JPS63156851A - Delustered thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having matte appearance and excellent impact resistance, rigidity, heat-deformation resistance and moldability, by compounding a specific graft copolymer, a vinyl copolymer and a polycarbonate resin at specific ratios. CONSTITUTION:The objective composition can be produced by compounding (A) 5-40pts.wt. of a graft copolymer produced by polymerizing (A1) 40-95pts. wt. of a rubbery polymer (e.g. polybutadiene rubber) with (A2) 60-5pts.wt. of a vinyl compound while reacting (A3) 0.1-40wt.% alpha,beta-unsaturated acid glycidyl ester compound, (A4) 10-40wt.% vinyl cyanide compound, (A5) 59-89wt.% aromatic vinyl compound and (A6) 0-30wt.% other copolymerizable vinyl compound and (B) 5-60pts.wt. of a copolymer produced by reacting (B1) 10-40wt.% vinyl cyanide compound, (B2) 60-90wt.% aromatic vinyl compound and (B3) 0-30wt.% other copolymerizable vinyl compound to (C) 10-90pts.wt. of a polycarbonate resin.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a thermoplastic resin composition that has a matte appearance and has excellent impact resistance, rigidity, heat deformation resistance, and moldability. It is something.

(Prior Art and Problems) A resin composition obtained by blending AB8 resin with polycarbonate resin is known as a material with excellent impact resistance and heat deformation resistance. On the other hand, in areas such as automobile interior parts and 5-light electrical parts, there is a sense of calm and luxury.

In order to ensure safety by suppressing light reflection, there is a growing demand for parts with less glossy surfaces. Methods to suppress gloss and obtain matte parts include improving the mold surface, applying matte coating, or adding inorganic or rubber components to resin. but,
At present, these methods have not yielded sufficient results.

In other words, it is difficult to repair and manage the mold by improving the mold surface, and the state of the gloss changes depending on the molding conditions, making it difficult to obtain a molded product with a constant gloss.

A material-free formulation results in a significant drop in impact resistance, while a rubbery formulation reduces heat deformation resistance and rigidity, and tends to cause flow marks and weld lines, making it difficult to obtain a molded product with an excellent appearance.

(Means and Effects for Solving the Problems) As a result of intensive study by the present inventors regarding a composition comprising an ABS resin and a polycarbonate resin that has excellent physical properties as well as excellent matting properties, A composition obtained by blending a graft copolymer (A) containing a specific component with a vinyl copolymer) and a polycarbonate resin (C) has a matte appearance and has a thermal resistance of 5. It was discovered that the material has excellent physical properties and moldability, leading to the present invention.

That is, in the present invention, when 60 to 5 parts by weight of a vinyl compound is polymerized to 40 to 95 parts by weight of a rubbery polymer, α,
Glycidyl ester compound of β-unsaturated acid 0.1-40
Weight%, vinyl cyanide compound 10-40% by weight, aromatic vinyl compound 59-89% by weight, other copolymerizable vinyl compounds 0-30% by weight (total of 100% by weight)
) with 5 to 40 parts by weight of a graft copolymer (A), 10 to 40% by weight of a vinyl cyanide compound, 60 to 90% by weight of an aromatic vinyl compound, and 0 to 40% of other copolymerizable vinyl compounds. 30% by weight (total of 100% by weight)
5 to 60 parts by weight of a copolymer obtained by reacting ), and 10 to 90 parts by weight of a polycarbonate resin ((A),
The composition consists of a total of 100ii parts of components (B) and (C).

Particularly important in the present invention is the graft copolymer (A). That is, when reacting 40 to 95 parts by weight of a rubbery polymer with 60 to 5 parts by weight of a vinyl compound, 0.1 to 40% by weight of a glycidyl ester compound of an α,β-unsaturated acid,
Preferably, the essential components are 0.5 to 30% by weight, including 10 to 40% by weight of vinyl cyanide compounds, 59 to 89% by weight of aromatic vinyl compounds, and 0 to 30% by weight of other copolymerizable vinyl compounds. This is a graft copolymer obtained by reacting the following compounds.

In this graft copolymer (A), if the rubber-like polymer is less than 40 parts by weight, impact resistance etc. will be reduced, and if it exceeds 95 parts by weight, moldability etc. will be deteriorated, which is not preferable. α
If the content of the glycidyl ester compound of a β-unsaturated acid is less than 0.1% by weight, the matting effect will be insufficient, and if it exceeds 40% by weight, moldability, impact resistance, etc. will deteriorate, which is not preferable. Further, if the vinyl cyanide compound exceeds 40% by weight, heat coloring occurs during molding, and if it is less than 10% by weight, the impact resistance decreases, which is not preferable. Aromatic vinyl compound is 59
If it is less than 89% by weight, the moldability will deteriorate, and if it exceeds 89% by weight, the impact resistance will decrease, which is not preferable.

