WO2000000540A1

WO2000000540A1 - Stabilizer containing vitamin e for organic polymeric material

Info

Publication number: WO2000000540A1
Application number: PCT/JP1998/005829
Authority: WO
Inventors: Takeshi Inoue; Shoichi Horie
Original assignee: Yoshitomi Fine Chemicals, Ltd.
Priority date: 1998-06-26
Filing date: 1998-12-21
Publication date: 2000-01-06

Abstract

A stabilizer composition for organic polymeric materials which comprises a compound represented by general formula (1) (wherein R?1, R2, and R3¿ are the same or different and each represents hydrogen or methyl), a phenolic antioxidant, and a phosphorus compound antioxidant, wherein the compound represented by formula (1) is contained in a specific amount relative to the sum of the three ingredients. By using the composition as a stabilizer for an organic polymeric material, a stabilized organic polymeric material can be provided which is excellent in heat resistance and especially in processing stability.

Description

W 0

Specification

Stabilizer for organic polymer materials containing vitamin E

Technical field

The present invention relates to a stabilized organic material composition. More specifically, organic polymer materials that are degraded by oxidation, heat, and light are stabilized so as not to cause deterioration in quality such as changes in physical properties and appearance even when subjected to heat history during processing and use. The present invention relates to an organic polymer material composition and a stabilizer for an organic polymer material.

Background art

Organic polymer materials composed of organic compounds such as natural polymers, synthetic polymers, oils and fats, lubricating oils, and hydraulic oils are degraded by oxidation, heat, light, etc., reducing their usefulness. Stabilizers called stabilizers have been researched and developed, and added to these organic polymers to obtain organic polymer material compositions that are less susceptible to deterioration. These antioxidant stabilizers were researched and developed for phenolic compounds in the 1930s and for phosphorus compounds in the 1920s, and various types of antioxidants have been developed since then. Many antioxidants are widely used depending on the application, and in particular, some antioxidants are very widely used.

It is also widely used to combine different types of antioxidants in order to simultaneously achieve different effects or obtain synergistic effects. For example, coloring has been improved by adding a phosphorus-based antioxidant to a phenol-based antioxidant.

By the way, in the 1980s, compounds with higher safety were demanded because of the hygiene and safety issues of funinol-based antioxidants, and as a substitute for phenol-based antioxidants, vitamin E derived from natural products was used. A 6-hydroxycycloman compound having a structure similar to that of vitamin E has been proposed. Instead of combining a funinol antioxidant and a phosphorus antioxidant together, a 6-hydroxychroman compound and a phosphorus antioxidant are used. An organic polymer material composition blended together has been proposed. These phenolic antioxidants are primary antioxidants, and the phosphorus antioxidants are secondary antioxidants. Are used together from the viewpoint that they exhibit different effects, but the compounding ratio is usually described as about the same amount to about several times of the phosphoric antioxidant with respect to the phenolic antioxidant. In many cases, only specific ratios are described in Examples. Further, a composition containing a 6-hydroxychroman compound as a primary antioxidant has not been widely used as an antioxidant because the problem of coloring property has not been solved.

In recent years, 3-arylbenzofuranone compounds have been developed as synergists for phosphorus antioxidants and phenolic antioxidants, but more effective ones are being sought.

The above-mentioned prior art will be described in detail with reference to literature names.

General formula (1), which is one of the essential components of the stabilizer for organic polymer materials in the present invention.

(R ¹ , R ² and R ³ may be the same or different and each represent a hydrogen atom or a methyl group.) The compounds shown in the above are compounds widely known as antioxidants such as oils and fats and polyolefins. It is.

Japanese Unexamined Patent Publication (Kokai) No. 60-72880 discloses a stabilizer for an organic substance containing a 6-hydroxychroman derivative in an amount of about 0.001% to about 5% by weight based on the organic substance. However, in the examples, only examples in which 0.01% by weight was blended are described, and no description is given of the use with other components, and there is no description about the processing stability. Neither described nor suggested.

Japanese Patent Application Laid-Open No. Hei 3_411135 discloses that polyolefin, an inorganic filler, a lubricant and / or an antistatic agent are added in an amount of 0.01% by weight based on 100 parts by weight of polyolefin. There is a description of a food container with improved odor containing from 6 parts to 2.0 parts by weight of a 6-hydroxychroman compound.

A phenol-based antioxidant, which is another essential component of the stabilizer for organic polymer materials in the present invention, is well known as an antioxidant for organic polymers, and is used as a general-purpose antioxidant today. Used.

The phosphorus antioxidant used as a component of the stabilizer for organic polymer materials in the present invention is well known as an antioxidant for organic polymers. For example, phosphite compounds and phosphonate compounds are used in combination with hindered phenol compounds as stabilizers during the processing of synthetic resins. It is described in gazettes such as No. 6-32, 339, and is used as a general-purpose antioxidant today.

Next, a conventional technique in which a 6-hydroxychroman compound is combined with another antioxidant will be described.

Japanese Patent Application Laid-Open No. Sho 49-112124 describes a composition comprising a polyolefin and a vitamin E derivative in an amount of about 0.005% by weight to about 5% by weight. In addition, a synergistic effect can be observed by combining the vitamin E derivative with thiodialkanates, which are sulfur-based antioxidants, and the compound can be further stabilized, and further combined with phosphites However, it is described that a synergistic effect can be similarly obtained by blending the polyolefins and that the polyolefins can be further stabilized. However, in the examples, only examples in which 0.1% by weight were blended are described. When used in combination with the above component, only the case where 30% by weight or more of 6-hydroxychroman is added to the total amount of the antioxidant is described. There is no description or suggestion about processing stability.

Japanese Patent Application Laid-Open No. 54-55043 discloses a polyolefin compound comprising vitamin E and tris (nonylphenyl) phosphite, which is excellent in processing stability and hue. 0.005 to 0.5 part by weight of vitamin E and 0.05 to 0.5 part by weight of phosphite compound per 100 parts by weight of Described polyolefin compositions.

Further, in Examples of this publication, with respect to 100 parts by weight of polypropylene, 0.03 parts by weight of vitamin E and 0.05 or 0.1 parts by weight of three kinds of phosphite compounds were used. It describes the amount of change in yellowness of a resin containing 0.01 part by weight of 2,6-ditertiary butyl-p-cresol as a phenolic antioxidant.

Also, when used in combination with other stabilizers, for example, phenolic antioxidants such as tetrakis [methylene-13- (3,5-di-tert-butyl-14-hydroxyphenyl) propionate] methane, a synergistic effect is obtained. It states that there may be cases where it is acceptable, but does not specifically state the conditions.

JP-A-62-86036 also discloses that vitamin E and a specific phosphorus-based antioxidant tris (2,4-di-tert-butylphenyl) phosphite and bis (2, 4-Gee tertiary butylphenyl) pentaerythritol diphosphite and the like are described as in JP-A-54-55043.

In Japanese Patent Publication No. 1986/657, the 6-hydroxycyclomane compound and tetrax (2,4-di-tert-butylphenyl) -14,4,1-biphenylenediphosphite are disclosed. The polyolefin composition containing 0.01 to 1% by weight is described in each case. However, there is no particular description of the blending ratio, and the examples show that the blending ratio is 1: 1. Is only described.

Japanese Patent Application Laid-Open No. Hei 8-224580 discloses an α-tocopher solution consisting of a-tocoprole, glycerol, a glyceride surfactant, and polyethylene glycol, and a tetrakis [methylene- ( 3,5-Di-tert-butylbutyl-4-hydroxyphenyl) propionate] A stabilizer composition that solves the coloring property of a composition containing a phenolic antioxidant such as methane is described. The description is for a case where the ratio of α_tocoprolol, which is a 6-hydroxycycloman compound, to the antioxidant is 20% by weight or more.

