JPS60226553A - Stabilized synthetic resin composition - Google Patents

Abstract

PURPOSE:A stabilized synthetic resin composition that is obtained by adding a specific hindered piperidine compound, a phenolic antioxidant and a sulfur antioxidant, thus showing improved stability to heat, oxidation and light. CONSTITUTION:The objective composition is obtained by adding, to 100pts.wt. of a synthetic resin, (A) a hindered piperidine compound of the formula (R1, R2 are H, methyl, preferably H; R3 is 1-4C alkylene, preferably of 1-2 carbon atoms), which is prepared by reaction between tetramethylpiperizine and a halogenated carbonic ester, followed by reaction of the product with 2,2,6,6-tetramethyl-4- hydroxypiperidine, (B) a phenolic antioxidant such as 2,6-di-t-butyl-4-methylphenol and (C) a sulfur antioxidant such as dilauryltio dipropionate so that the total becomes 0.01-5pts.wt., preferably 0.05-2pts.wt. and the weight ratio of A:B:C becomes (1-20):1:(1-15).

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, and ABS resin deteriorate due to the effects of heat, light, and oxygen, and their mechanical properties deteriorate significantly with phenomena such as softening, embrittlement, surface cracks, and discoloration. It is well known to do so.

For the purpose of preventing such deterioration due to heat and oxidation, for example, 2,6-di-t-butyl-4-methylphenol, tris(8,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, etc. Various phenolic compounds such as oxidation compounds such as dilauryl thiodipropionate and sulfur compounds such as pentaerythritol tetraquine (8-dodecylthiopropionate) are used in combination with these phenolic oxidation compounds for the purpose of improving antioxidant performance. Furthermore, for the purpose of preventing deterioration due to light, for example 2-
Penzophenone compounds such as hydroxy-4-n-octoxybenzophenone, 2-(2-hydroxy-8-t
Benzotriazole compounds such as -butyl-6-methylphenyl)-5-chloro-benzotriazole, 2-(2-hydroxy-8,5-dipentylphenyl)benzotriazole, ethyl 2-cyano-8,8-diphenylacrylate cyanoacrylate compounds such as Ni salt of bis(8,5-di-t-butyl-4-hydroxybenzylphosphoric acid) monoethyl ester, and NI compounds such as 4-benzoyloxy-2,2,
6,6-titramethylpiperidine, bis(2,2,6,
6-tetramethyl-4-piperidyl) sepate, N
, N'-bis(2,2,6,6-tetramethyl-4-
piperidylhexylene diamine) and 2,4-dichloro-
It is known that a light stabilizer such as a hindered piperidine compound such as a reactant of 6-t-octylamino-1,8,5-triazine 7 is used 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 satisfactory. 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 sulfur-based stabilizers are not used and only phenol-based stabilizers are used in combination to take advantage of light resistance, sacrificing heat resistance and oxidation resistance, or sulfur-based stabilizers are also used in combination. Heat resistance,
It was not possible to fully satisfy both oxidation resistance and light resistance.

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 a normal hindered piperidine compound and a sulfur-based antioxidant can be achieved. The present inventors have discovered 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 without the extreme decrease in light resistance seen in the above, and the present invention has been completed.

That is, the present invention provides synthetic resins with general formula (I) (wherein R
1 and R2 each independently represent a hydrogen atom or a methyl group, and R8 represents an alkylene group having 1 to 4 carbon atoms. ) An extremely excellent product that satisfies not only heat resistance and oxidation resistance but also light resistance, which is characterized by being made by blending the hindered piperidine compound represented by () with a phenolic antioxidant and a sulfur antioxidant. A stabilized synthetic resin composition is provided.

The hindered piperidine compound represented by the above general formula (1) is composed of tetramethylaminopiperidines represented by the general formula (]I) (wherein R1 has the same meaning as above) and the general formula (to). 1 X -Rs -C-0-R4 (2) (wherein, and further react with 2,2,6,6-tetramethyl-4-hydroxypiperidines represented by the general formula (g) (wherein R2 has the same meaning as above). be able to.