Examples of the rubbery polymer used in the graft copolymer (A) include diene-based polymers such as polybutadiene rubber, styrene-butadiene copolymer rubber (SBR), and acrylonitrile-butadiene copolymer rubber (NBR'). Rubber; acrylic rubber such as polybutyl acrylate; and ethylene-propylene-nonconjugated diene terpolymer rubber (
Polyolefin rubber such as EPDM) is used.

Examples of glycidyl esters of α,β-unsaturated acids include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Examples of vinyl cyanide compounds include acrylonitrile and methacrylnitrile; examples of aromatic vinyl compounds include styrene, methylstyrene, and chlorostyrene.

Examples include α-methylstyrene. Furthermore, examples of copolymerizable vinyl compounds include methyl methacrylate, ethyl methacrylate, acrylic acid, methacrylic acid, ethyl acrylate, butyl acrylate, and phenylmaleimide.

In the copolymerization process of the present invention, the vinyl cyanide compound is preferably used in an amount of 10 to 40% by weight, and if it exceeds 40% by weight, heat coloring may occur during molding, which is undesirable. If it is less than 10% by weight, impact resistance etc. deteriorate, which is not preferable. The aromatic vinyl compound is preferably 60 to 90% by weight, and 60% by weight.
If it is less than 90% by weight, the molding processability deteriorates, and if it exceeds 90% by weight, the impact resistance decreases, which is not preferable. Examples of vinyl cyanide compounds include acrylonitrile and methacrylnitrile, and examples of aromatic vinyl compounds include styrene.

Examples of vinyl compounds that can be copolymerized include methylstyrene, chlorostyrene, and α-methylstyrene, and examples of copolymerizable vinyl compounds include acrylic acid, methacrylic acid, ethyl acrylate, methyl methacrylate, butyl acrylate, and phenyl maleimide.

The above graft copolymer (A) and copolymer) are:
It is preferably obtained by emulsion polymerization, but is not limited to emulsion polymerization. i.e. bulk polymerization.

Polymerization can be carried out by commonly known methods such as suspension polymerization, solution polymerization, and bulk-suspension polymerization. Further, there is no particular restriction on the method of charging the compound and the rubbery polymer, and any of initial batch charging, seven-part charging, and continuous charging may be used. In the case of dividing or continuous charging, the composition may be changed during the polymerization.

There is no particular restriction on the intrinsic viscosity of the graft copolymer (A) and copolymer (), but the intrinsic viscosity of the methyl ethyl ketone-soluble component of the graft copolymer (A) and copolymer () is A range of 0.15 to 1.5 dl/I (N,N'-dimethylformaldebide solution, 30°C) is preferred.

The polycarbonate resin Ω in the present invention is an aromatic polycarbonate having an aromatic residue in the main chain. Polycarbonate resin can be produced by either the transesterification method or the phosgene method.

The composition is preferably a polycarbonate resin derived from 2.2-(A,4'-dioxydiphenyl)propane, but a blend of so-called modified polycarbonate resins, copolycarbonate resins, and polycarbonate resins with different molecular weights is used. It is also possible. Although there is no particular restriction on the molecular weight of the polycarbonate resin, an average molecular weight of 15,000 to 50,000 is preferred.

The properties such as matteness, impact resistance, and heat deformation resistance of the thermoplastic resin composition comprising the graft copolymer (A), copolymer a3), and polycarbonate resin (C) of the present invention are the same as those described above (
It is greatly influenced not only by the composition of components A), (■), and (C), but also by their blend ratio. A preferred blend ratio is 5 to 40 parts by weight of the graft copolymer (A);
5 to 60 parts by weight of copolymer), polycarbonate resin (
C) 10 to 90 parts by weight [components (A), ■), and (C)) totaling 100 parts by weight]. Copolymer (A) is 5
If it is less than 40 parts by weight, the matte effect and impact resistance will decrease.
If the amount is more than 1 part by weight, heat resistance to modification, molding processability, etc. will deteriorate, which is not preferable. If the amount of copolymer) is less than 5 parts by weight, molding processability,
Heat deformation resistance, etc. decreases, and if it exceeds 60 parts by weight, impact resistance,
This is not preferable because the matting effect etc. deteriorates. Polycarbonate resin (If Q is less than 10 parts by weight, impact resistance, heat deformation resistance, etc. will decrease, and if it is 90 parts by weight or more, matting effect, moldability, etc. will decrease, which is not preferable.)

Blending, granulation, and shaping can be carried out by methods known per se. For example, a mixture of latexes of graft copolymer (A) and copolymer) is salted out, coagulated, dehydrated,
The powder obtained by drying and the powder or pellets of polycarbonate resin (C) may be blended and kneaded under heating using a roll, screw, Banbury mixer, kneader, etc., and then used for molding. Furthermore, stabilizers, pigments, lubricants, fillers, etc. may be added during blending, if necessary. Other thermoplastic resins, such as PET resin, PBT resin.

