JPH06299045A - Matte thermoplstic resin composition - Google Patents

Abstract

PURPOSE:To obtain a matte thermoplastic resin compsn. which gives a molded article having a matte appearance and excellent thermal and mechanical properties by compounding a vinyl polymer with a graft copolymer obtd. by the graft polymn. of a specific monomer mixture in the presence of a diene rubber having a specified particle diameter. CONSTITUTION:The compsn. is produced compounding 80-5 pts.wt. graft copolymer obtd. by the graft polymn. of a monomer mixture comprising 0.1-40wt.% glycidyl ester of an alpha,beta-unsatd. acid, 10-40wt.% vinyl cyanide monomer, 50-90wt.% arom. vinyl monomer, and 0-30wt.% other copolymerizable monomer (the sum being 100wt.%) in the presence of 40-95wt.% diene rubber having a mean particle diameter of 150nm or lower with 20-95 pts.wt. copolymer obtd. by copolymerizing a monomer mixture comprising 10-40wt.% vinyl cyanide monomer, 60-90wt.% arom. vinyl monomer, and 0-30wt.% other copolymerizable monomer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention provides a molded article having a matte appearance, excellent impact resistance, rigidity and heat distortion resistance, and a thermoplastic resin composition excellent in molding processability. It is about.

[0002]

2. Description of the Related Art ABS resins have excellent impact resistance,
It is used for various purposes because it has heat distortion resistance, moldability and good surface gloss. Meanwhile, car interior parts,
In the field of light electrical components and the like, there is an increasing demand for a matte component surface for calming, high-class feeling, and ensuring safety by suppressing light reflection. As a method for obtaining a matte surface, improvement from the mold surface, matte coating, or a method of blending a resin with an inorganic substance or a rubber component has been adopted. However, under the present circumstances, sufficient results have not been obtained by these methods. That is, it is difficult to repair and manage the mold by improving the mold surface, and the shape of the gloss changes depending on the molding conditions, and it is difficult to obtain a molded product having a certain gloss. Further, in the case of performing matte coating, there is a drawback that not only an extra step is added but also the product cost is increased. Furthermore, the inorganic compound causes a large decrease in impact resistance, and the rubber compound causes a decrease in heat distortion resistance and rigidity, which easily causes flow marks and weld lines, making it difficult to obtain a molded product having an excellent appearance.

Further, it has been proposed to blend ABS polymer with glycidyl methacrylate and a copolymer of ethylene, styrene, acrylonitrile, acrylic ester and the like, but this method also lowers impact resistance and molding processability. In addition, it is difficult to obtain a molded product having an excellent appearance due to uneven color and the like. Furthermore, when manufacturing a large number of molded products by injection molding, substances volatilized from the resin melted in the mold adhere to the mold and contaminate the mold, filling the crevices on the mold surface. As a result, the matting effect is reduced, and a substance that contaminates the mold is transferred to the molded product, resulting in a significant loss of the appearance of the surface of the molded product.

[0004]

In view of the above situation, the present invention has a matte appearance and is excellent in thermal and mechanical properties and molding processability, and further, the appearance of a molded article due to contaminants during molding. The present invention provides a matte thermoplastic resin composition in which the problem of deterioration of the composition is improved.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors used a diene rubber (A1) having a specific particle size and contained a specific component (A2). Graft copolymer (A) and vinyl copolymer (B)
Was found to have a matte appearance, a molded article having excellent thermal and mechanical properties, and excellent molding processability. Diene rubber (A
1), the graft copolymer (A) and the copolymer (B) were found to be improved by selecting the type of the emulsifier used in the production by the emulsion polymerization method, and the present invention was completed.

That is, according to the present invention, in the presence of 40 to 95 parts by weight of a diene rubber (A1) having an average particle size of 150 nm or less, a glycidyl ester compound (a) of an α, β-unsaturated acid (a) of 0.1 to 0.1 is used. 40% by weight, vinyl cyanide monomer (b) 10 to 40% by weight, aromatic vinyl monomer (c) 5
Monomer mixture (A2) consisting of 0 to 90% by weight and other copolymerizable vinyl monomer (d) 0 to 30% by weight
[(A), (b), (c), (d) 100 wt% in total] 60 to 5 parts by weight of a graft copolymer (A) 80 to 5 parts by weight, and a vinyl cyanide monomer 10 to 40% by weight of the monomer (e) and the aromatic vinyl monomer (f) 6
0 to 90% by weight and other copolymerizable monomer (g) 0 to
30% by weight of a monomer mixture [(e), (f),
(G) 100 wt% in total], and a matte thermoplastic resin composition comprising 20 to 95 parts by weight of a copolymer (B).

