JPH052705B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to stabilized synthetic resin compositions. Specifically, the present invention relates to a synthetic resin composition that has extremely excellent stability not only against heat and oxidation but also against light. Synthetic resins such as polyethylene, polypropylene, polyvinyl chloride, polyurethane, ABS resin, etc.
Deteriorates due to the action of light and oxygen, causing softening, embrittlement,
It is well known that the mechanical properties are significantly degraded with phenomena such as surface cracking or discoloration. In order to prevent such deterioration due to heat and oxidation, for example, 2,6-di-t-butyl-4-methylphenol, tris(3,5-di-
Various phenolic compounds such as t-butyl-4-hydroxybenzyl) isocyanurate, and furthermore, for the purpose of improving antioxidant performance, these phenolic compounds are combined with dilauryl thiodipropionate, pentaerythritol tetrakis(3-
Sulfur-based compounds such as 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, etc. are also used in combination to prevent deterioration due to light.
-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole,
Benzotriazole compounds such as 2-(2-hydroxy-3,5-dipentylphenyl)benzotriazole, cyanoacrylate compounds such as ethyl 2-cyano-3,3-diphenyl acrylate, bis(3,5-dipentylphenyl) Ni-based compounds such as Ni salt of monoethyl ester (t-butyl-4-hydroxybenzyl phosphoric acid) and 4-
Benzoyloxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, N,N'-
Hindered reaction material of bis(2,2,6,6,-tetramethyl-4-piperidylhexylene diamine) and 2,4-dichloro-6-t-octylamino-1,3,5-triazine, etc. It is known to use a light stabilizer such as a piperidine compound in combination. However, even when these known stabilizers are used in combination, the resulting stabilized synthetic resin composition cannot satisfy all of heat resistance, oxidation resistance, and light resistance at the same time. For example, if a phenol compound and a sulfur compound are used as antioxidants, and a benzophenone compound, benzotriazole compound, cyanoacrylate compound, or Ni compound is used as a light stabilizer, light resistance may be affected. It was not completely satisfying. In addition, when using hindered piperidine compounds, which are commonly used as photostabilizers, if a sulfur-based stabilizer is used together, the original excellent photostabilizing effect of hindered piperidine compounds may be extremely impaired, perhaps due to an antagonistic effect. A major problem arises in that the sulfur-based stabilizer is not used and only a phenol-based stabilizer is used in combination to take advantage of the light resistance, but the heat resistance and oxidation resistance are sacrificed, or the sulfur-based stabilizer is also used in combination. There is no choice but to either take advantage of heat resistance and oxidation resistance and sacrifice light resistance, and even in combination with hindered piperidine compounds, heat resistance, oxidation resistance, and light resistance are sufficiently satisfied at the same time. It wasn't something to force. The present inventors have conducted intensive studies to solve these problems, and have found that if a specific hindered piperidine compound is used, the combination of various ordinary hindered piperidine compounds and sulfur-based antioxidants can be used. The present invention was completed by discovering that heat resistance, oxidation resistance, and light resistance can be satisfied simultaneously by using a sulfur-based antioxidant and a phenolic antioxidant without causing the extreme decrease in light resistance. That is, the present invention provides synthetic resin with the general formula () (In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and R ₃ represents an alkylene group having 1 to 4 carbon atoms.) A hindered piperidine compound and a phenolic antioxidant The object of the present invention is to provide an extremely excellent stabilized synthetic resin composition which is characterized by being blended with a sulfur-based antioxidant and which satisfies not only heat resistance and oxidation resistance but also light resistance. The hindered piperidine compound represented by the above general formula () has the general formula () (In the formula, R ₁ has the same meaning as above.) 2,2,6,6-tetramethyl-4-
Aminopiperidines and general formula () (In the formula, X represents a halogen atom, R ₄ represents a lower alkyl group, and R ₃ has the same meaning as above). (In the formula, R ₂ has the same meaning as above.) 2,2,6,6-tetramethyl-4-
It can be produced by reacting hydroxypiperidines. Representative examples of such hindered piperidine compounds are shown in Table 1. From the viewpoint of light resistance, substituents R ₁ and R ₂ in the general formula () are preferably hydrogen atoms, and substituent R ₃ has 1 carbon
-2 alkylene groups are preferred.

