JP2550474B2 - Light-resistant thermoplastic resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition having excellent heat resistance and light stability, more specifically, a polymer having an imide group in its side chain, a specific light stabilizer and a specific hindered polymer. The present invention relates to a thermoplastic resin composition containing a phenol compound as an essential component. The composition of the present invention is used for automobile parts, electricity,
It can be preferably used for electronic parts, office equipment parts, heat appliances and the like.

[0002]

2. Description of the Related Art A polymer having an imide group in its side chain, particularly a resin composition comprising this and a styrene-butadiene-acrylonitrile copolymer, polyester, polyamide, and / or polycarbonate has heat resistance, impact resistance, and
It retains excellent electrical properties and is therefore injection molded,
Wide applications are expected for general molded products, film and sheet materials obtained by extrusion molding, press molding or other various molding methods.

[0003]

When these polymers having an imide group in the side chain are continuously used, the molded product is discolored or the physical properties, particularly impact resistance and elongation are remarkably lowered due to the influence of ultraviolet rays. Have.

[0004]

Means for Solving the Problems The present inventor has conducted diligent studies to improve the above-mentioned drawbacks of a polymer having an imide group in a side chain and a composition containing the same. By adding a specific hindered phenol compound, the light resistance was remarkably improved, and a thermoplastic resin composition having excellent heat resistance was also successfully obtained.

That is, in the present invention, 0.01 to 100 parts by weight of a hindered amine compound having a melting point of 50 ° C. or more per 100 parts by weight of a thermoplastic resin containing a polymer having an imide group in its side chain.
A thermoplastic resin composition comprising 5 parts by weight and 0.01 to 5 parts by weight of a hindered phenol compound having a molecular weight of 300 or more.

The polymer having an imide group in the side chain in the present invention includes i) a copolymer obtained by polymerizing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride in the presence or absence of a rubbery polymer. A polymer obtained by imidizing a polymer, ii) polymerizing an aromatic vinyl monomer, an unsaturated dicarboxylic acid anhydride and a vinyl monomer copolymerizable therewith in the presence or absence of a rubbery polymer. A polymer obtained by imidizing the above copolymer,
iii) a polymer obtained by imidizing a copolymer obtained by polymerizing olefin and unsaturated carboxylic acid in the presence or absence of a rubber-like polymer, iv) acrylic acid in the presence or absence of a rubber-like polymer And / or a polymer obtained by imidizing a copolymer obtained by polymerizing a monomer copolymerizable with methacrylic acid, v) an aromatic vinyl monomer in the presence or absence of a rubber-like polymer,
Polymer prepared by polymerizing maleimide and / or N-substituted maleimide, vi) Aromatic vinyl monomer, maleimide and / or N-substituted maleimide and copolymerizable with them in the presence or absence of rubbery polymer There are polymers obtained by polymerizing various vinyl monomers.

Further, the thermoplastic resin containing a polymer having an imide group in the side chain in the present invention includes the above-mentioned i) to v
Acrylonitrile-butadiene-styrene and / or α-methylstyrene copolymer, methylmethacrylate-
Butadiene-styrene copolymer, acrylonitrile-ethylene / propylene-styrene copolymer, acrylonitrile-styrene and / or α-methylstyrene copolymer, rubber modified styrene polymer, polycarbonate, polyetherimide, polyamide, polyester, polyarylate Examples of the thermoplastic resin include one or more polymers selected from polyether sulfone, polysulfone, styrene-butadiene block copolymer, polyphenylene oxide, polyphenylene sulfide, polyester elastomer, and Nanron elastomer. As a matter of course, a thermoplastic resin containing a polymer having an imide group in the side chain also includes a polymer having an imide group in the side chain alone.

In the present invention, a hindered amine compound having a melting point of 50 ° C. or higher is used as the specific light stabilizer added to the thermoplastic resin containing the polymer having an imide group in the side chain.