The graft copolymer (A) is particularly important in the present invention. That is, the diene rubber 40 to 95 having an average particle size of 150 nm or less, preferably 40 to 100 nm.
In the presence of parts by weight, 0.1 to 40% by weight, preferably 0.1% by weight of the glycidyl ester compound (a) of the α, β-unsaturated acid.
5 to 30% by weight, vinyl cyanide monomer (b) 10 to 4
0% by weight, aromatic vinyl monomer (c) 50 to 90% by weight, other copolymerizable vinyl monomer (d) 0 to 30% by weight [(a), (b), (c) ( d) A total of 100% by weight] is a graft copolymer obtained by graft-polymerizing 60 to 5 parts by weight of the monomer mixture (A2).

In this graft copolymer (A), the average particle size of the diene rubber (A1) which is the base for graft polymerization is 150 nm or less, preferably 40 to 10
It must be in the range of 0 nm, and if it exceeds 150 nm, the matte effect is reduced. The average particle size of the diene rubber can be controlled by the type and amount of emulsifier used during polymerization. Further, it is industrially difficult and impractical to produce a rubber having a particle size of less than 40 nm by an emulsion polymerization method. As the diene rubber (A1), either a polymer of diene alone or a copolymer with other components can be used, but it is preferable that the diene component is 50% by weight or more, specifically, polybutadiene rubber and styrene. -Butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, etc. are illustrated, and these are used individually or in combination of 2 or more types. These diene rubbers are usually produced by an emulsion polymerization method using an alkali metal salt of rosin acid or a higher fatty acid as an emulsifier, but these emulsifiers contain a free organic acid component, If it remains as an impurity, it is not preferable because it has a low melting point and volatilizes as a gaseous substance to cause mold contamination.

In order to improve the problem of mold contamination, it is preferable to use the diene rubber (A1) of the present invention that is polymerized with a sulfonic acid or sulfuric acid ester emulsifier. Examples of the sulfonic acid-based emulsifier include alkylbenzene sulfonic acid, paraffin sulfonic acid, alkali metal salt of succinic acid dialkyl ester sulfonic acid, and examples of the sulfuric acid ester-based emulsifier include alkali metal salt of sulfuric acid ester of higher alcohol. Alone or 2
Used in combination of two or more species.

Glycidyl ester compound (a) of α, β-unsaturated acid used for producing the graft copolymer (A)
Examples thereof include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like, and these may be used alone or in combination of two or more. As the vinyl cyanide monomer (b), acrylonitrile, methacrylonitrile, etc. are used alone or in combination, and as the aromatic vinyl monomer (c), styrene, methylstyrene, chlorostyrene, α-methylstyrene, etc. Are exemplified, and these are used alone or in combination of two or more kinds. Further, as the copolymerizable vinyl compound (d),
Methyl methacrylate, methacrylic acid esters such as ethyl methacrylate, methyl acrylate, acrylic acid esters such as butyl acrylate, acrylic acid, methacrylic acid, phenylmaleimide and the like can be exemplified, and these can be used alone or Used in combination of two or more.

In the graft copolymer (A), when the diene rubber (A1) is less than 40 parts by weight, the impact resistance is lowered, and when it exceeds 95 parts by weight, the moldability is lowered. α,
When the glycidyl ester compound (a) of β-unsaturated acid is 0.
If it is less than 1% by weight, the matting effect is insufficient, and if it exceeds 40% by weight, moldability and impact resistance are deteriorated. When the vinyl cyanide monomer (b) exceeds 40% by weight, thermal coloring occurs during molding, and when it is less than 10% by weight, the impact resistance decreases. If the amount of the aromatic vinyl monomer (c) is less than 50% by weight, the molding processability will deteriorate, and if it exceeds 90% by weight, the impact resistance will decrease. When the graft copolymerization of (A1) and (A2) is performed, the graft copolymerization is possible without using an emulsifier, but if necessary, use the sulfonic acid-based or sulfuric ester-based emulsifiers described above. Is preferable from the viewpoint of preventing mold contamination.

