in the graft copolymer (A) can be used.

The composition of the present invention is preferable because the matting effect is improved when the vinyl copolymer (D) is a vinyl copolymer containing a hydroxyl group.

As a vinyl polymer containing a hydroxyl group, an aromatic vinyl monomer 40 to 90% by weight, a vinyl cyanide monomer 60 to
A polymer obtained by copolymerizing 10% by weight, 0.1 to 10% by weight of a monomer having a hydroxyl group in the molecule, and 0 to 40% by weight of another monomer copolymerizable therewith is preferred.

As the monomer having a hydroxyl group in the molecule, the same monomer as the monomer having a hydroxyl group in the molecule disclosed in (d) of the modified vinyl copolymer (B ₁ ) can be used.

Hydroxyl-containing vinyl polymer (D) is a composition of composition 10
It is preferable to mix 1 to 30 parts by weight in 0 part by weight, since the matting effect of the composition is improved.

Further, it is preferable to use a maleimide-based monomer as the copolymerizable monomer because the heat resistance of the resin composition is improved.

Maleimide monomers include maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide, N-phenylmaleimide, Nm-methylphenylmaleimide,
-O-methylphenylmaleimide, Np-methylphenylmaleimide, N-cyclohexylmaleimide, N-
o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methoxyphenylmaleimide, N-
Examples thereof include m-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, No-chlorophenylmaleimide, Nm-chlorophenylmaleimide, Np-chlorophenylmaleimide, and N-naphthylmaleimide.

Among these, especially N-phenylmaleimide, N-
Cyclohexylmaleimide, Nt-butylmaleimide, N-isopropylmaleimide and Nm-methylphenylmaleimide are preferred. These can be used alone or in combination of two or more.

The copolymerization amount of the maleimide monomer is preferably from 1 to 50% by weight, particularly preferably from 1 to 40% by weight. In this case, mechanical properties such as impact resistance and thermal stability are good.

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 components, and they may be charged all at once in the initial stage.Also, in order to prevent the formation of a composition distribution of the copolymer, a part or all of the charged monomers are continuously charged. Alternatively, the polymerization may be carried out while being charged separately.

The resin composition of the present invention has a total amount of (A) to (D) of 100.
(A) 1 to 98 parts by weight of the graft copolymer based on parts by weight,
Preferably 2 to 90 parts by weight, more preferably 5 to 90 parts by weight, and 1 to 40 parts by weight, preferably 1 to 30 parts by weight of (B ₁ ) modified vinyl copolymer or (B ₂ ) modified olefin copolymer Parts, more preferably 1 to 25 parts by weight, (C) 1 to 60 parts by weight of the imidized acrylic resin, preferably 2 to 30 parts by weight, more preferably 2 to 20 parts by weight, and (D) a vinyl copolymer. It is composed of 0 to 90 parts by weight, preferably 0 to 70 parts by weight, more preferably 1 to 65 parts by weight.

Here, when the proportion of (A) is less than 1 part by weight, the impact resistance of the molded article is low, while when it exceeds 48 parts by weight, a sufficiently low gloss resin cannot be obtained. If the proportion of (B) is less than 1 part by weight, a sufficiently low gloss resin cannot be obtained. On the other hand, if it exceeds 40 parts by weight, the moldability will be remarkably deteriorated and the appearance of the molded article will be impaired.

The composition of the present invention, by blending (A) with (B) and (C) together, significantly reduces the surface gloss of a molded article, that is, provides a high-grade matte, and has good moldability and moldability. A molded article having an excellent surface appearance can be obtained.
When (C) is not present in the composition of the present invention and the amount of epoxy group, carboxyl group and amino group is large, the surface gloss of the molded product is low, but the moldability and the surface appearance of the molded product are poor. .

The rubbery polymer in the resin composition of the present invention is suitably from 5 to 40% by weight, particularly preferably from 5 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, the graft copolymer (A), the copolymer (B), the polyglutarimide (C) and, if necessary, the copolymer (D) are used. Various methods can be adopted, such as a method of uniformly mixing in a pellet powder or a strip state using a high-speed stirrer or the like, followed by melt-kneading with a single-screw or multi-screw extruder having sufficient kneading ability.