Japanese Patent Application Laid-Open No. 6-55041812 discloses that in order to suppress oxidation of polyether, It is described that 50 to 1000 ppm, particularly preferably 50 to 200 pm, of a 6-hydroxychroman compound is blended based on the weight of the polyester. Further, an additional phenolic antioxidant, hindered phenol, is used in an amount of 100 to 200 ppm based on the weight of polyether, and an organic phosphorous acid, which is a phosphorus-based antioxidant, is polyether. It is stated that 20 to 2000 ppm can be added based on the weight of Further, it is described that a preferred antioxidant composition contains about 0.5 to 5 parts by weight of hindered phenol and 0.5 to 3 parts by weight of phosphorous acid per 1 part by weight of tocopherol, which is 6-hydroxychroman. Have been. From these results, the upper limit of the ratio of the 6-hydroxycycloman compound to the total amount of these antioxidants can be reduced to 50%, and the lower limit can be calculated to be approximately 11%. In Examples, this ratio is 33% by weight. Japanese Unexamined Patent Publication (Kokai) No. Sho 61-32324 describes the case of polyolefin, vitamin E which is a 6-hydroxychroman derivative, and phosphorus-based antioxidant. A polyolefin blend having excellent stability and hue by using a specific phosphite in combination is described. With respect to these blending amounts, 0.005 to 0.5 parts by weight of bismuth E and 0.005 to 0.5 parts by weight of phosphite are added to 100 parts by weight of polyolefin. It is also described that 0.01 parts by weight to 1 part by weight of a phenolic antioxidant is further added.However, there is no description or suggestion about the blending ratio, and the examples do not mention these. It describes an example containing about 21% to about 38% by weight of vitamin E based on the total amount of antioxidants.

Japanese Unexamined Patent Publication (Kokai) No. 63-150600 or U.S. Pat. No. 4,806,580 discloses that 1 part by weight of a chroman derivative containing vitamin E and a specific phosphorus-based antioxidant It describes a stabilizer composition for synthetic resins which is more stabilized against discoloration and contains 14 parts by weight. The lower left column on page 2 of the description describes the background of using vitamin E and 6-hydroxychroman derivatives derived from natural products as alternatives to funor-based antioxidants due to hygiene problems. By the way, when the above mixing ratio is converted, By containing about 6.7% by weight to about 16.7% by weight of the 6-hydroxychroman derivative containing vitamin E with respect to the total amount of the 6-hydroxychroman compound containing min E and the phosphorus antioxidant. is there. In the examples, the above ranges are described, and in the comparative examples, compositions having the above compounding ratios of 1:15 and 1:16 are described. When the compounding ratio of this comparative example is converted into the ratio of the 6-hydroxychroman derivative containing vitamin E to the total amount of the 6-hydroxychroman compound containing vitamin E and the phosphorus-based antioxidant, each is about 6.3. % By weight, about 5.9% by weight o

Japanese Patent Application Publication No. 6-504457 discloses a radiation-resistant resin composition using a chroman compound containing vitamin E and a specific phosphorus compound and a polyhydroxy compound such as glycerol. The compounding ratio of the specific phosphorous compound to the 6-hydroxychroman compound is described as 0.5 to 20, preferably 1 to 10, more preferably 1 to 5, and most preferably 4. In the examples, examples in which the compounding ratio is 1, 2, 4, and 9 are described. When this compounding ratio is converted, the amount of the 6-hydroxychroman derivative is about 67% by weight to about 4.76% by weight, preferably about 6% by weight, based on the total amount of the 6-hydroxycycloman compound and the phosphorus-based antioxidant. 50% by weight to about 9.52% by weight, more preferably 50% by weight to 16.7% by weight, and most preferably 20% by weight. Examples of 3% by weight, 33.3% by weight, 20.0% by weight, and 10.0% by weight are described.

However, the content of the invention described in these publications is that "the chroman compound containing vitamin E is an excellent antioxidant or processing stabilizer even though the resin is colored, but it is used together with other antioxidants." The problem is solved by preventing the coloring or by using a chroman compound containing vitamin E in such a small amount that the coloring does not occur.

Therefore, the description of vitamin E is also described as an example of a phenol-based antioxidant, and the amount of addition is usually 0.05 to 0.5 parts by weight based on the resin as in the case of the phenol-based antioxidant. It is characterized by a blending amount of 5 parts by weight. In addition, even if it describes processing stability, the proportion of the 6-hydroxychroman compound is usually 50% by weight to 10% by weight with respect to the total amount of the antioxidant incorporated in the organic polymer. Examples of the use of a 6-hydroxychromane compound and a phenolic antioxidant in combination with a 6-hydroxychroman compound, a phosphorus-based antioxidant and a phenol-based antioxidant There is no specific description of an example in which the three agents are used together.

Further, vitamin E and tris (2,4-di-tert-butylbutyl) phosphite and tetrakis described in Japanese Patent Application Laid-Open No. 63-150600 (US Pat. No. 4,680,580) are disclosed. (2,4-di-tert-butylphenyl) Stabilizing compositions for synthetic resins containing certain phosphorus compounds with 1,4,4,1-biphenylenediphosphonite include vitamins based on the total amount of these antioxidants. The proportion of E is from 6.7% by weight to 16.7% by weight, which is different from the composition of the present invention in terms of the proportion of vitamin E and in the components.

By the way, Example 14 described in Paragraph No. 0226 of JP-A-7-233160 can be used for the same purpose as the present invention. Dimethylphenyl) -5,7-di-tert-butyl-13H-benzofuran-2-one (in the same application, designated as compound 103) is described. Breakthrough by polymer stabilization announced at the Polyolefins X international conference on February 23-26, 1997 in Heuston, Texas, USA ( A major breakthrough in polymer stabilization) is also described in the material of a lecture by C. Krohnke, and is described as a synergizing agent for phenolic antioxidants and phosphorus antioxidants. However, the synergistic effect is not satisfactory, and a more effective synergist is needed.

In addition, recently, due to the high molding temperature for high-speed molding and the high-temperature molding by alloying with engineering plastics, etc., in addition to heat resistance, excellent oxidation that is effective for processing stability The demand for inhibitors is increasing, and these known Stabilizing compositions are not yet fully satisfactory for that purpose. Further, in addition to heat resistance, there is an increasing demand for an antioxidant which is effective even in a small amount with respect to processing stability.

Accordingly, an object of the present invention is to provide an excellent antioxidant which maintains the anti-coloring property, and which is effective for heat resistance and processing stability in a small amount.

Disclosure of the invention

That is, the present invention is as follows.

[1]: General formula (1)

(R ¹ , R ² and R ³ may be the same or different and each represent a hydrogen atom or a methyl group.) The compound represented by the formula (1), a fuanol-based antioxidant and a phosphorus-based antioxidant are contained. The general formula (1)

0.5 to 5.5% by weight of the compound represented by the formula, and 99.5 to 94.5% by weight of the total amount of the phenolic antioxidant and the phosphorus antioxidant. Stabilizer composition for organic polymer materials.

[2]: General formula (1)

(R ¹ , R ² and R ³ may be the same or different and represent a hydrogen atom or a methyl group.) The proportion of the compound represented by the formula is 1.0 to 4.5% by weight. ] The stabilizer composition for organic polymer materials as described in [1].

[3]: [1] or [2], wherein the weight ratio of the compounding amount of the phenolic antioxidant to the compounding amount of the phosphorus-based antioxidant is 1: 0.2 to 1: 5. The stabilizer composition for an organic polymer material according to the above.