With respect to the composition of the copolymer (B) in the present invention, the vinyl cyanide monomer (e) is 10 to 40% by weight, and if it exceeds 40% by weight, thermal coloring occurs during molding.
The aromatic vinyl monomer (f) is 60 to 90% by weight,
If it is less than 90% by weight, the moldability is deteriorated, and if it exceeds 90% by weight, the impact resistance is deteriorated. The vinyl cyanide monomer (e) used in the production of the copolymer (B) is acrylonitrile, methacrylonitrile or the like, and the aromatic vinyl monomer (f) is styrene, methylstyrene or chlorostyrene. , Α-methylstyrene and the like are exemplified, and these are used alone or in combination of two or more kinds. Further, as the copolymerizable vinyl compound (g),
Methyl methacrylate, methacrylic acid esters such as ethyl methacrylate, methyl acrylate, acrylic acid esters such as butyl acrylate, acrylic acid, methacrylic acid, phenylmaleimide and the like can be exemplified, and these can be used alone or Used in combination of two or more. When the copolymer (B) is produced by emulsion polymerization, it is preferable to use the above-mentioned sulfonic acid-based or sulfuric ester-based emulsifier from the viewpoint of preventing mold contamination.

The matte thermoplastic resin composition of the present invention comprises
It is produced by blending the graft copolymer (A) and the copolymer (B). The matte appearance of the molded body,
Impact resistance, heat resistance, rigidity, and moldability are
Not only each composition and degree of polymerization of (B), but also (A),
It also depends on the blending ratio of (B). The blending ratio for obtaining the target properties of the present invention is 80 to 5 parts by weight of the graft copolymer (A) and 2 for the copolymer (B).
0 to 95 parts by weight [100 parts by weight of ((A) and (B) combined], preferably 6 parts by weight of the graft copolymer (A).
0 to 10 parts by weight, and the copolymer (B) is 40 to 90 parts by weight. That is, if the graft copolymer (A) exceeds 80 parts by weight, moldability, rigidity and heat distortion resistance will decrease, and if it is less than 5 parts by weight, impact resistance will decrease.

Graft copolymer (A) and copolymer (B)
The intrinsic viscosity of the composition of the present invention is preferably in the range of 0.25 to 1.5 (N, N′-dimethylformamide solution, 30 ° C.) in terms of methyl ethyl ketone soluble content. If it is less than 0.25, the mechanical strength such as impact resistance tends to decrease, and if it exceeds 1.5, the moldability tends to decrease.

In carrying out the present invention, the diene rubber (A1), the graft copolymer (A) and the copolymer (B) are preferably obtained by emulsion polymerization, but are not necessarily limited to emulsion polymerization. A usual method can be applied to the emulsion polymerization. That is, it is produced by polymerizing a monomer mixture, which is supplied all at once, intermittently or continuously, in an aqueous medium in the presence of an emulsifier, by a radical initiator. As described above, it is preferable to use a sulfonic acid-based and / or sulfate-based emulsifier as the emulsifier from the viewpoint of preventing mold contamination. Examples of the radical initiator include potassium persulfate, ammonium persulfate, cumene hydroperoxide, and water-soluble or oil-soluble peroxides such as paramenthane hydroperoxide.
These are used alone or in combination of two or more. Other polymerization accelerators and polymerization degree regulators may be appropriately selected from those used in known emulsion polymerization. A usual method can be used to adjust the particle size of the diene rubber. For example, a diene rubber having a small particle size can be easily obtained by increasing the amount of the emulsifier added at the initial stage of polymerization.

Blending, granulation and molding may be carried out by known methods. For example, a mixture of the latex of the graft copolymer (A) and the copolymer (B) is coagulated,
The resin powder obtained by dehydration and drying may be melt-kneaded with a roll, a screw, a Banbury mixer, a kneader or the like, and then used for molding. Alternatively, the latex of the graft copolymer (A) and the latex of the copolymer (B) are separately coagulated, dehydrated,
It is also possible to melt-knead the resin powder obtained by drying after powder blending. In addition, it is possible to add a stabilizer, a lubricant, a pigment, an antistatic agent, etc. in the blending, if necessary.

