JPS60245670A - Stabilized polymer composition - Google Patents

Abstract

PURPOSE:To provide a stabilized polymer compsn. having excellent resistance to heat, oxidation and light, by blending a sulfur antioxidant, a phenolic antioxidant and a specified hindered piperidine compd. CONSTITUTION:A hindered piperidine compd. of formula I (wherein R1 is H, a 1-3C alkyl; R2, R3 are each H or together form a group of formula II) such as 1,3:2,4:5,6-tris-O-(2,2,6,6-tetramethyl-4-piperidinylidene)sorbitol is used. 0.01- 5pts.wt. stabilizer compsn. composed of a mixture of said piperidine derivative, a phenolic antioxidant (e.g. 2,6-di-t-butyl-4-methylphenol) and a sulfur antioxidant (e.g. dilauryl thiodipropionate) in a weight ratio of 1-20:1:1-15 is blended with 100pts.wt. synthetic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to stabilized polymeric compositions. Specifically, the present invention relates to a polymer composition having extremely excellent stability not only against heat and oxidation but also against light.

Synthetic resins such as polyethylene, polypropylene, polyvinyl chloride, polyurethane, 'AB8 resin, etc. deteriorate due to the effects of heat, light, and oxygen, resulting in significant deterioration of their mechanical properties with phenomena such as softening, embrittlement, surface cracks, or discoloration. It is well known that there is a decline in

For the purpose of preventing such deterioration due to heat and oxidation, for example, 2,6-di-t-butyl-4-methylphenol, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, etc. Various phenolic compounds such as dilauryl thiodipropionate, pentaerythritol tetrakis (3-
Sulfur-based compounds such as (dodecylthiopropionate) are used in combination, and furthermore, for the purpose of preventing deterioration due to light, for example,
-Hydroxy-4-+pentuphenone compounds such as 1-octoxybenzophenone, 2-(2-hydroxy-3
Benzotriazole compounds such as -t-butyl-5-methylphenyl)-5-chloropenzotriazole, 2-(2-hydroxy-3,5-dipentylphenyl)benzotriazole, ethyl 2-cyano-8,3 - Cyanoacrylate compounds such as diphenyl acrylate, Ni-based compounds such as Ni salt of bis(3,5-di-t-butyl-4-hydroxybenzylphosphoric acid) monoethyl ester, and 4-benzoyloxy-2, 2
,6,6-titramethylbiperidine, bis(2,2,6
, 6-tetramethyl-4-piperidyl) sebacate%
N IN'-bis(2,2,6,6-tetramethyl-
A light stabilizer such as a hindered piperidine compound such as a reaction product of 4-biperidylhexylene diamine) and 2,4-dichloro-6-t-octylamino-1,3゜5-triazine may be used in combination. Are known.

However, even when these known stabilizers are used in combination, the stabilized Zhao molecular derivatives obtained cannot satisfy all of heat resistance, oxidation resistance, and light resistance at the same time.

For example, phenolic compounds and sulfur compounds are used as antioxidants, and benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, or Ni-based compounds are used in combination as photostabilizers. However, it was not sufficiently self-sufficient in terms of light resistance. In addition, when using hindered piperidine compounds, which are commonly used as photoanxifying agents, if a sulfur-based antifungal agent is used together, the excellent photostabilizing effect of hindered piperidine compounds may be diminished, perhaps due to an antagonistic effect. As a result, a major problem arises in which 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.
In combination with hindered piperidine-based compounds, heat-resistant However, the oxidation resistance and light resistance were not sufficiently satisfied at the same time.

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 at the same time by using a sulfur-based antioxidant and a phenol-based antioxidant in combination without causing the extreme decrease in light resistance.

That is, the present invention provides supermolecules with the general formula (11 (wherein Rr
represents a hydrogen atom or an alkyl group of 0x-Cs,
R2 and Rs are hydrogen atoms or S. ) It is characterized by being made by blending at least one kind of hindered piperidine compound selected from the compounds represented by the following, and a phenolic antioxidant and a sulfur antioxidant.It has not only heat resistance and oxidation resistance but also light resistance. The object of the present invention is to provide an extremely excellent feminized polymer composition that simultaneously satisfies the following.