[4]: The fuanol-based antioxidant is

n-octadecyl 3- (4-hydroxy-3,5-di-tert-butylphenyl) probionate,

Tetrakis [3- (3,5-ditert-butyl-4-hydroxyhydroxy) propionyloxymethyl] methane,

1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) socyanurate, and

1,3,5-trimethyl-2,4,6-tris (3,5-ditert-butyl-4-hydroxybenzyl) At least one selected from the group consisting of benzene and phosphorus-based antioxidant Agent

Tris (2,4-ditert-butylphenyl) phosphite,

Tetrakis (2,4-ditertiary butylphenyl) 1-4,4, -biphenylenediphosphonate,

Tetrakis (2,4-ditertiary butyl-5-methylphenyl) 1-4,4, -biphenylenediphosphonite, Bis (2,4-di-tert-butyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate,

2,2'-methylenebis (46-di-tert-butylphenyl) -1-ethyl ester

Bis [2-methyl-1,4,6-bis (1,1-dimethylethyl) phenyl] ethyl phosphite, and

2, 2,, 2 "— a group consisting of two-necked [triethyltris (3,3,, 5,5, -tetra-primary-tert-butyl-1, Γ-biphenyl-2,2, -diyl) phosphite] The stabilizer composition for an organic polymer material according to any one of [1] to [3], which is at least one member selected from the group consisting of:

[5]: A stabilized organic polymer material obtained by blending the organic polymer with the stabilizer composition for an organic polymer material according to any one of [1] to [4]. .

[6]: A composition comprising the stabilizer composition for an organic polymer material according to any one of [1:] to [4], and a sulfur-based antioxidant and Z or a light stabilizer [5] 2. The organic polymer material according to item 1.

[7]: For organic polymer, general formula (1)

(R ¹ , R ^2, and R ³ may be the same or different and each represent a hydrogen atom or a methyl group.) The compound represented by the formula (1), a fininol antioxidant, and a phosphorus antioxidant are contained. Organic polymer material, wherein 100 parts by weight of the organic polymer material is represented by the general formula (1)

(R ¹ , R ² and R ³ may be the same or different and each represent a hydrogen atom or a methyl group.) The compound represented by the formula (1) is in the range of 0.0005 to 0.25 parts by weight. An organic polymer material characterized by being compounded by:

[8]: General formula (1)

(R ¹ , R ² and R ³ may be the same or different and represent a hydrogen atom or a methyl group.) The compounding ratio of the compound represented by the following formula is from 0.01 to 0.000. The organic polymer material according to [7], wherein the amount is 5 parts by weight.

[9]: [7] or [8], wherein the weight ratio of the compounding amount of the fuanol-based antioxidant to the compounding amount of the phosphorus-based antioxidant is 1: 0.2 to 1: 5. The organic polymer material described.

[10]: The phenolic antioxidant is

n-octadecyl 3- (4-hydroxy-3,5-di-tert-butylphenyl) probionate,

Tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane,

1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) W

The socialist, and

1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) At least one selected from the group consisting of benzene and phosphorus-based antioxidant Agent

Tris (2,4-di-tert-butylphenyl) phosphite,

Tetrakis (2,4-ditertiary butyl phenyl) 1,4,4-biphenylenediphosphonate,

Tetrakis (2,4-di-tert-butyl-5-methylphenyl) —4,4, —biphenylenediphosphonite,

Bis (2,4-di-tert-butyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl_4-methylphenyl) pentaerythritol diphosphite,

2,2, -methylenebis (4,6-ditert-butylphenyl) — 2-ethylhexyl phosphite,

Bis- [2-methyl-4,6-bis (1,1-dimethylethyl) phenyl] ethyl phosphite, and

2, 2,,, 2 "—two-mouth [triethyltris (3,3 ', 5,5' -tetra-tertiary-butyl-1,2-biphenyl-2,2, -diyl) phosphite] The stabilized organic polymer material according to any one of [7] to [9], which is at least one selected from the group consisting of:

[11]: The stabilized organic polymer material according to any one of [7] to [: 10], wherein the organic polymer is a synthetic resin.

[12]: The stabilized organic polymer material according to any one of [7] to [10], wherein the organic polymer is a polyolefin resin.

[13]: The organic polymer is a polyethylene resin, a polypropylene resin, a mixture or a compatible polymer of the polyethylene resin and the polypropylene resin, or a polyethylene. Compatible polymer containing lene resin and / or polypropylene resin, ethylene

— The stabilized organic polymer material according to any one of [7] to [10], which is a vinyl acetate copolymer or an ethylene-propylene copolymer.

[14]: The stabilized organic polymer material according to any one of [7] to [10], further comprising a sulfur-based antioxidant and Z or a light stabilizer.

That is, the present invention relates to an organic polymer such as a synthetic resin, in addition to a general-purpose phenol-based antioxidant and a phosphorus-based antioxidant which are generally used, a compound represented by the general formula

(R ¹ , R ² and R ³ may be the same or different and each represent a hydrogen atom or a methyl group.) An extremely small amount of the compound represented by On the ability to obtain the material.

Here, the extremely small amount refers to 0.0005 to 0.025 parts by weight, and preferably 0.001 to 0.005 parts by weight, based on 100 parts by weight of the organic polymer material. The ratio of the compound represented by the general formula (1) to the total amount of the general-purpose funinol antioxidant, the phosphorus antioxidant, and the compound represented by the general formula (1) is 0.5 to 5. O in an amount of about 5% by weight, preferably 1.0 to 4.5% by weight o

The composition of the present invention, wherein the compound represented by the general formula (1) is based on the total amount of the general-purpose phenol-based antioxidant, the phosphorus-based antioxidant, and the compound represented by the general formula (1). When the content exceeds 5.5% by weight, it is difficult to obtain a solid and easy-to-handle stabilizer composition in addition to coloring of the resin, and when the compound represented by the general formula (1) is less than 0.5% by weight, the effect is satisfactory. Is not shown.

In addition, the weight ratio with general-purpose fuanol-based antioxidant Z-phosphorus-based antioxidant exceeds 5 When it is obtained, the anti-coloring property cannot be maintained, and when it is less than 0.2, satisfactory processing stability is not exhibited. It is preferred that this ratio be 1: 0.2 to 1: 5.

Japanese Patent Application Laid-Open No. Hei 8_2, 548,330 and Japanese Patent Laid-Open Publication No. Hei 6-504,577 contain no phenol-based antioxidants (excluding vitamin E) or phosphorus-based antioxidants. It is described that a composition containing a small amount of vitamin E using other compounds such as glycerol can solve the problems of phenol-based antioxidants and phosphorus-based antioxidants. However, these descriptions are expressed by a very small amount of the general formula (1) in addition to the phosphorus-based antioxidant which has a synergistic effect with the phenol-based antioxidant in the ordinary processing stability which is the object of the present invention. Leap while maintaining the heat resistance of the phenolic antioxidant and the anti-coloring property of the phosphorus antioxidant by using a stabilizer composition containing a compound as a processing stability efficacy enhancer. This is not the same as enhancing the overall processing stability.

The compounds included in the general formula (1) include the following.

a - tocopherol ^{^{(R 1, R 2, R}} 3 both methyl group)

; 8—Tocoprole (R ² is a hydrogen atom, R ¹ and R ³ are methyl groups)

7—Tocoprole (R ¹ is a hydrogen atom, R ² and R ³ are methyl groups)

5-tocoprole (R ¹ and R ² are hydrogen atoms, R ³ is methyl group)

Toco Ichiru ^{^{(R 1, R 2, R}} 3 are both hydrogen atoms)

Examples of the synthetic resin stabilized by the composition of the present invention include resins such as thermoplastic resins and thermosetting resins.