[Table] Examples of the phenolic antioxidants used in the present invention include 2,6-di-t-butyl-4-methylphenol, n-octadecyl 3-(3,
5-di-t-butyl-4-hydroxyphenyl)
Propionate, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 4,4'-thiobis(3-methyl -6-
t-butylphenol), 2-t-butyl-6-
(3-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenyl acrylate,
1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,
5-trimethyl-2,4,6-tris(3-alkyl-5-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-alkyl-5-t-butyl-4-hydroxy benzyl)
Isocyanurate, 1,3,5-tris(3-
(3-Alkyl-5-t-butyl-4-hydroxyphenyl)propionyloxyethyl)isocyanurate, ethylene glycol bis(3,3
-bis(4-hydroxy-3-t-butylphenyl)butanate), pentaerythritol tetrakis(3-(3-alkyl-5-t-butyl-
(4-hydroxyphenyl) propionate) and the like. Examples of the sulfur-based antioxidants used in the present invention include dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate), 3,9-bis(2-dodecylthioethyl)
-2,4,8,10-tetraoxaspiro [5.5]
An example is undecane. The stabilized synthetic resin of the present invention contains a specific hindered piperidine compound represented by the above general formula (), a phenolic antioxidant, and a sulfur antioxidant, but the total content is higher than that of the synthetic resin. It is usually 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight per 100 parts by weight, and the weight ratio of each stabilizer is usually compound (): phenolic antioxidant: sulfur antioxidant = 1 to 20. :1:1-15. As for the compounding method, most of the known devices and operating methods for mixing and compounding stabilizers, pigments, fillers, etc. into synthetic resins can be applied as they are. When using the stabilizer for synthetic resins of the present invention, other additives such as antioxidants, light stabilizers, metal deactivators, metal soaps, nucleating agents, lubricants, and antistatic agents are required. , flame retardants, pigments, fillers, etc. may be used in combination. In particular, by using a phosphite antioxidant in combination, the hue can be improved. These phosphite antioxidants include:
For example, tris(nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(2-t-butyl-4
-methylphenyl)phosphite, bis(2,4
-di-t-butylphenyl) pentaerythritol diphosphite, tetrakis(2,4-di-t
-butylphenyl)-4,4'-biphenylene diphosphonite. Further, by adding a light stabilizer other than hindered piperidine compounds to the composition of the present invention, the light resistance can be further improved. Examples of these light stabilizers include 2-hydroxy-
Benzophenone compounds such as 4-n-methoxybenzophenone, 2-hydroxy-n-octoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-(2-hydroxy- 3-t-butyl-5-methylphenyl)-
5-chlorobenzotriazole, 2-(2-hydroxy-3,5-dipentylphenyl)benzotriazole, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)benzotriazole, 2-(2-hydroxy -5-methylphenyl)
Benzotriazole, 2-(2-hydroxy-3,
5-di-t-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-t-butylphenyl)-5-chlorobenzotriazole,
Benzotriazole compounds such as 2-(2-hydroxy-5-t-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl)benzotriazole, enyl salicylate, p-t-
Butylphenyl salicylate, 2,4-di-t-
Butylphenyl-3',5'-di-t-butyl-4'-
Hydroxybenzoate, hexadecyl-3,5
-benzoate compounds such as di-t-butyl-4-hydroxybenzoate, Ni salt of N,N-dibutyldithiocarbamic acid, [2,2'-thiobis(4-t-octylphenolate)]-n-butylamine Ni complexes, Ni-based compounds such as Ni salt of bis(3,5-di-t-butyl-4-hydroxybenzylphosphoric acid) monoethyl ester, and cyano compounds such as ethyl 2-cyano-3,3-diphenyl acrylate. Acrylate compounds and N-2-ethylphenyl-N'-2-ethoxy-5-t-butylphenyl oxalic acid diamide, N