As the stabilizer, hindered phenol type stabilizers, phosphorus type stabilizers and sulfur type stabilizers which are usually used in ABS resins are preferable. As a hindered phenol-based stabilizer, 1,1,3-tris (2-methyl-4)
-Hydroxy-5-tert-butylphenyl-butane (AO-30), n-octadecyl-3- (3 ', 5'
-Di-tert-butyl-4-hydroxyphenyl) propionate (AO-50), tetrakis [methylene-
3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (AO-60), triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) ) Propionate] (1R245), pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (1R1010).
AO-60), 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6). -Tert-butylphenol), tris- (3,5-di-tert-butyl-4-)
Hydroxybenzyl) -isocyanurate (AO-2
0, IR-3114) and the like.

Examples of sulfur stabilizers include 3,3'-thiodipropionic acid, dialkyl-3,3'-thiodipropionate, pentaerythrityl-tetrakis (3-alkylthiopropionate), and tetrakis [methylene. −
Examples include 3- (alkylthio) propionate] methane and bis [2-methyl-4 (3-alkyl-thiopropionyloxy) -5-tert-butylphenyl] sulfide.

Examples of phosphorus-based stabilizers include stearylphenyl phosphite and tris (mono, di, nonylphenyl)
Phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, di (2,4-di-tert-butylphenyl) pentaerythritol diphosphite,
Tetrakis (2,4-di-tert-butylphenyl)
4,4-diphenylene phosphonite, bis (2,6-
Examples thereof include di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. These stabilizers may be used alone or in combination of two or more.

As the lubricant, organopolysiloxane,
Aliphatic hydrocarbons, esters of higher fatty acids and higher alcohols, amides or bisamides of higher fatty acids and modified products thereof, and metal salts of higher fatty acids are used. Examples of the organopolysiloxane include polydimethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane and the like. Examples of the aliphatic hydrocarbon include synthetic paraffin, polyethylene wax and polypropylene wax. Examples of esters of higher fatty acids and higher alcohols include esters of montanic acid, stearyl stearate, behener behenate and the like. Higher fatty acid amides, bisamides and modified products thereof are synthesized by dehydration reaction from higher fatty acids such as stearic acid amide, ethylenebisstearic acid amide, stearic acid, dicarboxylic acids such as succinic acid and diamines such as ethylenediamine. Examples thereof include compounds having a melting point higher than that of bisamide. Metal salts of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid,
Examples thereof include calcium, magnesium salts, aluminum, and cadmium salts of higher fatty acids such as oleic acid. These lubricants may be used alone or in combination of two or more. Further, the thermoplastic resin composition of the present invention is a conventional ABS resin, AS resin, polyvinyl chloride,
It is also possible to use by blending with polycarbonate or the like.

[0021]

EXAMPLES The present invention will be specifically described below with reference to examples, but these examples do not limit the present invention. In the following description, "part" means "part by weight" and "%".
Represents% by weight. Examples 1 to 6 and Comparative Examples 1 to 3 1) Preparation of diene rubber (A1) The following substances were charged in a polymerization machine equipped with a stirrer. Water 150 parts Potassium persulfate 0.2 parts t-Dodecyl mercaptan 0.2 parts After degassing the system, a predetermined amount of emulsifier and butadiene, or a monomer copolymerizable with butadiene, is further charged, and then the polymerization temperature Polymerization was performed at 60 ° C to obtain a polybutadiene latex or a butadiene copolymer latex.

[0022]

[Table 1] (Note) 1 ABS sodium alkylbenzenesulfonate 2 rosin potassium rosinate 3 In addition to the initial emulsifier, 3 parts of rosin was continuously added while the polymerization conversion rate was 20 to 90%.

2) Preparation of Graft Copolymer (A) The following substances were charged in a polymerization machine equipped with a stirrer. Water 250 parts Sodium formaldehyde sulfoxylate 0.3 parts Ferrous sulfate 0.003 parts Ethylenediaminetetraacetic acid disodium 0.01 parts Polybutadiene (co) polymer latex (A1-1 to A1-5) Predetermined amount After substituting with nitrogen, the temperature was raised to 60 ° C., and then the monomers and polymerization initiators shown in the table below were continuously added to obtain a graft copolymer.