The hindered piperidine compound represented by the above general formula (1) is a triacetocyamine derivative or its salt represented by the general formula (n) (wherein 1 has the same meaning as above) and the formula (( 2) It can be produced by reacting sorbitol shown in the following.

Here, examples of salts of triacetonamine derivatives include salts with mineral acids such as hydrochloric acid, phosphoric acid, and sulfuric acid, carboxylic acids such as acetic acid and oxalic acid, and sulfonic acids such as para-toluenesulfonic acid.

In addition, as the alkyl group of C1 to CB, a methyl group,
Examples include ethyl group, n-propyl group, and isopropyl group.

The piperidine derivative of the present invention thus obtained is 1
．． 3:2.4+5.6-Dorissu 0-(2,2,6,6
-Tetramethyl-4-piperidinylidene) sorbitol, 1.3:2.4=5,6-Tris-
0-(1,2,2,6,6-bentamethyl-4-piperidine derivative) sorbitol, 1,3:2,4:5,6-
Dolisu o-(2,2,,6,6-tetramethyl-l-
Propyl-4-piperidinyritene) sorbitol 1.8
:2,4-His-〇-(2,2,6,6-tetramethyl-4-biperidinylidene)sorbitol, 1.8:2.
4-bis-〇-(1゜2.2,6.6-bentamethyl-4-piperidine derivative) sorbitol, 1.3:2.4
-bis-〇-(2,2,6,6-tetramethyl-l-proyl-4-piperidinylidene) sorbitol and the like are exemplified.

Examples of the phenolic antioxidants used in the present invention include 2,6-di-1-butyl-4-methylphenol, n-ophtateryl 3-(3,5-di-t-butyl-
4-hydroxyphenyl)propionate, 2,2
'-Methylenehis(4-methyl-6-t-butylphenol), 4,4-butyritenebis(3-methyl-6-t-butylphenol),
-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 2-1-butyl-6
-(8-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenyl acrylate, 1,1.
8-1-Lis(2-methyl-4-hydroxy-5-t-
butylphenyl)butane, 1,8.5-trimethyl-2
,4,6-tris(3-alkyl-5-t-butyl-4
-hydroxybenzyl)benzene, 1.8.5-1-lis(3-alkyl-5-t-phthyl-4-hydroxybenzyl)isocyanurate, 1,8.5-tris(8-
(8-alkyl-5-1-butyl-4-hydroxyphenyl)propionyloxyethyl) isocyanurate.
, ethylene glycol bis(8,1-bis(4-hydroxy-B-t-butylphenyl)butanate), pentaerythritol tetrakis(8-(8-alkyl-
5-t-butyl-4-hydroxyphenyl)propionate) and the like.

In addition, the sulfur-based antioxidant used in the present invention includes:
For example, dilaurylthiodipropionate, simiristylthiodipropionate, distearylthiodipropionate, pentaerythritol tetrakis(3-dodecylthiopropionate), 8.9-his(2-dodecylthioethyl)-2 , 4,8,10-tetraoxaspiro(5,5) lanthican.

The stabilized polymer composition of the present invention contains a specific hinted piperidine compound represented by the general formula (11), a phenolic antioxidant, and a sulfur antioxidant, and the total amount thereof is It is usually 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight per 100 parts by weight of the synthetic resin, and the weight ratio of each stabilizer is usually compound (■): phenolic antioxidant: sulfur type antioxidant Antioxidant = 1-20
:1:1-15.

As for the compounding method, almost all known equipment and operating methods for mixing and compounding stabilizers, pigments, fillers, etc. into polymers can be applied as is.

In producing the stabilized polymer composition of the present invention, other additives such as antioxidants, light stabilizers, metal deactivators, metal soaps, nucleating agents, lubricants, antistatic agents, and Fuels, pigments, fillers, etc. may be used in combination.

In particular, by using a phosphite antioxidant in combination, the hue can be improved.

These phosphite-based antioxidants include evatris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, and tris(2,4
-di-t-butylphenyl) phosphite, tris(2
-1-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.