Examples of the hindered amine compound having a melting point of 50 ° C. or higher include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, 1, 2, 3,
4-tetrakis (2,2,6,6-tetramethyl-4-
Piperidyloxycarbonyl) butane, 1,2-bis (2-oxo-3,3,5,5-tetramethylpiperidyl) ethane, 1, (3,5-di-tert-butyl-4-hydroxyphenyl) -1 , 1-bis (2, 2, 6, 6-
Tetramethyl-4-piperidyloxycarbonyl) pentane, poly [1-oxyethylene (2,2,6,6-tetramethyl-1,4-piperidyl) oxysuccinyl], poly [2- (1,1,4- Trimethylbutylimino) -4,6-triazinediyl- (2,2,6,6-
Tetramethyl-4-piperidyl) iminohexamethylene- (2,2,6,6-tetramethyl-4-piperidyl)
Imino], N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (2,2
2,6,6-Tetramethyl-4-piperidyl) amino]
-6-Chloro-1,3,5-triazine condensate and N-methyl compounds thereof are mentioned.

The hindered phenol compound having a specific molecular weight of 300 or more added to the thermoplastic resin containing the polymer having an imide group in the side chain in the present invention is octadecyl-3- (4-hydroxy-3, 5-di-tert-butylphenyl) propionate, tocopherol, 2,2'methylenebis (4-methyl-6-tert-)
Butylphenol), 2,2'-methylenebis (4-ethylene-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol),
4,4'-thiobis (6-tert-butyl-m-cresol), styrenated cresol, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocinnamid) 1, 1,3-tris (2-methyl-
4-hydroxy-5-tert-butylphenyl) butane,
1,3,5-Trimethyl-2,4,6-tris (3,5
-Di-tert-butyl-4-hydroxybenzyl) benzene, 6- (4-hydroxy-3,5-di-tert-butylanilino) -2,4-bisoctylthio-triazine 2,2'-oxamidebis [ethyl 3 -(3,5-di-
tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol bis 3 (2-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,3,5-tris (4-tert-butyl-3) -Hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 1,3,5-tris (3 ', 5'-di-tert-butyl-4-hydroxybenzyl) s-triazine-2,
4,6- (1H, 3H, 5H) trione, 2,2'-methylenebis [6- (1-methylcyclohexyl) p-cresol], 2,2'-dihydroxy-3,3'-dicyclohexyl-5,5 '-Dimethyl-diphenylmethane, 1,6-hexanediol-bis [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3', 5'-di-
tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4
-Methylphenyl acrylate, 2'-vinyloxyethyl 3,5-di-tert-butyl-4-hydroxybenzoate and the like.

The amount of the light stabilizer hindered amine used in the present invention is 0.01 to 5 parts by weight per 100 parts by weight of the thermoplastic resin containing the polymer having an imide group in the side chain. It is more preferably 0.05 to 4 parts by weight. When the amount of the light stabilizer is less than 0.01 part, the light stability of the composition is poor, and when the molded product is irradiated with ultraviolet rays for a long period of time, it is discolored or its mechanical properties are significantly deteriorated. on the other hand,
If it exceeds 5 parts by weight, the heat resistance may be lowered, the light stabilizer may bleed on the surface during use at high temperature, and the impact resistance and tensile stress may be lowered. As the specific light stabilizer used in the present invention, a hindered amine compound and another light stabilizer may be used in combination.

The amount of the specific hindered phenol compound used in the present invention is 0.01 per 100 parts by weight of the thermoplastic resin containing the polymer having an imide group in the side chain.
~ 5 parts by weight. More preferably, it is 0.03 to 3 parts by weight. The amount of hindered phenol compound is 0.01
If the amount is less than the amount by weight, the composition tends to deteriorate during extrusion molding, the impact resistance remarkably deteriorates, and there are disadvantages that the molded product is liable to burn or flash. Further, when the amount of the hindered phenol compound exceeds 5 parts by weight, heat resistance is lowered, and impact resistance, tensile stress and the like are also seriously disadvantageous.