Also, two of the four components, such as the graft copolymer (A) and the copolymer (B), the graft copolymer (A) and the copolymer (B), and the copolymer (D), or A method is also possible in which the three components are preliminarily kneaded and then stretched and kneaded at a predetermined mixing ratio.

The resin composition of the present invention may contain other thermoplastic polymers such as styrene / acrylonitrile copolymer, α-methylstyrene / acrylonitrile copolymer, α-methylstyrene / styrene / acrylonitrile copolymer, styrene /
By mixing methyl methacrylate / acrylonitrile copolymer, styrene / acrylamide copolymer, polymethyl methacrylate, etc., the balance of melt fluidity, heat resistance and impact resistance can be further improved.

For example, when the concentration of the rubbery polymer in the graft copolymer (A) is high, a method of adding one or more of the above copolymers such as a styrene / acrylonitrile / methyl methacrylate copolymer is generally used. It is a target.

In addition, depending on the purpose, pigments and dyes, glass fibers, metal fibers, metal flakes, reinforcing agents and fillers such as carbon fibers, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants,
Plasticizers, antistatic agents, flame retardants and the like can also be added.

[Examples] The present invention will 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 “%” by weight unless otherwise specified. The imide content in the imidized acrylic resin is ¹ H-NMR
Was measured by 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-256 1/2 inch, with notch, 23 ° C (kg · cm / cm) Thermal deformation temperature: ASTM D-648 1/2 inch, 18.6 kg / cm ² load (° C) Formability ： Resin temperature 27
The melt viscosity under the condition of 0 ° C. and an excess of 50 kg was measured.

Flexural modulus: ASTM D-790 1/4 inch, 23 ° C (kg / cm ² ) Surface gloss: Suga Test Instruments Co., Ltd., digital variable gloss meter UG
Using a V-5D, the surface reflected light of the mirror surface of the molded article was measured at an incident angle of 60 degrees.

Surface appearance: The molded product was visually evaluated.

◎: very good ；: good ×: bad (large surface roughness, large gloss distribution, etc.) Reference Example 1 (Production of graft copolymer (A)) A-1: polybutadiene latex (rubber average particle diameter 0.25
In the presence of 35 parts (solid content basis) of 35 parts (μ, gel content 80%), 65 parts of a monomer mixture composed of 70% styrene and 30% acrylonitrile were emulsion-polymerized. The obtained graft copolymerization resistance is
Coagulated with sulfuric acid, neutralized with caustic soda, washed, dried and dried to prepare a powdery graft copolymer (A-1).

A-2: In the presence of 65 parts (in terms of solid content) of the polybutadiene latex used in A-1, 35 parts of a monomer mixture composed of 65% styrene, 30% acrylonitrile, and 5% methyl methacrylate was emulsion-polymerized, -1 to prepare a powdery graft copolymer (A-2).

A-3: In the presence of 15 parts (in terms of solid content) of the polybutadiene latex used in A-1, 85 parts of a monomer mixture composed of 74% of styrene and 26% of acrylonitrile was emulsion-polymerized.
-1 to prepare a powdery graft copolymer (A-3).

A-4: In the presence of 35 parts (in terms of solid content) of the polybutadiene latex used in A-1, 65 parts of a monomer mixture composed of 74% of styrene, 25.3% of acrylonitrile, and 0.7% of glycidyl methacrylate were emulsion-polymerized. The same treatment as in Example -1 was performed to prepare a powdery graft copolymer (A-4).

Reference Example 2 (Production of Copolymer (B)) B-1: 76% of styrene, 23% of acrylonitrile, and 1% of glycidyl acrylate were subjected to suspension polymerization to prepare a bead-shaped copolymer (B-1).

B-2: Styrene 69%, acrylonitrile 30.5%, and glycidyl methacrylate 0.5% were subjected to suspension polymerization to prepare a bead-like copolymer (B-2).

B-3: Styrene 24%, acrylonitrile 5.5%, glycidyl methacrylate 0.5%, methyl methacrylate 70%
Was subjected to suspension polymerization to prepare a bead-like copolymer (B-3).

B-4: 70% of styrene, 25% of acrylonitrile, and 5% of glycidyl methacrylate were subjected to suspension polymerization to prepare a bead-like copolymer (B-4).