Further, by adding a light stabilizer other than the hinted piperidine compound to the composition of the present invention, the light resistance can be further improved. Examples of these light stabilizers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-n-octoxybenzophenone, and 2-hydroxy-4-methoxybenzophenone.
Benzophenone compounds such as phenone, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5
-Chlorbenzotriazole, 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-8,5-di-t-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-t-
butylphenyl)-5-chloro-benzotria boule, 2-(2-hydroxy-5-t-octylphenyl)
Benzotriazole, 2-(2-hydroxy-3゜5-
Benzotriazole compounds such as his(α,(It-dimethylbenzyl)phenyl)benzotriazole, phenyl salicylate, p-butylphenyl salicylate, 2,4-di-t-butylphenyl 8,5-di-
Benzoate compounds such as t-butyl-4-hydroxybenzoate, hexatecyl 3.5-di-1-butyl-4-hydroxybenzoate, N1 salt of N,N-dibutyldithiocarbamic acid, [2゜2'-thiohis(4-
1-octylphenolate)]-]n dithylamine N
Nl-based compounds such as Ni salt of i-complex his(8,5-di-t-butyl-4-hydroxybenzylphosphoric acid) monoethyl ester, ethyl 2-cyano-3
, 3-diphenylacrylate, 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.

Polymers stabilized by the present invention include poly-alpha-olefins such as low-density polyethylene, medium-high density polyethylene, linear low-density polyethylene, polypropylene, polybutene-1, propylene-ethylene random or block copolymers, ethylene- Polyα-olefin copolymers such as butene-1-lantum copolymers, copolymers of polyα-olefins and vinyl monomers such as maleic anhydride-modified polypropylene, and mixtures thereof, chlorinated polyethylene, EVA resin, polyvinyl chloride , meccrylic resin, polystyrene, high-impact polystyrene, AB8 resin, AE8 resin, MBS resin, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, polycarbonate, polyacetal, polyurethane, unsaturated polyester resin, and the like. Furthermore, rubbers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, and styrene-butadiene copolymer rubber, or blends of these resins may also be used.

EXAMPLES Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Example 1 The following formulation was mixed with a mixer for 5 minutes and then heated to 180°C.
The compound obtained by melting and kneading with a mixing roll is
Form into a sheet with a thickness of 15 cm using a heat press at 10°C.
A 0X30X1 dark test piece was created.

This test piece was tested using a sunshine weather meter (light source: carbon arc, black panel temperature: 83±3°C, spray period: 120 minutes).

The material was irradiated with light in a spray (spray time: 18 minutes), bent into a shrimp shape every 60 hours, and the time until it broke was measured to evaluate weather resistance.

On the other hand, a 40X40Xl test piece was prepared, and 160
The time required for the 30th area of the specimen to become brittle in a gear oven at °C was measured, and this was taken as the thermal embrittlement induction period to evaluate thermal and oxidative stability.

The results are shown in Table-1.

Blend> Unstabilized polypropylene 100 parts by weight Calcium stearate 0.1 2.6-di-t-butyl-4-methylphenol 0.0
5 In the table, l-1-AO-3 represents the following compound.