Nylon resin, PVC resin, polyacetal resin.

It is also possible to use it in combination with ABS resin or the like.

The thermoplastic resin composition of the present invention thus obtained has a matte appearance, impact resistance, and rigidity.

It has excellent heat deformation resistance and moldability.

(Examples) The present invention will be specifically explained below using Examples and Comparative Examples, but these Examples do not limit the present invention.

In addition, hereinafter, unless otherwise specified, "part" and ".%" each indicate a weight part of 5% by weight.

(a) Production of graft copolymer (5) The following materials were charged into a reaction vessel equipped with a stirrer.

water 250
Part Sodium Formaldehyde Sulfoxylate 0.2
0.0025 parts Ferrous sulfate 0.0025 parts Disodium ethylenediaminetetraacetate 0.001 parts Rubber-like polymer After deoxidizing the specified amount shown in Table 1,
After heating to 60°C without stirring in a nitrogen stream, the table
The monomer mixture shown in 1 was continuously added dropwise at a rate of 10 parts/hour, and after the addition was completed, the mixture was stirred at 60°C for 1 hour to complete the polymerization.

(b) Production of copolymer) The following materials were charged into a reaction vessel equipped with a stirrer.

Water 250 parts Sodium laurate 3 parts Sodium formaldehyde sulfoxylate 0.4 parts Ferrous sulfate 0.0025 parts Disodium ethylenediaminetetraacetate 0.01 parts After deoxygenation, heat to 60°C without stirring in a nitrogen stream. After heating, monomer (I) shown in Table 2 was charged.

After thorough stirring and emulsification, the monomer mixture (I) shown in Table 2 was added dropwise continuously. After the dropwise addition was completed, stirring was further continued at 60°C for 1 hour to complete the polymerization.

e→ Production of thermoplastic resin composition The graft copolymer produced as in (a) and (b) above (
A) and the copolymer) are mixed in a predetermined ratio in a latex state, a phenolic antioxidant is added to this mixed latex, and after coagulating with aluminum sulfate,
After washing with water, separating and drying, the mixture was blended with polycarbonate resin, extruded in a vented extrusion mode at 270'C (setting), pelletized, and injection molded, and various measurements were performed.

Table-1 (Note-1) PBd: Polybutadiene rubber (latex form) with an average particle size of 2,600^ PBA: Polybutyl acrylate rubber (latex form) with an average particle size of 2,400^ EPDM: Ethylene-propylene with an average particle size of 81,000λ Non-conjugated diene rubber (latex form) GMA: Glycidyl methacrylate N: Acrylonitrile St: Styrene BA = Butyl acrylate CUP: Cumene hydroperoxide tDM
: Tertiary dodecyl mercaptan (blank below) Table 2 (Note 2) αMSt : α-methylstyrene (blank below) PC: Polycarbonate manufactured by Konjin Kasei (K-1250W) Izot impact value: ASTM D-256 notched .

-20°C (kq-α/α) Heat distortion temperature: ASTM D-64818, 6kg/c
a Load (°C) Tensile Crab ASTM D-68623°C (kq/ca
) Fluidity: Koka formula B method flow 260'C.

Load 100 kti/cyj (X 10-”cc/s
ec) Reflectance: Using an uncolored pellet, a box-shaped molded product with a length of 180πM5 width of 100mm and a thickness of 3mm is formed using an injection molding machine, and the reflectance at a certain position (mirror surface) is 60°7 (%). ) Surface appearance: The same molded product as above was obtained using uncolored pellets and black colored pellets, and visually observed flow marks and uneven yellowing in 5 colors.

Evaluate the weld line and use the following criteria It was displayed in

○...Good △...Slightly bad ×...Bad Table-1
, 2 and 3, those within the scope of the present invention have a matte appearance, and are impact resistant and rigid.

It can be seen that the product has excellent heat deformation resistance and moldability (5) and surface appearance.

Claims (1)

[Claims] (1) When polymerizing 60 to 5 parts by weight of a vinyl compound to 40 to 95 parts by weight of a rubbery polymer, 0.1 to 40% by weight of a glycidyl ester compound of an α,β-unsaturated acid, a vinyl cyanide compound 10-40
5 to 40 parts by weight of a graft copolymer (A) obtained by reacting 59 to 89 weight % of an aromatic vinyl compound and 0 to 30 weight % of another copolymerizable vinyl compound, and 10 to 40 parts by weight of a vinyl cyanide compound. 40% by weight, aromatic vinyl compound 60~
5 to 60 parts by weight of a copolymer (B) obtained by reacting 90% by weight with 0 to 30% by weight of another copolymerizable vinyl compound,
and 10 to 90 parts by weight of polycarbonate resin (C) [
A matte thermoplastic resin composition consisting of (A), (B), and (C) (100 parts by weight in total)].