B-5: 71% of styrene, 24% of acrylonitrile, 5% of methacrylic acid are subjected to suspension polymerization, and a bead-like copolymer (B-5)
Was prepared.

B-6: Suspension polymerization of 68% of styrene, 24% of acrylonitrile, 4% of acrylic acid, and 4% of methyl methacrylate was performed to prepare a bead-like copolymer (B-6).

B-7: 72% of styrene, 23% of acrylonitrile, 4% of acrylamide, and 1% of methacrylic acid were subjected to suspension polymerization to prepare a bead-like copolymer (B-7).

B-8: A bead-like copolymer (B-8) was prepared by suspending and polymerizing 72% of styrene, 26% of acrylonitrile, 1% of methacrylic acid, and 1% of glycidyl methacrylate.

B-9: 73% of styrene, 24.5% of acrylonitrile, 1.8% of methacrylic acid, and 0.7% of glycidyl methacrylate were subjected to suspension polymerization to prepare a bead-like copolymer (B-9).

B-10: 70% of styrene, 25% of acrylonitrile and 5% of 2-aminoethyl methacrylate were emulsion-polymerized to prepare a powdery copolymer (B-10).

B-11: 65% styrene, 20% acrylonitrile, 8% methyl methacrylate, 7% 4-vinylphenylamine were emulsion polymerized to prepare a powdery copolymer (B-11).

B-12: 74% of styrene, 24% of acrylonitrile and 2% of 4-vinylphenylamine were emulsion-polymerized to prepare a powdery copolymer (B-12).

B-13: Ethylene monomer and glycidyl methacrylate compressed to 1800 kg / cm ² together with a catalyst (di-t-butyl peroxide) were added to a usual autoclave-type polyethylene production apparatus and kept at about 250 ° C. while stirring.
Bulk polymerization was performed for 0 minutes. The obtained copolymer (B-1
3) was separated through a separator.

B-14: A copolymer (B-14) was produced in the same manner as in B-13, except that ethylene, glycidyl methacrylate and methyl methacrylate were used as monomers.

B-15: A copolymer (B-15) was produced in the same manner as in B-13, except that ethylene, glycidyl methacrylate, and vinyl acetate were used as monomers.

B-16: A copolymer (B-16) was produced in the same manner as in B-13, except that ethylene, methacrylic acid, and methyl methacrylate were used as monomers.

B-17: A copolymer (B-17) was produced in the same manner as in B-13, except that ethylene, propylene, methacrylic acid, and vinyl acetate were used as monomers.

B-18: Styrene 70%, acrylonitrile 24.5%, glycidyl methacrylate 0.5%, 2-hydroxyethyl methacrylate 5% were subjected to suspension polymerization to prepare a copolymer (B-18).

B-19: Styrene 73%, acrylonitrile 23.5%, glycidyl methacrylate 1.5%, 2-hydroxyethyl methacrylate 2% were subjected to suspension polymerization to prepare a copolymer (B-19).

B-20: Emulsion polymerization of 75% styrene, 24.8% acrylonitrile, 0.2% divinylbenzene, copolymer (B-20)
Was prepared.

Reference Example 3 (Production of imidized acrylic resin (C)) C-1: Pellets of polymethyl methacrylate were charged into an extruder together with ammonia, and the resin temperature was measured while degassing the generated gas from an exhaust port attached to the extruder. Extrusion was performed at 270 ° C. to produce an imidized acrylic resin (C-1) having an imide content of 40 mol%.

C-2: imide content in the same manner as C-1 except that methylamine was used instead of ammonia as the imidizing agent
A 52 mol% imidized acrylic resin (C-2) was produced.

Reference Example 4 (Production of copolymer (D)) D-1: 50% of styrene, 20% of acrylonitrile, 30% of N-phenylmaleimide were subjected to suspension polymerization to obtain copolymer (D-1).
Was prepared.

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

D-3: A copolymer (D-3) was prepared by subjecting 40% of styrene, 10% of α-methylstyrene, 20% of acrylonitrile, and 30% of N-phenylmaleimide to suspension polymerization.

D-4: 75% of styrene and 25% of acrylonitrile were subjected to suspension polymerization to prepare a copolymer (D-4).