The composition of the present invention is a mixture of a thermoplastic resin containing a polymer having an imide group in the side chain, a hindered amine compound and a specific hindered phenol compound, but the mixing method is not particularly limited. Well-known means can be used. Examples of the means include a Banbury mixer, a tumbler mixer, a mixing roll,
Examples thereof include a single-screw or twin-screw extruder. Examples of the mixing form include ordinary melt mixing, multi-stage melt mixing using master pellets and the like, and solution blending.

Further, other antioxidants, flame retardants, ultraviolet absorbers, plasticizers, lubricants, glass fibers, carbon fibers, fillers such as calcium carbonate, colorants, metal powders, etc. are added to the composition of the present invention. It is also possible to do so.

[0015]

EFFECT OF THE INVENTION By containing a thermoplastic resin containing a polymer having an imide group in the side chain, a hindered amine compound having a melting point of 50 ° C. or higher, and a hindered phenol compound having a molecular weight of 300 or higher, heat resistance is improved. In a property and accelerated exposure test, a resin composition excellent in retention of mechanical properties such as impact resistance, small discoloration, and excellent in bleeding stability can be obtained. If a light stabilizer having a melting point of less than 50 ° C. is used, the heat resistance is greatly reduced, and in the accelerated exposure test, the light stabilizer is liable to bleed on the surface. In addition, when a hindered phenol compound having a molecular weight of less than 300 is used, the initial impact resistance and heat resistance of the molded product are greatly reduced, and even in the accelerated exposure test, the impact resistance is further greatly reduced. .

[0016]

EXAMPLES The present invention will be described below in greater detail by giving Examples. All parts and percentages in the examples are expressed on a weight basis.

Experimental Example (1) Aroma in the presence of a rubbery polymer
Polymerize group vinyl monomer with unsaturated dicarboxylic acid anhydride
In the autoclave equipped with a stirrer, 60 parts of styrene, 100 parts of methyl ethyl ketone (MEK) and 10 parts of polybutadiene cut into small pieces were charged, and the system was replaced with nitrogen gas. Then, the rubber was dissolved by stirring at room temperature for a whole day and night. After adjusting the temperature to 85 ° C., a solution prepared by dissolving 40 parts of maleic anhydride and 0.2 part of benzoyl peroxide in 50 parts of MEK was continuously added over 6 hours. The temperature was kept at 85 ° C. for a further 4 hours after the addition. As a result of sampling a part of the viscous reaction liquid and quantifying the unreacted monomer by gas chromatography, the polymerization rate was 97%. To the copolymer solution obtained here, 38.0 parts of aniline and 0.5 parts of triethylamine, which are equivalent to maleic anhydride, were added and the mixture was heated to 140 ° C.
And reacted for 6 hours. Methyl ethyl ketone 1 in the reaction solution
50 parts of it was added, cooled to room temperature, poured into 1000 parts of vigorously stirred methanol, precipitated, filtered, and dried to obtain an imidized polymer. This is referred to as polymer A.

Experimental Example (2) Fragrance in the presence of rubbery polymer
Group vinyl, unsaturated dicarboxylic acids and copolymerizable with these
Imidization of a copolymer obtained by polymerizing a functional vinyl monomer
Except that 60 parts of styrene and 10 parts of acrylonitrile were used in place of 60 parts of styrene in Production Example (1) of the polymer , 30 parts of 40 parts of maleic anhydride and 28.5 parts of 38.0 parts of aniline were used. The same operation as in Experimental Example (1) was performed to obtain an imidized polymer. This is referred to as polymer B. At this time, the polymerization rate was 95% and the conversion rate to an imide group was 99%.

Experimental Example (3) Acrylonitrile-Butadier
Production of styrene-styrene copolymer (ABS) 80 parts of polybutadiene latex (solid content 50%, average particle size 0.35 μ, gel content 90%), sodium stearate 1 part, sodium formaldehyde sulfoxylate 0.1 Part, tetrasodium ethylenediaminetetraacetic acid 0.03 part, ferrous sulfate 0.003 part and water 200 parts were heated to 65 ° C., and a monomer mixture 60 consisting of acrylonitrile 30% and styrene 70% was added thereto.
Parts, 0.3 parts of t-dodecyl mercaptan, and 0.2 parts of Kyumen hydroperoxide were continuously added over 4 hours, and after the addition was completed, polymerization was carried out at 65 ° C. for 2 hours. Polymerization rate is 96
%Met. After adding an antioxidant to the obtained latex, it was coagulated with calcium chloride, washed with water and dried to obtain a white powdery polymer. This is indicated as ABS.