Examples include oxalic acid diamides such as -2-ethylphenyl-N'-2-ethoxyphenyl oxalic acid diamide. The synthetic resins stabilized by the present invention include:
Poly-α-olefins such as low-density polyethylene, medium-high density polyethylene, linear low-density polyethylene, polypropylene, polybutene-1, propylene-ethylene random or block copolymers, ethylene-butene-1 random copolymers, etc. Copolymers, copolymers of polyα-olefins and vinyl monomers such as maleic anhydride-modified polypropylene, and mixtures thereof, chlorinated polyethylene, EVA resin, polyvinyl chloride, methacrylic resin, polystyrene, high-impact polystyrene, ABS resin , AES resin, MBS resin, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, polycarbonate, polyacetal, polyurethane,
Examples include unsaturated polyester resin. Further, rubbers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, and blends of these resins may also be used. EXAMPLES Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto. Example 1 After mixing the following formulation with a mixer for 5 minutes,
The compound obtained by melt-kneading with a mixing roll at 180°C was molded into a sheet with a thickness of 1 mm using a hot press at 210°C, and a test piece of 150 x 30 x 1 mm was prepared. This test piece was attached to a sunshine weather meter (light source: carbon arc, black panel temperature:
The weather resistance was evaluated by irradiating the film with light at 83±3°C (spray cycle: 120 minutes, spray time: 18 minutes), bending it into a shrimp shape every 60 hours, and measuring the time until it broke. On the other hand, a test piece of 40 x 40 x 1 mm was created,
The time until 30% of the specimen area became embrittled in a gear oven at 160°C was measured, and this was taken as the thermal embrittlement induction period to evaluate thermal and oxidation stability. The results are shown in Table-2. <Formulation> Unstabilized polypropylene 100 parts by weight Calcium stearate 0.1 2,6-di-t-butyl-4-methylphenol
0.05 Test compound Listed in Table-2 In the table, UVA-1 to AO-3 indicate the following compounds. UVA-1 2-hydroxy-4-n-octoxybenzophenone UVA-2 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole UVA-3 2-(2- Hydroxy-3,5-dipentylphenyl)benzotriazole UVA-4 Ethyl-2-cyano-3,3-diphenyl acrylate UVA-5 Bis(3,5-di-t-butyl-4
-Hydroxybenzylphosphoric acid)
Ni salt of monoethyl ester UVA-6 Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate UVA-7 Tinuvin 944 (Ciba Geigy) (hindered piperidine light stabilizer) AO-1 Tris ( 3,5-di-t-butyl-4
-Hydroxybenzyl)isocyanurate AO-2 Dilauryl-3,3'-thiodipropionate AO-3 Pentaerythritol Tetrakis(3-dodecylthiopropionate)

[Table] Example 2 25% urethane dope (25 parts polyurethane resin, 3.75 parts dimethylformamide and 71.25 parts
After adding 1% of the test compounds shown in Table 3 to the above polyurethane resin (Tetrahydrofuran), it was coated on a polyester film to a thickness of 1.2 mm and dried in a dryer at 45°C for 1 hour. The sheet obtained in this way was punched out with a No. 3 dumbbell,
After 60 and 120 hours of light irradiation with a fade meter (light source: ultraviolet carbon arc, black panel temperature: 63±3°C), a tensile test (pulling speed: 200 mm/min, measurement temperature: 25°C) was performed to maintain the breaking strength. The rate was calculated. The results are shown in Table-3.

【table】

【table】

Claims (1)

[Claims] 1 General formula () in synthetic resin (In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and R ₃ represents an alkylene group having 1 to 4 carbon atoms.) A hindered piperidine compound and a phenolic antioxidant and a sulfur-based antioxidant.