JPH047385B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilizer for synthetic resins that provides excellent stability to synthetic resins. Polyethylene, polypropylene, vinyl chloride resin, polystyrene, high-impact polystyrene,
Styrenic synthetic resins such as ABS, engineering plastics such as polyacetal and polyamide, and various synthetic resins such as polyurethane are widely used in various fields, but when these synthetic resins are used alone, ,
During processing or use, the product may deteriorate due to the effects of heat, light, and oxygen, resulting in softening, embrittlement, surface cracks, or discoloration, resulting in a significant decrease in mechanical properties and problems with its stability. well known. In order to solve these problems, it has been well known to use various phenol-based, phosphorus-based, and sulfur-based antioxidants, such as 2,6-di-t-butyl-based antioxidants. 4-methylphenol, 2,2'-methylenebis(4-methyl-6-
t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol),
n-octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1,1 , 3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, tetrakis[3-(3,
5-di-t-butyl-4-hydroxyphenyl)
Phenolic antioxidants such as propionyloxymethyl]methane may be used alone, or these phenolic antioxidants may be used in combination with phosphorus antioxidants such as tris(nonylphenyl)phosphite and distearylpentaerythritol diphosphite. Alternatively, a method is known in which the above-mentioned phenolic antioxidant is used in combination with a sulfur-based antioxidant such as dilaurylthiodipropionate, dimyristylthiodipropionate, and distearylthiodipropionate. However, these methods are still unsatisfactory in terms of thermal and oxidative stability, thermal discoloration resistance, evaporation resistance, and the like. As a result of various studies to solve these points, the present inventors found that a mixture consisting of a specific phenol compound and a specific sulfur compound in a specific ratio is effective as an antioxidant for synthetic resins. It has been discovered that the present invention provides extremely excellent thermal and oxidative stability that could not be expected from a combination of techniques. That is, the present invention provides 1,3,5-tris{2-
The ratio of [3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}isocyanuric acid () to the sulfur-based compound () represented by the following general formula is ():()=0.5~ 15
The present invention provides a stabilizer for synthetic resins containing a mixture as an active ingredient (weight ratio). (In the formula, R ₁ is an alkyl group having 3 to 18 carbon atoms, R ₂
and R ₃ are each independently a hydrogen atom or a carbon number 1
~6 alkyl group is shown. ) 1,3,5-tris[2-
[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]isocyanuric acid is a combination of 3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionic acid and 1,3, It can be easily produced using a normal esterification reaction with 5-tris(2-hydroxyethyl)isocyanuric acid. In the sulfur-based compound represented by the general formula (), the substituent R ₁ represents an alkyl group having 3 to 18 carbon atoms, but from the viewpoint of thermal and oxidative stability, the substituent R 1 represents an alkyl group having 12 carbon atoms.
~18 alkyl groups are preferred. Further, R ₂ and R ₃ each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and hydrogen or an alkyl group having 1 to 3 carbon atoms is preferred from the viewpoint of thermal and oxidative stability. Representative examples of such compounds are shown in Table-1.