Reference Example 5 (Production of copolymer (E)) E-1: 71% of styrene, 24% of acrylonitrile, 5% of 2-hydroxyethyl methacrylate were subjected to suspension polymerization, and a bead-like copolymer (E-1) Was prepared.

E-2: styrene 68%, acrylonitrile 24%, 2-hydroxyethyl methacrylate 4%, methyl methacrylate 4
% By suspension polymerization to prepare a bead-like copolymer (E-2).

E-3: 74% of styrene, 25% of acrylonitrile, and 1% of 2-hydroxypropyl methacrylate were subjected to suspension polymerization to prepare a beaded copolymer (E-3).

Examples 1 to 13 and Comparative Examples 1 to 6 As the graft copolymer (A) and the copolymer (B) prepared in the reference example, epoxy group-containing copolymers (B-1) to
(B-4), the imidized acrylic resin (C) and the copolymer (D) were mixed in a Henschel mixer at the mixing ratios shown in Table 1, respectively, and then extruded with a 40 mmφ extruder.
After extrusion at 270 ° C. and pelletization, each pellet was subjected to injection molding under the conditions of a molding temperature of 270 ° C. and a mold temperature of 80 ° C., and each test piece was prepared. Table 1 shows these results.

Examples 14 to 25, Comparative Examples 7 to 11 As the graft copolymer (A) and the copolymer (B) prepared in the above reference examples, the carboxyl group-containing copolymer (B-
5) to (B-7), the imidized acrylic resin (C) and the copolymer (D) were mixed in a Henschel mixer in the proportions shown in Table 2, respectively, and then extruded at a temperature of 270 ° C. using a 40 mmφ extruder. Then, each of the pellets was subjected to injection molding under the conditions of a molding temperature of 270 ° C. and a mold temperature of 80 ° C. to produce test pieces, and the physical properties of the test pieces were evaluated. Table 2 shows these results.

Examples 26 to 40, Comparative Examples 12 to 14 As the graft copolymer (A) and the copolymer (B) prepared in the above Reference Examples, copolymers containing epoxy groups and carboxyl groups (B-1), B-2), (B-6) to (B
-9), the imidized acrylic resin (C) and the copolymer (D) were mixed in a Henschel mixer in the proportions shown in Table 3, respectively.
After extruding at 0 ° C. 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, which was evaluated for physical properties. Table 3 shows these results.

Examples 41 to 53, Comparative Examples 15 to 18 The graft copolymers (A) and the copolymers (B) prepared in the above Reference Examples were amino group-containing copolymers (B-10) to
(B-12), the imidized acrylic resin (C) and the copolymer (D) were mixed at the mixing ratio shown in Table 4 by a Henschel mixer, and then extruded by a 40 mmφ extruder.
After extruding at 270 ° C. 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, which was evaluated for physical properties. Table 4 shows these results.

Examples 54 to 66, Comparative Examples 19 to 23 Modified olefin copolymers (B-13) to graft copolymers (A) and copolymers (B) prepared in the above Reference Examples
(B-17), the imidized acrylic resin (C) and the copolymer (D) were mixed in a mixing ratio shown in Table 5 by a Henschel mixer, and then extruded by a 40 mmφ extruder.
After extruding at 270 ° C. 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, which was evaluated for physical properties. These results are shown in Table-5.

Examples 67 to 79, Comparative Examples 24 to 28 As the graft copolymer (A) and the copolymer (B) prepared in the above reference examples, a hydroxyl group-containing copolymer (B-18), (B
-19), imidized acrylic resin (C), copolymer (D)
And copolymer (E) were mixed in a Henschel mixer at the mixing ratios shown in Table-6, then extruded at an extrusion temperature of 270 ° C. using a 40 mmφ extruder, and pelletized. 270 ℃, mold temperature 80 ℃
Was subjected to injection molding under the conditions described above, and each test piece was prepared, and the physical properties of the test piece were evaluated. These results are shown in Table-6.

The following is clear from the examples and comparative examples.

That is, any of the thermoplastic resin compositions obtained by the present invention has a uniformly reduced gloss on the surface of the molded product, a high-quality matting effect, and excellent impact resistance.