Examples of the thermoplastic resin include an olefin resin, a halogen-containing polymer, a styrene resin, an acrylic resin, a thermoplastic polyester resin, a polyamide resin, an aromatic polycarbonate resin, a polyacetal resin, a polyethylene oxide resin, and a polyolefin resin. Penylene ether resin, polysulfone resin, polyurethane resin, petroleum resin, polyvinyl acetate resin, vinyl acetal resin, cellulose (cellulose) resin, polyether sulfone resin, polyphenylene sulfide resin, polyester ketone resin, Polyetherimide resin, polyoxybenzoyl resin, polyimide tree For example, a resin, a polymer imide resin, a polyamide imide resin, a polyamide resin, a fluorine resin, an ionomer, a thermoplastic elastomer, and the like, and a mixture thereof can be used.

Examples of the olefin resin include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-high-molecular-weight polyethylene, polypropylene, polybutene-11, polypentene, and poly-3-methylbutylene. Α-olefin homopolymer having 2 to 8 carbon atoms; ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene * butene-1 random copolymer, propylene-ethylene-butene-1 random Α-methyl olefin copolymers such as copolymers; copolymers of α-methyl olefins with other monomers such as maleic anhydride-modified polypropylene and ethylene / vinyl acetate copolymer; It is also possible to use two or more of these or a mixture of these with other compatible polymers. Kill.

After polymerization, these olefinic resins have been subjected to a slight purification treatment with a step of removing catalyst residues, and to a relatively high degree of purification, as well as a catalyst removal step using a highly active catalyst. Olefin-based resin containing no or simplified catalyst residue, in particular, a catalyst residue obtained using a zigzag-type catalyst or a chromium-based catalyst using a halogen-containing magnesium compound as a catalyst carrier, and still having a catalyst residue It may be a crystalline olefin-based resin that has not been subjected to a removal step (Japanese Patent Publication No. 62-44418, Japanese Patent Publication No. 3-52642, U.S. Pat. No. 4,115,633). No. 9). Further, it may be an olefin resin having a very narrow molecular weight distribution obtained by a metasite-based single-site catalyst (Journa 1 of J. Op. Polymer Polymer Science. Polymer 1 Chemistry Edition). Pollymer Chemistry Edition, Vol. 23, pp. 2151 (1989)).

Examples of the halogen-containing polymer include polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, vinyl chloride and acrylic acid. Examples include a kill ester copolymer and chlorinated polyethylene.

Examples of the styrene-based resin include polystyrene and impact-resistant polystyrene.

Styrene-acrylonitrile copolymer, styrene-MMA copolymer, ABS resin, AES resin, ACS resin, AAS resin, ESS resin, and the like, and mixtures thereof.

Examples of the acryl-based resin include polyacrylate and polymethacrylate.

Examples of the thermoplastic polyester resin include polyethylene terephthalate and polybutylene terephthalate.

Examples of the polyamide resin include Nylon 4, Nylon 6, Nylon 4 • 6, Nylon 6.6, Nylon 6 • 10, Nylon 7, Nylon 8, Nylon 12, Nylon 6 • 12, Nylon 11 · 12 and alamide, and mixtures thereof.

Examples of the thermosetting resin include unsaturated polyester resin, phenol resin, urine resin, melamine resin, epoxy resin, polyimide resin, silicone resin, diyl phthalate resin, polyurethane resin, and furan resin.

As the synthetic resin of the stabilized synthetic resin composition of the present invention, an excellent antioxidant effect is exhibited particularly when it is blended with an olefin resin, especially an α-olefin homopolymer or an α-olefin copolymer. . Most preferred as alpha-refins are polypropylene and polyethylene.

General formula (1) used in the present invention

(RR ² and R ³ may be the same or different, and Represents a tyl group. ) Can be synthesized according to the method described in JP-B-45-231346. Naturally occurring vitamin Es can also be used.

The content of the compound of the general formula (1) in the organic polymer material of the present invention is 0.0005 to 0.025 parts by weight based on 100 parts by weight of the organic polymer material. Parts, preferably 0.001 to 0.005 parts by weight.

The total amount of the compound of the general formula (1), the fuanol-based antioxidant and the phosphorus-based antioxidant in the organic polymer material composition of the present invention is 0. 0.1 to 1 part by weight, preferably 0.02 to 0.2 part by weight. By setting the amount to 0.01 to 1 part by weight, it is possible to obtain an organic polymer material that is hardly colored and has excellent processing stability.

The ratio of the compound represented by the general formula (1), the phenolic antioxidant, and the phosphorus-based antioxidant is defined by the compound represented by the general formula (1), the phenolic antioxidant, and the phosphorus-based antioxidant. 0.5 wt% to 5.5 wt% of the compound represented by the general formula (1) based on the total amount of the compound, and the total amount of the phenol-based antioxidant and the phosphorus-based antioxidant is 99.5 wt%. % To 94.5% by weight, preferably 1.0% to 4.5% by weight of the compound represented by the general formula (1), and 99.0% of a phenolic antioxidant and a phosphorus-based antioxidant. % By weight to 95.5% by weight. By using the stabilizer composition for an organic polymer material of the present invention in which the proportion of the compound represented by the general formula (1) is within the above range, an organic polymer material that is hardly colored and has excellent heat stability can be obtained. Obtainable.

In the present invention, the weight ratio of the compounding amount of the phenolic antioxidant to the compounding amount of the phosphorus antioxidant may be arbitrary, but is preferably 1: 0.2 to 1: 5, and more preferably 1: 5. 0.25 to 1: 4. By using the stabilizer composition for an organic polymer material of the present invention having a weight ratio within this range, an organic polymer material having excellent anti-coloring properties and processing stability can be obtained.

The phenolic antioxidant used in the present invention is represented by the following general formula (2)

(R ⁴ represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.) Compounds containing one or more of the structures represented by Specifically, for example,

n-tactadecyl 3- (4-hydroxy-3,5-di-tert-butylphenyl) probionate,

Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane,

1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -socyanurate,

1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-4-hydroxybenzyl) benzene,

1,1,3-tris [2-methyl-4-[3-(3,5-ditert-butyl-4 -hydroxyphenyl) propionyloxy] -5-tert-butylbutylbutane,

Bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentagen,

1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid,

3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] —1,1-dimethylethyl] —2,4,8,10-tetra Oxaspiro [5.5] pendecane, 2,6-di-tert-butyl-4-methylphenol,

2,4—dimethyl _ 6 —tertiary butyl phenol,

2, 6-ditertiary butyl, 4-hydroxymethylphenol,

2,6-di-tert-butyl_4—ethylphenol,

2, 4, 6 — tritertiary butyl phenol,

Butylated hydroxyanisole,

Isoctyl 3- (4-hydroxy-3,5-di-tert-butylphenyl)

Distearyl '(4-hydroxy-3-methyl-5-tertiary butyl) benzyl malonate,

2,2,1-methylenebis (4-methyl-1-6-tert-butylphenol), 2,2, -methylenebis (4-ethyl-6-tert-butylphenol), 4,4,1-methylenebis (2,6 —Di-tertiary butylphenol),

2,2, -butylidenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,2, -thiobis (4-methyl-6) _ Tertiary butyl phenol),

4,4, -Chobis (3-methyl-6-tert-butylphenol), Styrene phenol,

N, N'-Hexamethylenebis (3,5-di-tert-butyl-4-4-hydroxy-hydrocinamide),

Bis (3,5-ditertiary butyl-ethyl 4-hydroxybenzylphosphonate) calcium,

1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane,

1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxy xyphenyl) propionate],

2,2'-methylenebis (4-methyl-16-cyclohexylphenol), 2,2, -methylenebis [6- (1-methylcyclohexyl) -14-methylphenol],

Triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate],

Ethylene glycol-bis (3,3_bis (3_tert-butyl_4-4-hydroxyphenyl) butyrate),

2-tert-butyl- 6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) 1-4-methylphenylacrylic acid,

2,2, -oxamido-bis [ethyl-3 ((3,5-ditert-butyl-4-4-hydroxyphenyl) propionate],

6 _ (4-hydroxy-1,3,5-di-tert-butylanilino) 1,2,4-dioctylthio-1,3,5-triazine,

Bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-1-5-methylbenzyl) phenyl] terephthalate,

3,9-bis [2- [3- (3,5-di-tert-butyl_4-hydroxypropyl) propionyloxy] —1,1,1-dimethylethyl] —2,4,8,10-te Toloxaspiro [5.5] Pendecane,

1,3,5-tris [3- (3,5-di-tert-butyl_4—hydroxyphenyl) propionyloxy] ethyl isocyanate,

2,2-thioethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyhydroxy) propionate],

2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl]-4,6-di-tert-pentylphenyl atalylate, and 2,4-bis [(Octylthio) methyl] 10-cresol, propyl gallate, octyl gallate, and dodecyl gallate, but are not limited thereto.

Preferred phenolic antioxidants include W

n-octadecyl 3- (3,5-di-tertiary butyl-4-hydroxyphenyl) propionate,

Tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane,

1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -socyanureto,

1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene,

1,1,3—tris [2-methyl—4— [3— (3,5—di-tert-butyl—4—hydroxyphenyl) propionyloxy] 1.5-tert-butylbutyl] butane,

2,5,7,8-tetramethyl-2 (4 ', 8', 12, -trimethyltridecyl) chroman-6-ol,

2,4-bis [(octylthio) methyl] -1-o-cresol,

Bis (3-tert-butyl-14-hydroxy-5-methylphenyl) dicyclopentagen,

1,3,5-tris (4-tert-butyl-3 -hydroxy-2,6-dimethylbenzyl) isocyanuric acid,

3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] —1,1,1-dimethylethyl] —2,4,8,10-tetra Oxaspiro [5.5] didecane.

Particularly preferred funinol-based antioxidants include:

n—Taitadecyl 3 — (3,5-ditertiary butyl—4—hydroxyphenyl) probionate,

Tetrakis [3- (3,5-di-tert-butyl-4-hydroxypropyl) propionyloxymethyl] methane,

1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Socinurate,

1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene.

In the present invention, one or more of these phenolic antioxidants can be used.

As the phosphorus antioxidant used in the present invention, a compound represented by the following general formula (3)

0-R ⁵

—— P (3)

0-R ⁵

(R ⁵ represents an alkyl group or a phenyl group which may be substituted with 1 to 3 alkyl groups.) A compound having one or more structures represented by the following formulas in the molecule:

Tris (2,4-di-tertiary butylphenyl) phosphite,

Bis [2-methyl-4,6-bis (1,1-dimethylethyl) phenyl] ethyl phosphite,

Tetrakis (2,4-di-tert-butylphenyl) — 4,4,1-biphenylenediphosphonite,

Tetrakis (2,4-di-tert-butyl-5-methylphenyl) —4,4, —biphenylenediphosphonite;

Or, in the molecule, the general formula (4)

― CH ₂ CH ₂ 1 0

C P-0-R ⁶ (4)

― CH ₂ CH ₂ —0

(Wherein, R ⁶ represents a phenyl group which may be substituted with an alkyl group or a aryl group.) A compound having one or more structures represented by the following formulas in a molecule:

Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphate, Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate,

Bis [2,4-bis (na, α-dimethylbenzyl) phenyl] pentaerythritol phosphate,

(2,4,6—tri-tert-butylphenyl) —2-butyl—2-ethyl—1,3-propanediol phosphate,

Distearyl pentaerythritol diphosphite;

Or, in the molecule, the general formula (5)

(R ⁷ represents an alkyl group having 1 to 4 carbon atoms, R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ represents a direct bond or an alkylene group having 1 to 4 carbon atoms.) Compounds containing one or two or more in the molecule, such as

2,2'-methylenebis (4,6-di-tert-butylphenyl) -1-2-ethylhexyl phosphite,

2,2 ', 2 "—Tri-tri [triethyltris (3,3', 5,5, -tetra-tert-butyl- 1 ,，-biphenyl2,2'-diyl) phosphite], W

2,2-ethylidene-bis (4,6-di-tert-butylphenyl) fluorophosphonite,

2,10-dimethyl-4,8-ditert-butyl-6- {2- [3— (3-tert-butyl-4-hydroxy-15-methylphenyl) propionyloxy] ethoxy} —12H —Dibenzo [d, g] [1,3,2] dioxaphosphosine;

Hexatridecyl 1,1,3-tris (2-methyl_4-hydroxy-5_tertiary butylphenyl) butanetriphosphite.

Preferred phosphorus antioxidants include:

Tris (2,4-di-tertiary butylphenyl) phosphite,

Tetrakis (2,4-di-tert-butylphenyl) 1-4,4'-biphenylenediphosphonite,

Tetrakis (2,4-ditertiary butyl-5-methylphenyl) 1-4,4, -biphenylenediphosphonite,

Bis (2,4-ditertiary butylphenyl) pentaerythritol diphosphite,

Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate,

2,2, -methylenebis (4,6-di-tert-butylphenyl) -1-2-ethylhexyl phosphite,

Bis [2-methyl-1,4,6-bis (1,1-dimethylethyl) phenyl] ethyl phosphite,

2,2,, 2 "12-triethyl [triethyltris (3,3 ', 5,5, -tetra-tert-butyl-1, 1-biphenyl-2,2'-diyl) phosphite],

2,2-ethylidene-bis (4,6-di-tert-butylphenyl) fluorophosphonite,

2,10-Dimethyl-4,8-ditertiary tertyl 6- {2— [3— (3—third W

Tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethoxy} 1-12H-dibenzo [d, g] [1,3,2] dioxaphosphin, bis [2,4-bis] (Α, α-dimethylbenzyl) phenyl] pentaerythritol phosphite,

(2,4,6—tri-tertiary butyl) —2-butyl—2-ethyl-1,

3 -propanediol phosphite.

Particularly preferred phosphorus antioxidants include:

Tris (2,4-di-tertiary butylphenyl) phosphite,

Tetrakis (2,4-ditert-butylphenyl) 1-4,4,1-biphenylenediphosphonate,

Tetrakis (2,4-ditertiary butyl-5-methylphenyl) _4,4, -biphenylenediphosphonate,

Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite,

Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate,

2,2, -methylenebis (4,6-di-tert-butylphenyl) _2-ethylhexylphosphite

Bis [2-methyl-1,4,6-bis (1,1-dimethylethyl) phenyl] ethyl phosphite,

2,2,, 2 "-ditrilo [triethyltris (3,3,, 5,5'-tetra-tert-butyl-1, 2-diphenyl-2,2'-diyl) phosphite].

In the present invention, one or more of these phosphorus-based antioxidants can be used.