Representative examples of such hindered piperidine compounds are shown in Table 1.
However, from the viewpoint of light resistance, substituents R1 and R1 in the general formula (I) are preferably hydrogen atoms, and substituent R8 is preferably an alkylene group having 1 to 2 carbon atoms.

Table 1 Examples of phenolic antioxidants used in the present invention include 2,6-di-t-butyl-4-methylphenol, n-octadecyl 8-(8,5-di-t-butyl-
4-Hydroxyphenyl)propionate, 2,2'
-methylenebis(4-methyl-6-t-butylphenol), 4,4'-butylidenebis(8-methyl-6-t-butylphenol),
-butylphenol), 4,4'-thiobis(8-methyl-6-t-butylphenol), 2-t-butyl-6
-(8-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenyl acrylate, 1,1.
8-) Lis(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,8.5-)dimethyl-2,
4,6-tris(8-alkyl-5-butyl-4-
hydroxybenzyl)benzene, 1.8.5-tris(
8-alkyl-5-t-butyl-4-hydroxybenzyl)isocyanurate, 1,8.5-tris(8-(8
-Alkyl-5-t-butyl-4-hydroxyphenyl)propionyloxyethyl)in cyanurate, ethylene glycol bis(8,8-bis(4-hydroxy-3-1-butylphenyl)butanate), pentaerythritol tetrakis( 8-(8-alkyl-5-t
-butyl-4-hydroxyphenyl)propionate)
etc.

In addition, the sulfur-based antioxidant used in the present invention includes:
For example, dilaurylthiodipropionate, simiristylthiodipropionate, distearylthiodipropionate, pentaerythritol tetrakis(8-dodecylthiopropionate L8,9-bis(2-dodecylthioethyl)-2,4, 8,10-tetraoxaspiro[
5,5] undecane and the like.

The stabilized synthetic resin of the present invention contains a specific hindered piperidine compound represented by the general formula (I), a phenolic antioxidant, and a sulfur antioxidant, but 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 resin, and the weight ratio of each stabilizer is usually compound (1): phenolic antioxidant: sulfur oxidant. Inhibitor = 1-20:1
:l~16.

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 stabilization agents, metal deactivators, metal soaps, nucleating agents, lubricants, antistatic agents, and flame retardants are required. , pigments, fillers, etc. may be used in combination.◎ In particular, the hue can be improved by using a phosphite antioxidant in combination.

These phosphite-based antioxidants include hatris (nonylphenyl) phosphite, 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.

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-4-methoxybenzophenone, 2-hydroxy-n-octoxybenzophenone, and 2-hydroxy-4-methoxybenzophenone.
゜Benzophenone compounds such as 2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-(2-hydroxy-B-t-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy -8,
5-dipentylphenyl)benzotriazole, 2-(
2-Hydroxy-B-t-butyl-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-8,5-di-t-butylphenyl) ) Benzotriazole, 2-(2-hydroxy-8,5-di-t-butylphenyl)-5-chloro-benzotriazole, 2-
(2-hydroxy-5-t-octylphenyl)benzotriazole, 2-(2-hydroxy-8゜5-di(
Benzotriazole compounds such as α,α-dimethylpencyl)phenyl)benzotriazole, phenyl salicylate, P-'-b? 51 rurate, 2,4-ge-t
-butylphenyl-8', 5'-di-t-butyl-
4'-Hydroxybenzoate, hexadecyl-8,5
-benzoate compounds such as di-t-butyl-4-hydroxybenzoate, Ni salt of dibutyl-dithiocarbamic acid, [2,2'-thiobis(4-1-octyl phenolate)]-]n dithylamine Ni complex bis (8,
Ni salt such as Ni salt of 5-di-t-butyl-4-hydroxybenzylphosphoric acid) monoethyl ester
cyanoacrylate compounds such as ethyl 2-cyano-8,8-diphenylacrylate and N-
Examples of oxalic acid diamides include 2-ethylphenyl-N'-2-ethoxy-5-t-butylphenyl oxalic acid diamide and N-2-ethylphenyl-N'-2-ethoxyphenyl oxalic acid diamide. Synthetic resins stabilized by the 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, and ethylene-butene. Poly-α-olefin copolymers such as -1 random copolymers, copolymers of poly-α-olefins and vinyl monomers such as maleic anhydride-modified polypropylene, and mixtures thereof, chlorinated polyethylene, EVA resins, polyvinyl chloride, Methacrylic resin, polystyrene, high impact polystyrene, ABS
Examples include resin, AES resin, MBS resin, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, polycarbonate, polyacetal, polyurethane, and unsaturated polyester resin. Furthermore, 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 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 mixing with an E-kissing roll is
Form into a 1m+ sheet with a heat press at 10°C, and
A test piece of 50×BOX 1 m was prepared.