Example 1 70 parts of the polymer A obtained in Experimental Example (1), 30 parts of ABS obtained in Experimental Example (3), a light stabilizer having a melting point of 50 ° C. or higher, and a hindered substance having a molecular weight of 300 or higher. The phenol compound was mixed with a hexshell mixer, then extruded with an extruder with a vent, and pelletized. The physical properties of the composition thus obtained were measured and are shown in Table 1.

Examples 2 to 6 and Comparative Examples 1 to 3 Imidized polymers of polymers A and B and ABS obtained in Experimental Example (3), nylon 6 (Amylan 1017: manufactured by Toray Industries, Inc.,
Hereinafter referred to as 6PA), polybutylene terephthalate (Novadul 5020S: manufactured by Mitsubishi Kasei Co., Ltd., hereinafter PBT)
And a light stabilizer having a melting point of 50 ° C. or higher and a hindered phenol compound having a molecular weight of 300 are mixed with each other to produce a composition.
Each physical property was measured and shown in Table 1.

[0022]

[Table 1]

Sanol LS-770: Bis- (2,2,6,6, -tetramethyl-4-piperidyl) sebacate mp 82 ° C Mark LA-57: 1,2,3,4-tetrakis- (2,2, 6,6-
Tetramethyl-4-piperidioxycarbonyl) -butane mp139 ° C. Timasolve 119FL: N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N
-(1,2,2,6,6, -Pentamethyl-4piperidyl) amino] -6-chloro-1,3,5-triazine condensate mp 130
-140 ° C Tinuvin 326: 2- (3-tert-butyl-5-
Methyl-2-hydroxyphenyl) -5-chlorobenzotriazole mp 138-141 ° C Mark LA-67: 1,2,3,4-tetrakis- (2,2,6,6-
Tetramethyl-4-piperidyloxycarbonyl, tridecyloxycarbonyl) -butane mixture mp liquid (melting point less than 50 ° C) Irganox 1010: tetrakis- [methylene-3-
(3 ', 5'-di-tert-butyl-4'-hydroxyphenyl (propionate)] methane MW 1178 Irganox 1076: octadecyl 3- (3,5-di-
tert-Butyl-4-hydroxyphenyl) -propionate Molecular weight (MW) 531 Sumilizer GM: 2-tert-butyl-6- (3'-
tert-Butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenylacrylate MW 352 Irganox 1098: N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy- Hydroxynnamid) MW 637 BHT: 2,6-di-tert-butyl-p-cresol MW 220

The physical properties were measured by the following methods. (1) Impact resistance: Notched Izod strength / ASTM
According to D-256. (2) Vicat softening point: load 5 kg, ASTM D-15
According to 25. (3) Accelerated exposure test: A sunshine weather meter (black panel temperature 80 ° C, relative humidity 50%, no rainfall) was used to measure the impact surface of an unnotched Izod test piece to 1000
Irradiated for an hour. (4) Discoloration: The discoloration before and after irradiation was visually judged. (5) Bleed: It was visually judged whether there was any bleeding on the irradiated surface. ○ You cannot see bleeding. × Bleeds can be seen.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-54-70350 (JP, A) JP-A-60-4544 (JP, A) JP-A-58-183729 (JP, A) JP-A-60- 168755 (JP, A) JP 59-15446 (JP, A) JP 58-42638 (JP, A) JP 53-47453 (JP, A)

Claims (1)

(57) [Claims] 1. Hindered amine compound having a melting point of 50 ° C. or higher of 0.01 to 5 parts by weight and a molecular weight of 300 or more per 100 parts by weight of a thermoplastic resin containing a polymer having an imide group in a side chain. A thermoplastic resin composition comprising 0.01 to 5 parts by weight of a phenol compound.