By combining the stabilized synthetic resin composition of the present invention with a sulfur-based antioxidant, a synthetic resin material having more excellent stability can be obtained. Other sulfur-based antioxidants are not particularly limited, but are preferably dilauryl thiodipropionate,

Lauryl stearyl thiodipropionate,

Jimi ristylthiodiprobionet,

Distearyl thiodipropionate,

Ditridecylthiodiprobionet,

Tetrakis [(3-laurylthiopropionyloxy) methyl] methane, tetrakis [(3-stearylthiopropionyloxy) methyl] methane, bis [2-methyl-4-4- (3-n-alkyl (C12) CC 14) thiopropionyloxy) —5-tert-butylbutyl] sulfide. One or more sulfur-based antioxidants can be added to the organic polymer material composition of the present invention. The sulfur-based antioxidant is preferably added in a proportion of 0.005 to 5 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the organic polymer material composition. can do. When two or more sulfur-based antioxidants are used, they are preferably added so that the total amount is within the above range.

By combining the stabilized synthetic resin composition of the present invention with an ultraviolet stabilizer or a light stabilizer, an organic polymer material having more excellent stability can be obtained. Examples of ultraviolet absorbers and light stabilizers include salicylic acid compounds, benzofunone compounds, benzotriazole compounds, benzoate compounds, cyanoacrylate compounds, nickel compounds, and pyrididine compounds. Salicylic acid-based compounds that can be used as an absorbent include phenylsalicylate,

P—Third-class pet saliva relet,

p-tactile distillate, etc.

As a benzophenone-based compound that can be used as an ultraviolet absorber,

2, 4—dihydroxybenzophenone, 2—Hydroxy_4-methoxybenzophenone,

2,2,1-dihydroxy-1,4,4'-dimethoxybenzophenone,

2—Hydroxy 4—n—Cytoxy benzophenone,

2—Hydroxy 4-Isooctyloxybenzophenone,

2 — hydroxy 4 1 dodecyloxybenzophenone,

2 — Hydroxy-1 4-octadecyloxybenzone,

2—Hydroxy-1-methoxy-1,2,4-hydroxyl-benzophenone, bis (5-benzoyl_4—hydroxy-2-methoxyphenyl) methane, 2-hydroxy-1-4-methoxy-5-sulfo Benzophenone 'tri-no-drain,

2,2,, 4,4'-tetrahydrophenone,

2 Hydroxy-1 4 All compounds such as phenone! / Ru.

As a benzotriazole-based compound that can be used as an ultraviolet absorber,

2- (2-hydroxy-1-5-methylphenyl) benzotriazole,

2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole,

2- (2-Hydroxy-1-3-tert-butyl-5-methylphenyl) -1-5-chlorobenzotriazole,

2- (2-Hydroxy-3 5-di-tert-butylphenyl) -5-chlorobenzene

2- [2-hydroxy-5 (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole,

2-[2 -Hydroxy 35 -bis (α, α-dimethylbenzyl) phenyl] — 2 ベンゾ -benzotriazole,

Methyl '3— [3—tert-butyl—5— (2-benzotriazo-1-yl-2-yl) -1-hydroxyphenyl] propionate, and polyethylene glycol A condensate of

2- (2-hydroxy-3,5-ditertiary-amylphenyl) benzotriazole,

2,2-methylenebis [4- (1,1,3,3—tetramethylbutyl) -1-6- (2H-benzotriazoyl-2-yl) phenol],

2- (2-Hydroxy-5-tert-octylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidometyl) -5-methylphenyl] benzotriazole Compounds. As a benzoate-based compound that can be used as a light stabilizer,

n_Hexadecyl .3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-butylphenyl · 3,5-di-tert-butyl_4-hydroxybenzoate Compounds.

As cyanoacrylate compounds that can be used as an ultraviolet absorber, ethyl 2-cyano 3,3-diphenyl acrylate,

Octyl * 2-cyano3,3-diphenylacrylate. As a nickel-based compound that can be used as an ultraviolet absorber,

2—Ethylhexylamine nickel

Dimethyldithi talent Nickel rubamate,

[2,2,1-thiobis [4-1 (1,1,3,3-tetramethylbutyl) phenolate]] — n _butylamyl nickel,

[2,2, -thiobis [4- (1,1,3,3-tetramethylbutyl) phenolate]] Nickel and other compounds.

As a piperidine compound that can be used as a light stabilizer,

Bis (2,2,6,6-tetratetramethyl 4-piperidyl) sebaguete, Bis (1-year-old octyloxy 2,2,6,6-tetramethyl-1-piperidyl) sebaguet, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) 1-2- (3,5-ditert-butyl-4-hydroxybenzyl) 1-2-n-butylmalonate, tetrakis (2, 2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate,

Tetrakis (1,2,2,6,6-pentamethyl_4-piperidyl) —1,2,3,4-butanetetracarboxylate,

Poly [[6_ (1,1,3,3-tetramethylbutyl) imino_s-triazine-1,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] Hexamethylene [(2,2,6,6-tetramethyl_4-piperidyl) imino]],

Poly [(6-morpholino-s-triazine-1 2,4-diyl) [(2,2,6,6-tetramethyl-1-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl — 4-—Piperidyl) imino]] (Cyanuric chloride Z tertiary octylamine / ^ 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane condensate),

1-hydroxyxethyl-1,2,6,6-tetramethyl-1-4-piperidinol succinic acid condensate,

N, N'-bis (3-aminopropyl) ethyldiamine Z2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-14-piperidyl) amino] — 6-chloro-1 And compounds such as 3,3,5-triazine condensates. Preferred compounds that can be used as UV absorbers and light stabilizers

2-hydroxy-1-4-n-octyloxybenzophenone,

2- (2-hydroxy-1-5-methylphenyl) benzotriazole,

2- (2-hydroxy-13-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole,

2- (2-Hydroxy-1,3,5-di-tert-butylphenyl) -1-5-cyclopentene Zotriazole,

Bis (2,2,6,6-tetramethyl-1-piperidyl) sebacate, poly [[6- (1,1,3,3-tetramethylbutyl) imino-1s-triazine-1 2,4-diyl ] [(2,2,6,6-tetramethyl-1-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl_-4-piperidyl) imino]] (cyanuric chloride / third Class octylamine / 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane condensate). The organic polymer material composition of the present invention includes one or two types. The above ultraviolet absorbers or light stabilizers can be added. The ultraviolet absorber or the light stabilizer is preferably used in a proportion of 0.005 to 5 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the organic polymer material composition. Can be blended. When two or more UV absorbers or light stabilizers are used, they are preferably added so that the total amount is within the above range.

General formula (1)

(R ¹ , R ² and R ³ may be the same or different and represent a hydrogen atom or a methyl group.) In addition to the compound represented by the formula (1) and a phenolic antioxidant, More stable by blending other phenolic antioxidants, other phosphorus antioxidants, and, if necessary, sulfur antioxidants, ultraviolet absorbers, and light stabilizers into organic materials. A stabilized synthetic resin composition can be obtained. Further, if necessary, the performance of the stabilized synthetic resin composition of the present invention is significantly impaired. Other additives that do not dissolve, for example, hydrotalcites, metal tests such as calcium stearate, heavy metal deactivators such as hydrazine compounds, monoalkyltin tris (octyl thioglycolate) Organic tin stabilizers such as dialkyltin tris (octyl thioglycolate), monoalkyltin tris (monoalkyl maleate) or dialkyltin tris (monoalkyl maleate), epoxidized soybean oil or epoxy Epoxy compounds such as butyl stearate, various organic pigments, flame retardants such as phosphate esters, antistatic agents such as cation or anionic surfactants, lubricants such as lower alcohol esters of aliphatic amides or fatty acids , Acrylic polymer processing aid, di-2 Plasticizers such as hexyl phthalate or Kishiruaji base one preparative to G 2 Echiru to Echiru, charge 塡剤 of such as aluminum oxide, can also be used in combination with one or more such blowing agents such as sodium bicarbonate or Azojikarubona Mi de.