This test piece was irradiated with light in a sunshine weather meter (light source: carbon arc, black panel temperature: 88±8°C, spray cycle = 120 minutes, spray time = 18 minutes) and bent into a shrimp shape every 60 hours. The weather resistance was evaluated by measuring the time it took to break.

In addition, a test piece of 40 x 40 x 1 m was prepared, and 160
The time required for 80% of the specimen area to become brittle was measured in a gear oven at ℃.

This was defined as the thermal embrittlement induction period, and the thermal and oxidative stability was evaluated.

The results are shown in Table-2.

Blend> Unstabilized polypropylene 100 parts by weight Calcium stearate 0.1 2.6-di-t-butyl-4-methylphenol 0.0
5 Test Compounds Listed in Table 2 In the table, UVA-1 to AO-9 indicate the following compounds.

UVA-12-hydroxy-4-n-octoxybenzophenone UVA-22-(2-t:Fo4cy8-butyl-
5-Methylphenyl)-5-chlorobenzotriazole UVA-82-(2-hydroxy8,5-dipentylphenyl)benzotriazole UVA-4! -2-Schiff / -8,8-Diphenylacrylate UVA-5 bis(8,5-di-t-butyl-4-hydroxybenzyl phosphoric acid) monoethyl ester N1 salt UVA-6 bis( 2,2,6,6-tetramethyl-4-
Piperidyl) Sebacate UVA-7 Tinuvin 944 (Ciba Geigy) (Hindered piperidine light stabilizer) AO-1 Tris (8,
5-di-t-butyl-4-hydroxybenzyl) isocyanurate AO-2 dilauryl-8,8'-thiodipropionate AO-8 pentaerythritol tetrakis(8-dodecylthiopropionate) Example 2 25% urethane Dope (25 parts polyurethane resin, 8
．． The test compounds shown in Table 8 were added to 75 parts of dimethylformamide (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 wm and heated at 45°C.
The dried beef was dried for 1 hour using a drying method. The sheet obtained in this way was punched out using a No. 8 dumbbell, and a fade meter was used (light source: ultraviolet carbon arc, black panel temperature = 68 ± 8 ° C).
) after 60 hours and 120 hours of light irradiation, a tensile test (
Tensile speed: 2005 w+/m, measurement temperature: 25° C.) to determine the retention of breaking strength.

The results are shown in Table-8.

Continuing from page 1 ■Int, CI, 4 Identification code Office docket number 6681-4J Procedural amendment (voluntary) May 31, 1980 Commissioner of the Japan Patent Office Kazuo Wakasugi 2 Name of the invention Stabilized synthetic resin composition 3 , Relationship with the case of the person making the amendment Patent applicant 5, "Detailed description of the invention" column 6 of the specification to be amended, Table 2 (8) on page 20 of the specification of the contents of the amendment and page 28 Table-8
shall be corrected with the attached Tables 2(8) and 8, respectively.

that's all Table-8

Claims (1)

[Scope of Claims] A synthetic resin represented by the general formula (1) (wherein R1 and R2 each independently represent a hydrogen atom or a methyl group, and R8 represents an alkylene group having 1 to 4 carbon atoms). Stabilized synthetic resin-containing acid compound characterized by blending a hindered piperidine compound with a phenolic antioxidant and a sulfur antioxidant.