1-11,8:2,4:5,6-Dolys-0-(2,2,6,6-titramethyl-4-piperidinyritene)sorbitol 1-2 1,8:2,4:5,6-Tris- 0-
(1,2,2,6,6-bentamethyl-4-piperidinyritene)sorbitol 1-3 1.3:2.4-bis-〇-(2,,2,6,6-tetramethyl-4-piperidinyritene)sorbitol 1-4 1.9:2,4-his-〇- (1,2,2,6,6-pentamethyl-4-piperidinylidene) Sorbitol UVA-12-human t'roxy 4 nt toxybenzophenocy UVA- 22-(2-hydroxy-3-butyl-5
-methylphenyl) -5-chlorobenzotria'boule UvA-32-(2-t nitroxy-3,5-dipentylphenyl)benzotriazole UVA-4 Ethyl 2-cyano-3,3-diphenylacrylate UvA 5 His(3 ,5') Ni salt of t-butyl-4-hydroxybenzylphosporin acid) monoethyl ester (JVA-5 his(2,2,6,6-tetramethyl-4
- Piperidyl) Sebacate UVA-7 Tinuvin 944 (Ciba Geiki Co., Ltd.) (Hindered piperidine light stabilizer) UVA-8 His-0 (
2,2,6,6-tetramethyl-4-piperidinylidene) pentaerythritol AO-1 tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate AO-2 dilauryl 3,3-thiodipropio nate AO-3 pentaerythritol tetrakis(3-dodecylthiopropionate) Table-1 (1) Table-2 (2) Example 2 25% urethane dope (25 parts of polyurethane resin, 8
．． The test compounds shown in Table 2 were added to 75 parts of dimethylformamide and 71.25 parts of tetrahydrofuran at 1% based on the polyurethane resin, and then coated on a polyester film to a thickness of 1.2 mm and heated at 45°.
It was dried in a drying mold of C for 1 hour. The sheet obtained in this way was punched out with a No. 8 dumbbell, and a fade meter (light source:
Ultraviolet carbon arc, black panel temperature 268±8
After irradiation with light for 60 hours and 120 hours (°C), a tensile test (tensile rate: 200 rtan/wn, measurement temperature:
25°C) to determine the retention of breaking strength.

The results are shown in Table-2.

Table-2 Hand 1. Supplementary I-Kichi (voluntary) July 13, 1980 2, Komei no Nari, Stabilized polymer composition: 3. Compensation with the Swamp Incident (k. Patent applicant 5-15 Kitahama, Higashi-ku, Osaka (204J') Representative of Sumitomo Chemical T-Gyo Co., Ltd.
Hosei (4, Agent: Sumitomo Chemical Co., Ltd., 5-15 Kitahama, Higashi-ku, Osaka, Co., Ltd. 1)
: (85D 7) Moroishi Mitsuruji ゛Contact 7L (06) 220-3404"""'5-M
Detailed description of the invention in the subject specification of lf iL [3, Contents of Q 111- (1) Ming? 1IIl Antiquity, page 16, line 11 [""Sulfur series 1
The compound is 0.05J.
5”? +li Correct.

(2) Same No. 20', i4j I iryo 11 "People-2 (
2) It says -+, ``Table 1 (2) J and correction 1) Same 2 r) +'t-- Blank part of 1 ``n'' of ``15su'' in Table 1 (2) Insert 1Φ of "comparison" into.

2 Procedural amendments Manabu Shiga Director General of the Patent Office 1 Indication of the case 1982 Patent Application No. 103862 2 Name of the invention Stabilized polymer composition 3 Relationship to each case making the amendment Patent applicant address Osaka 5-15 Kitahama, Higashi-ku, City Name (209
) Sumitomo Chemical T-Gyo Co., Ltd. Representative: Takeshi Hijikata 4 Agent address: 5-15-1 Kitahama, Higashi-ku, Osaka, Japan Claims and detailed description of the invention in the specification to be amended; Contents of the amendment (1) Amend the claims as shown in the attached sheet.

C) Details @ 1 piperidine compound on the 7th line from the bottom of page 6.
Correct "with a piperidine compound."

(3) Page 19, line 6 of Table 1 (1), Example of the present invention
4. In the column of thermal embrittlement induction period, "760" is replaced by l.
Corrected to -670J.

Claims [General formula (+) l-0R2 CH,0R3 (wherein, R1 is a hydrogen atom or a C4-C3 alkyhindered pipezine compound, a phenolic antioxidant, and a sulfur-based antioxidant) Combined with a pressure agent? ＊＠
h t 697iE~Continuation of “14'・1 1st page oInt, CI,' Identification code Internal reference number [Co., Ltd.] Inventor Masahisa Shiotani Inside Haru Company, Konohana-ku, Osaka City

Claims (1)

[Claims] General formula (1) %Formula% (In the formula, R+ represents a hydrogen atom or an alkyl group of Ct-Cs, and R2 and ILs represent a hydrogen atom or a compound selected from the following. A stabilized polymer composition comprising a hindered piperidine compound, a phenolic antioxidant, and a sulfur antioxidant.