Further, the stabilized synthetic resin composition of the present invention can be used in combination with a crystal nucleating agent, a transparentizing agent, and the like, if necessary.

As crystal nucleating agent

Bis (p-tertiary butyl) hydroxyaluminum,

Bis (4-tert-butylphenyl) phosphate sodium,

2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphonate sodium salt,

Dibenzylidene sorbitol,

Bis (p-methylbenzylidene) sorbitol,

Bis (p-ethylethylbenzylidene) sorbitol,

Bis (p-chlorobenzylidene) sorbitol;

The method of blending the stabilizer with the organic polymer is not particularly limited, and includes, for example, a conventionally known method.For example, after mixing the organic polymer and the stabilizer, a process such as kneading and extrusion is performed. And the like.

To prepare the organic polymer material according to the present invention, the general formula (1)

(R ¹ , R ² and R ³ may be the same or different and each represent a hydrogen atom or a methyl group.); A phenolic antioxidant; a phosphorus antioxidant; Furthermore, if necessary, a predetermined amount of a sulfur-based antioxidant, an ultraviolet absorber, a light stabilizer, or other additives may be weighed and mixed with the organic polymer, and then mixed and kneaded. Is also good.

When mixing, the conventional mixers used for mixing the additives with the organic polymer, such as a ball mill, a pebble mill, a tumble mixer, a gas mixer, a super mixer (Hensile mixer), etc. In the case of kneading, kneading machines conventionally used for kneading additives into organic polymers, for example, mixing rolls, Banbury mixers, ∑blade type mixers, high-speed twin-screw continuous mixers First, an extruder-type kneader and the like can be mentioned.

The organic polymer material according to the present invention can be produced by various known molding methods for organic polymer materials, such as injection molding, extrusion molding, calendar molding, blow molding, and compression molding. However, it can be molded into the desired product. The products are not particularly limited and may be used indoors or outdoors.Specifically, parts for electric products, parts for electronic products, parts for agricultural machinery, agricultural products, fishery machinery Parts, marine products, automobile parts, daily necessities, sundries and so on. More specifically, it includes coating layers on heavy-duty oil high-temperature transport steel pipes, heating pipes (for hot water supply, underfloor heating, etc.), and parts for home appliances such as jars, pots, and washing machines. O

Example

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these. W

It is not something to be done.

Melt index (hereinafter also referred to as Ml value) is widely used industrially for the purpose of predicting the moldability of organic materials, especially synthetic resins, as a measure of fluidity, and for indicating standards and quality control. ing. The Ml value is a numerical value that expresses the flow rate for 10 minutes by weight (unit: g) when a polymer melted at a certain temperature is extruded from a circular die having a specified length and diameter under a certain load. Is used as an indicator of Among the high-molecular polymers, in the case of polypropylene, the smaller the value, the better the processing stability, and the larger the value, the worse the processing stability. In addition, by repeatedly measuring the Ml value, it is said that the one with little change in the numerical value has excellent processing stability o

In addition, when additives are kneaded into a resin, yellowness (hereinafter also referred to as YI value) is generally widely used as a measure of the degree of discoloration. The YI value is measured with a colorimeter. The larger the numerical value, the greater the degree of discoloration or coloring, and the smaller the value, the less the coloration during processing and the superior.

Furthermore, the stability at 40 was tested for handleability to determine the ease of handling of the stabilizer composition. As a test method of the ease of handling, a predetermined antioxidant was weighed, and a composition which was sufficiently mixed in a mortar was produced. The composition was placed in a polyethylene bag, heat-sealed, and stored in a constant temperature bath at 40 ° C for 4 weeks. After that, it was taken out of the thermostat, cooled, and touched by hand to check for stickiness, thereby evaluating the handleability of the stabilizer.

Example 1

After dry-mixing the blended ingredients according to the formulation shown in Table 1 for 5 minutes using a tumbler mixer, using a 20 mm diameter extruder, repeatedly extruding at a die set temperature of 280 ° C, Granulated. In order to check the processing stability, the MI value of the pellets extruded each time was measured at a measurement temperature of 230 ° C and a measurement load of 2.16 kgf according to JISK-7210. The YI value was measured according to JISK-7103 (yellowness of pellets by colorimeter-reflection method). W

Table 1 shows the measurement results.

The meanings of the symbols described in Table 1 are as follows.

PP: Polypropylene

C a— S t: Calcium stearate

S—14: Vitamin E (reagent manufactured by Tokyo Chemical Industry Co., Ltd.)

A O -2: Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane (manufactured by Yoshitomi Fine Chemical Co., Ltd., trade name: Tominox TT)

Ρ-1: Tris (2,4-di-tertiary butylphenyl) phosphite (manufactured by Yoshitomi Fine Chemical Co., Ltd., product name: "Tomiphos 202")

M I 1: Ml value measured by the pellet obtained at the first time was shown.

Ml 2: MI value measured by the pellet obtained the second time.

M13: The MI value measured by the pellet obtained the third time was shown.

Y I 1: Y I value measured by the first pellet obtained.

Y I 2: Y I value measured by the second pellet obtained.

Y I 3: Y I value measured by the pellet obtained the third time was shown.

X: Due to the deterioration of the resin, the resin could not be picked up by the strand method and pellets could not be obtained.

From the results shown in Table 1, it is found that vitamin E is 5 times the total amount of phenolic antioxidant (AO-2), phosphorus antioxidant (P-1) and vitamin E (S-14). %, 2% by weight, the organic polymer material composition containing the composition of the present invention was found to suppress coloration, have a small MI value, and have better processing stability than the composition of the comparative example. In particular, it can be seen that the addition of a small amount shows a synergistic effect and shows good processing stability. table 1

° ppM »acid mixed with b ^ w 文» s

Example 2

The compositions blended according to the formulation shown in Table 2 were mixed in the same manner as in Example 1, repeatedly extruded, and the Ml value of the pellets was measured.

Table 2 shows the measurement results.

The meanings of the symbols described in Table 2 are as follows.

PP: Polypropylene (Homopolymer)

C a-S t: Calcium stearate

AO-2: Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane (Yoshitomi Fine Chemical Co., Ltd., trade name: Tominox TT)

Ρ—1: Tris (2,4-di-tertiary butyl phenyl) phosphite (manufactured by Yoshitomi Fine Chemical Co., Ltd., trade name: “Tomiphos 202”)

Compound used in the composition of the present invention

S—14: Vitamin Ε (Reagent manufactured by Tokyo Chemical Industry Co., Ltd.)

Compound used in Comparative Example Composition

S-15: Vitamin acetate (Wako Pure Chemical Industries, Ltd. reagent)

S—16: 2,6-ditertiary tert-butyl—4-methylphenol (manufactured by Yoshitomi Fine Chemical Co., Ltd., trade name: “Yoshinox II”)

S-10: 3- (3,4-dimethylphenyl) —5,7-ditertiarybutyl—3Η-benzofuran-2-one (described in Japanese Patent Application Laid-Open No. 7-233160) It was synthesized by the method of

From the results shown in Table 2, the composition of the present invention containing vitamin E (S- 14) (Compound 1) has a small Ml value, is superior in processing stability to the composition of the comparative example, and is added in a small amount. It can be seen that a synergistic effect is exhibited by, and good processing stability is exhibited. However, a composition (formulations 2 and 3) containing a similar compound, vitamin E acetate (S-15) and 2,6-ditertiary butyl-4-methylphenol (S-16), The composition is almost the same as the composition without these ingredients (Formulation 5), and the effect of the composition is almost not recognized. Ma

Table 2

"M% of acid soup mixed in PP yarn weaving ^!