On the other hand, those without the functional group-containing copolymer (B) (Comparative Examples 1, 2, 24 to 26) show no decrease in gloss. Further, those without the imidized acrylic resin (C) (Comparative Examples 3, 4, 7 to 10, 12 to 19, 21, 22, and 27) had insufficient surface gloss reduction or surface appearance. Deteriorate.

Furthermore, in the prescription of grafting the epoxy group-containing monomer to the rubber component, the reduction in surface gloss is insufficient (Comparative Example 5). In addition, a formulation using a polyfunctional monomer has insufficient impact resistance (Comparative Example 6).

Further, those deviating from the prescribed compounding amount indicate that the surface gloss is insufficiently reduced (when the amount is small: Comparative Example 11), or the surface appearance is deteriorated while the surface gloss is reduced (when the amount is large: Comparative Example 20, 23, 28).

[Effects of the Invention] The thermoplastic resin composition obtained according to the present invention has remarkably improved surface low gloss without impairing the mechanical properties of the molded product, and is used for exterior parts of automobile interior parts and household electric appliances. It is suitable as a molding material for parts and the like. This effect is obtained by mixing the graft copolymer (A), the reactive functional group-containing copolymer (B), and the imidized acrylic resin (C) at a predetermined ratio. This is the first thing that can be demonstrated.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 33/24 C08L 33/24 51/04 51/04 // (C08L 55/02 25:12 33:24) (C08L 55 / 02 23:08 33:24 25:12) (C08L 25/12 55:02 33:24) (C08L 25/12 55:02 23:08 33:24) (C08L 33/24 55:02 25:12) (56) References JP-A-58-83058 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 23/08, 23/14, 25/12, 33/20, 33 / 2 4,51 / 04,55 / 02

Claims (4)

(57) [Claims] (A) (A) 5 to 80% by weight of a rubbery polymer, (b) 40 to 90% by weight of an aromatic vinyl monomer, 60 to 10% by weight of a vinyl cyanide monomer And 0 to 50% by weight of another vinyl monomer copolymerizable therewith
Graft copolymer with 95 to 20% by weight of a mixed monomer of
Parts by weight, (B) (B ₁ ). (A) 40 to 90% by weight of an aromatic vinyl monomer, (b) 60 to 10% by weight of a vinyl cyanide monomer,
(C) 0.01 to 10% by weight of a monomer having a functional group selected from an epoxy group, a carboxyl group and an amino group in the molecule, and (d) another vinyl monomer 0 copolymerizable therewith.
Modified vinyl copolymer obtained by copolymerizing 40% by weight, or (B ₂₎ (e) at least one monomer selected from ethylene and propylene from 50 to 95 wt%, (f) in the molecule 0.1-20% by weight of a monomer having a functional group selected from an epoxy group, a carboxyl group and an amino group and (g) 0-40% by weight of another vinyl monomer copolymerizable therewith. 1 to 40 parts by weight of the modified olefin copolymer obtained, (C) 1 to 60 parts by weight of an imidized acrylic resin, and (D) 40 to 90% by weight of an aromatic vinyl monomer, vinyl cyanide monomer 60 to 90% by weight of a vinyl copolymer and 0 to 90% by weight of a vinyl copolymer obtained by copolymerizing 0 to 40% by weight of another copolymerizable vinyl monomer. Resin composition for low-gloss molded articles, containing 5 to 40% by weight of a polymer. As wherein (B ₁₎ constituting the modified vinyl copolymer (d) other copolymerizable vinyl monomer, a monomer having a hydroxyl group in the molecule, (B ₁₎ modified The thermoplastic resin composition for a low-gloss molded article according to claim 1, which is contained in the vinyl copolymer in an amount of 0.1 to 10% by weight. 3. A vinyl copolymer (D) comprising from 40 to 90% by weight of aromatic vinyl, 60 to 10% by weight of vinyl cyanide, 0.1 to 10% by weight of a monomer having a hydroxyl group in the molecule. 2. A low-gloss molded article according to claim 1, comprising 1 to 30 parts by weight of a hydroxyl-containing vinyl polymer obtained by copolymerizing 0 to 40% by weight of another polymerizable vinyl monomer. Thermoplastic resin composition. 4. A molded article obtained by molding the thermoplastic resin composition according to any one of claims 1 to 3.