[Table] These sulfur-based compounds () have the following general formula with pentaerythritol: (In the formula, R ₁ , R ₂ and R ₃ have the same meanings as above.) It can be produced by reacting with an aldehyde represented by the following in a known acetalization reaction. When blending the stabilizer of the present invention into a synthetic resin, the total amount of compound () and compound () added is usually 0.01 to 5 parts by weight, preferably 0.05 to 1 part by weight, per 100 parts by weight of the synthetic resin. be. The combined weight ratio of compound () to compound () is 0.5 to 15, preferably 1 to 10, more preferably 2 to 6 per 1 of compound (). Here compound () is for compound ()
If the amount of the compound () is less than 0.5 times by weight, it is difficult to obtain the desired effect, and even if the amount of the compound () exceeds 15 times by weight, it is difficult to obtain a commensurate effect, which is economically disadvantageous. In the present invention, in order to blend compound () and compound () into a synthetic resin, the known apparatuses and operating methods for mixing and blending stabilizers, pigments, fillers, etc. into synthetic resins can be applied almost as they are. The synthetic resin composition containing the stabilizer of the present invention is
Other additives, such as UV absorbers, light stabilizers,
It may contain antioxidants, metal deactivators, metal soaps, nucleating agents, lubricants, antistatic agents, flame retardants, pigments, fillers, and the like. In particular, ultraviolet absorbers, hindered amine light stabilizers, etc., such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-
Octoxybenzophenone, 2(2-hydroxy-5-methylphenyl)benzotriazole, 2
(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chloro-benzotriazole,
2(2-hydroxy-3,5-di-t-butylphenyl)-5-chloro-benzotriazole, 2
(2-hydroxy-3,5-di-amyl phenyl)
Benzotriazole, [2,2'-thiobis(4-
t-octylphenolate)]-butylamine Ni
Salt, 2,2,6,6-tetramethyl-4-piperidinylbenzoate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 2
-[3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butyl-malonate bis(1,
2,2,6,6-pentamethyl-4-piperidyl), 1-[2-{3-3,5-di-t-butyl-
4-hydroxyphenyl)propionyloxy}
ethyl]-4-[3-(3,5 di-t-butyl-4
-Hydroxyphenyl)propionyloxy]-
2,2,6,6-tetramethylpiperidine, dimethyl succinate 1-(2-hydroxyethyl)-4
The light resistance can be improved by adding -hydroxy-2,2,6,6-tetramethylpiperidine polycondensate or the like. Moreover, by adding other phosphite-based antioxidants together with the stabilizer of the present invention, the hue of the synthetic resin can be improved. Examples of these phosphite antioxidants include distearyl pentaerythritol 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, and the like. Thus, by using the stabilizer for synthetic resins of the present invention, the stability of synthetic resins is greatly improved, but such synthetic resins include low density polyethylene, high density polyethylene, linear low density polyethylene, chlorinated polyethylene, and EVA. Resin, polypropylene, polyvinyl chloride, methacrylic resin,
Examples include polystyrene, high-impact polystyrene, ABS resin, AES resin, MBS resin, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, polycarbonate, polyacetal, polyurethane, unsaturated polyester resin, etc., and it is particularly effective for polypropylene. Next, the present invention will be explained in detail with reference to Reference Examples and Examples, but the present invention is not limited thereto. Reference Example 1 Production example of 1,3,5-tris{2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}isocyanuric acid [compound ()] Thermometer, stirring 1,3,5-tris(2-hydroxyethyl)isocyanuric acid in a 500 ml four-necked flask equipped with a Dean Stark trap.
7.84g (0.03mol), 3-(3-t-butyl-4-
Hydroxy-5-methylphenyl)propionic acid
After charging 23.39 g (0.099 mol) and 200 ml of toluene and replacing the air in the container with nitrogen, 1.14 g (0.006 mol) of para-toluenesulfonic acid was charged.
The temperature was raised while stirring, and the reaction was carried out at 112°C for 5 hours. During this time, a Dean-Stark trap is used to prevent water produced by azeotropic distillation from returning to the reaction system. After the reaction is complete, cool to room temperature and remove toluene layer.
Wash 3 times with 150ml of % carbonated soda water, then 150ml of water.
Wash 3 times with Then, by distilling off the toluene, 1,3,5-
Tris[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]isocyanuric acid 27.0g (yield 98.2
%) was obtained. Elemental analysis C ₅₁ H ₆₉ N ₃ O ₁₂ Calculated values in parentheses C: 66.76% (66.86%) H: 7.70% (7.59%) N: 4.62% (4.59%) FD-Mass spectrometry (M+1)+916 confirmed. H-NMR (CDCl ₃ , TMS, 60MH ₂ ) δ1.37 27H s δ2.16 9H s δ2.69 12H m δ4.25 12H br.s δ4.83 3H br.s δ6.82 3H br.s δ6. 94 3H br.s Example 1 After mixing the following composition with a mixer for 5 minutes,
The compound obtained by melt-kneading with a mixing roll at 180°C was formed into a sheet with a thickness of 1 mm using a hot press at 210°C, and a test piece of 40 x 40 x 1 mm was prepared. 30 of the specimen area in gear open at 160℃
% was measured, and this time was taken as the thermal embrittlement induction period, and the thermal and oxidation stability was evaluated. The results are shown in Table-2. <Formulation> Unstabilized polypropylene resin 100 parts by weight Calcium stearate 0.1 Test compound Variables In Table 2, the symbols of the test compounds indicate the following compounds. AO-1 n-octadecyl 3-(3,5-di-
t-Butyl-4-hydroxyphenyl)propionate AO-2 Tetrakis[3-(3,5-di-t-
Butyl-4-hydroxyphenyl)propionyloxymethyl]methane AO-3 1,3,5-tris{2-[3-(3,
5-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl}isocyanurate AO-4 1,1,3-tris(2-methyl-4
-hydroxy-5-t-butylphenyl)butane AO-5 dilaurylthiodipropionate AO-6 distearylthiodipropionate