[0024]

[Table 2] (Note) GMA Glycidyl Methacrylate AN Acrylonitrile St Styrene CHP Cumene Hydroperoxide

3) Production of copolymer (B) The following substances were charged in a polymerization machine equipped with a stirrer. Water 200 parts Emulsifier Predetermined amount Sodium formaldehyde sulfoxylate 0.3 parts Ferrous sulfate 0.003 parts Ethylenediaminetetraacetic acid disodium 0.01 parts After replacing the inside of the polymerization machine with nitrogen, raise the temperature to 60 ° C. The indicated monomer and polymerization initiator were continuously added to obtain a copolymer (B-1 was initially charged with α-methylstyrene at once).

[0026]

[Table 3]

(Note) DSS sodium dioctylsulfosuccinate fatty acid sodium oleate αMSt α-methylstyrene St styrene AN acrylonitrile PMI phenylmaleimide tDM tert-dodecyl mercaptan CHP cumene hydroperoxide

4) Production of thermoplastic resin composition The graft copolymer (A) produced in the above (2) and the copolymer (B) produced in the above (3) are mixed in a latex state and oxidized. After adding the inhibitor, it was solidified with calcium chloride. After washing with water, filtration and drying, pelletizing with an extruder,
After injection molding, it was subjected to measurement of various physical properties. The results are shown in Table 4. As is clear from the results in Table 4,
The composition of the present invention has a highly matt appearance and is a thermoplastic resin composition having excellent impact resistance and fluidity, and particularly the compositions of Examples 1 to 4 generate little gas during molding. I understand.

[0029]

[Table 4]

(Note) HDT heat distortion temperature ASTM D-648 18.
6kg / cm ² IZOD Izod Impact Strength ASTM D-256
Notched 23 ° C TS Tensile Strength ASTM D-636 23 ° C EL Tensile Elongation ASTM D-636 23 ° C SPIRAL Spiral Flow 250 ° C 1300
kg / cm ² 3mm thickness Gloss 60 degree reflectance Gas generation Evaluation of the degree of gas generation during injection molding by visual observation

[0031]

The composition of the present invention has a matte appearance and is excellent in impact resistance, rigidity, heat distortion resistance and moldability.

Claims (5)

[Claims] 1. A glycidyl ester compound (a) of an α, β-unsaturated acid (a) of 0.1 to 40% by weight in the presence of 40 to 95 parts by weight of a diene rubber (A1) having an average particle diameter of 150 nm or less, Vinyl cyanide monomer (b) 10 to 40% by weight,
Monomer mixture (A2) [(a), (b) comprising 50 to 90% by weight of an aromatic vinyl monomer (c) and 0 to 30% by weight of another copolymerizable vinyl monomer (d). , (C),
(D) 100 wt% in total] 60 to 5 parts by weight of graft copolymer (A) 80 to 5 parts by weight, vinyl cyanide monomer (e) 10 to 40% by weight, aromatic A monomer mixture consisting of 60 to 90% by weight of a vinyl monomer (f) and 0 to 30% by weight of another copolymerizable monomer (g) [(e), (f), (g) 100% by weight]
A matte thermoplastic resin composition comprising 20 to 95 parts by weight of a copolymer (B) obtained by copolymerizing the above. 2. The thermoplastic resin composition according to claim 1, wherein the diene rubber (A1) is emulsion-polymerized using a sulfonic acid emulsifier and / or a sulfuric ester emulsifier. 3. The thermoplastic resin composition according to claim 1, wherein the graft copolymer (A) is emulsion-graft-copolymerized using a sulfonic acid emulsifier and / or a sulfuric ester emulsifier. 4. The thermoplastic resin composition according to claim 1, wherein the copolymer (B) is emulsion-polymerized using a sulfonic acid emulsifier and / or a sulfuric ester emulsifier. 5. The thermoplastic resin composition according to claim 1, wherein the methyl ethyl ketone-soluble component has an intrinsic viscosity in the range of 0.25 to 1.5 (N, N′-dimethylformamide solution, 30 ° C.).