【table】

【table】

【table】

[Table] Example 2 Suspensions prepared by bead-decomposing the test compounds shown in Table 3 with an anionic surfactant were added to the grafted ABS latex in a predetermined amount as shown in Table 3. The ABS obtained by salting out with an aqueous magnesium sulfate solution, filtering, washing with water, and drying according to a conventional method.
A resin powder was used as a test sample. Using this ABS resin powder, thermal and oxidative stability was evaluated using the following method. The results are shown in Table-3. 1 After heat aging in a 180℃ gear oven
The degree of discoloration of ABC resin was observed. 2 The oxygen absorption induction period (IP) was measured in an oxygen atmosphere at 170°C using an oxygen absorption induction period measurement device. 3 ABS resin powder is processed using a small extruder (screw D=20mmφ, L/D=25, strand die D
= 3 mmφ, L/D = 10) under the following conditions, and the degree of discoloration of the fourth ABS pellet was evaluated by the color difference ΔYI from the first additive-free ABS pellet. Extrusion conditions Rotation speed: 40 rpm Temperature: C ₁ C ₂ C ₃ D 220°C 240°C 260°C 280°C 4 The ABS pellets obtained by method 3 above after four extrusions were compression molded at 180°C for 10 minutes to JISK7111. A specified No. 1 test piece was prepared. Next, the Shapey impact value was measured in accordance with JISK7111 using a Shapey impact tester. In addition, in the table, AO-7 indicates the following compound. AO-7 2,6-di-t-butyl-4-methylphenol

【table】

[Table] Example 3 The test compounds shown in Table 4 were added to 25% urethane dope (25 parts of polyurethane resin, 3.75 parts of dimethylformamide and 1.25 parts of tetrahydrofuran) to 100 parts by weight of the above polyurethane resin. After adding parts by weight, it was coated on a polyester film to a thickness of 1.2 mm and dried for 1 hour in a dryer at 45°C. 3 sheets obtained in this way
Punch out with No. 1 dumbbell, fade meter (light source: ultraviolet carbon arc, black panel temperature: 63±
After irradiation with light for 60 hours and 120 hours at 3℃), a tensile test (pulling speed: 200 mm/min, measurement temperature: 25
℃) to determine the fracture strength retention rate. The results are shown in Table 4.

【table】

【table】

Claims (1)

[Scope of Claims] 1 1,3,5-tris{2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}isocyanuric acid () and represented by the following general formula A stabilizer for synthetic resins, characterized in that the active ingredient is a mixture of sulfur-based compounds () in a ratio of ():()=1:0.5 to 15 (weight ratio). (In the formula, R ₁ is an alkyl group having 3 to 18 carbon atoms, R ₂
and R ₃ are each independently a hydrogen atom or a carbon number 1
~6 alkyl group is shown. ) 2 The sulfur compound () is 3,9-bis(2-
The stabilizer for synthetic resins according to claim 1, which is (dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane. 3. The stabilizer for synthetic resins according to claims 1 and 2, wherein the synthetic resin is a polyolefin resin. 4. The stabilizer for synthetic resins according to claim 3, wherein the polyolefin resin is polypropylene.