Example 3

Mixtures prepared according to the formulation shown in Table 3 were mixed in the same manner as in Example 1, and the Ml value and YI value of the pellets repeatedly extruded and granulated were measured. Table 3 shows the measurement results.

The meanings of the symbols described in Table 3 are the same as in Example 1.

From Table 3, the composition containing the composition of the present invention shows that when the amount of vitamin E added is 0.001 part by weight or less with respect to the total amount of the fuanol-based antioxidant, the phosphorus-based antioxidant and vitamin E, The coloring due to the deterioration of the resin causes no sufficient effect.If the amount exceeds 0.005 parts by weight, the discoloration of the resin due to the additive is caused. .

Table 3

1) M% of antioxidant S-14 compounded in

Example 4

The storage stability at 40 ° C. was measured to determine the ease of handling by changing the proportion of vitamin E in the stabilizer composition of the present invention. A composition with a weight ratio of AO-1 to P_1 of 1: 2 was prepared, and the ratio of vitamin E to the total amount of AO-1, P_1 and vitamin E was as specified in Table 4. After weighing and mixing in a mortar, the mixture was placed in a polyethylene bag, heat-sealed, and stored in a thermostat at 40 ° C for 4 weeks. Thereafter, it was determined whether or not the hands felt sticky.

The test results are shown in Table 4.

Table 4 Handling properties of stabilizer composition (powder)

The weight ratio of A 0-1 to P_1 = 1: 240 ° C. After 4 weeks, the stabilizer composition was touched by hand to determine stickiness.

The meanings of the symbols described in Table 4 are the same as in Example 1.

From Table 4, it was found that if the proportion of vitamin E to the composition of the present invention was 5% by weight or less, it was stable without any abnormality during the test period, but if it exceeded 6% by weight, stickiness occurred and storage stability It turned out to be bad.

Example 5

To check the processing stability of linear low-density polyethylene (L LDP E), knead it at 210 ° C and 60 rpm using a Labo Plast Mill (Toyo Seiki Seisakusho), and the torque starts to increase. (Hereinafter referred to as the torque rise start time). It can be said that the longer the torque rise start time, the better the thermal stability during processing. Table 5 shows the formulation.

The meanings of the symbols described in Table 5 are as follows.

L LDP E: Linear low density polyethylene

AO-1: n-octadecyl'3- (4-hydroxy-3,5-di-tert-butylphenyl) propionate (Yoshitomi Fine Chemical Co., Ltd., trade name: "Tominox SS") P-2: Tetrakis (2,4-ditertiary butyl-5-methylphenyl) 1-4,4'-biphenylenediphosphonite, (manufactured by Yoshitomi Fine Chemical Co., Ltd., trade name: "GSY_P101") )

S-14: Vitamin E (Reagent manufactured by Tokyo Chemical Industry Co., Ltd.)

Table 5 shows that 1% by weight and 5% by weight of vitamin E are based on the total amount of phenolic antioxidant (AO-1), phosphorus antioxidant (P-2) and vitamin E (S-14). It was found that the organic polymer material composition blended with the blended composition of the present invention exhibited extremely good stability as compared with the comparative composition containing no vitamin E.

Table 5

° LLDPE 酸 ^ ΦMixed with acid S_14 M%

Industrial applicability

By using the composition of the present invention as a stabilizer for a synthetic resin, a highly effective stabilized synthetic resin composition having excellent thermal processing stability can be obtained. This application is based on Japanese Patent Application No. 1811174 filed in Japan, filed in Japan, the contents of which are incorporated in full herein.

Claims

The scope of the claims

1. General formula (1)

(R ¹ , R ² and R ³ may be the same or different and represent a hydrogen atom or a methyl group.) Containing a phenolic antioxidant and a phosphorus antioxidant And the general formula (1)

(R ¹ , R ² and R ³ may be the same or different and each represent a hydrogen atom or a methyl group.) 0.5 to 5.5% by weight of a compound represented by the formula: phenolic antioxidant A stabilizer composition for an organic polymer material, comprising a total amount of 99.5 to 94.5% by weight of the compound and a phosphorus-based antioxidant.

2. General formula (1)

(RR ² and R ³ may be the same or different, and Represents a tyl group. 3. The stabilizer composition for an organic polymer material according to claim 1, wherein the proportion of the compound represented by) is 1.0 to 4.5% by weight.

3. The method according to claim 1, wherein the weight ratio of the compounding amount of the phenol-based antioxidant to the compounding amount of the phosphorus-based antioxidant is 1: 0.2 to 1: 5. Stabilizer composition for organic polymer materials.

4. The phenolic antioxidant

n-octadecyl-3— (3,5-ditertiary butyl—4-hydroxyphenyl) propionate,

Tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane,

Tris (3,5-di-tert-butyl-4-hydroxydibenzyl) isocyanurate, and

1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) At least one selected from the group consisting of benzene, phosphorus-based antioxidant Agent

Tris (2,4-di-tert-butylphenyl) phosphite,

Tetrakis (2,4-di-tert-butylphenyl) 1-4,4'-biphenylenediphosphonite,

Tetrakis (2,4-di-tert-butyl-5-methylphenyl) -1,4'-biphenylenediphosphonite,

Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate

2,2'-methylenebis (4,6-ditertiary butyl ester) — 2-ethylhexyl phosphite,

Bis [2-methyl-4,6-bis (1,1-dimethylethyl) phenyl] ethyl Lephosphite, and

2, 2 ', 2 "-from the group consisting of the two-mouth [triethyl tris (3, 3', 5, 5 '-tetra-tertiary tert-butyl 1'-biphenyl 2, 2'-diyl) phosphite] The stabilizer composition for an organic polymer material according to any one of claims 1 to 3, which is at least one selected from the group consisting of:

5. A stabilized organic polymer material characterized by comprising the organic polymer blended with the stabilizer composition for an organic polymer material according to any one of claims 1 to 4.

6. The method according to claim 5, wherein the stabilizer composition for an organic polymer material according to any one of claims 1 to 4 is further blended with a sulfur-based antioxidant and Z or a light stabilizer. The organic polymer material according to the above.

7. In the organic polymer, the general formula (1)

(R ¹ , R ² and R ³ may be the same or different and each represent a hydrogen atom or a methyl group.) Containing a phenolic antioxidant and a phosphorus antioxidant Wherein the organic polymer material has a general formula (1) based on 100 parts by weight of the organic polymer material.

(RR ² and R ³ may be the same or different, and

Four Shows a tyl group. An organic polymer material comprising the compound represented by the formula (1) in an amount of 0.0005 to 0.025 parts by weight.

8. General formula (1)

(R ¹ , R ² and R ³ may be the same or different and each represent a hydrogen atom or a methyl group.) The compounding ratio represented by the following formula is from 0.001 to 0.005. 8. The organic polymer material according to claim 7, which is in a range of parts by weight.

9. The method according to claim 7, wherein the weight ratio of the compounding amount of the phenol-based antioxidant to the compounding amount of the phosphorus-based antioxidant is 1: 0.2 to 1: 5. Organic polymer materials.

1 0. The phenolic antioxidant

n—Cactadecyl · 3— (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,

Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane,

Tris (3,5-di-tert-butyl-4-hydroquinbenzyl) isocyanurate, and

Tris (2,4-di-tert-butylphenyl) phosphite

Tetrakis (2,4-di-tert-butylphenyl) 1,4,4-biphenylenedithio Shonite,

Tetrakis (2,4-di-tert-butyl-5-methylphenyl) -1,4'-biphenylenediphosphonite,

Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite Bis (2,6-di-tert-butyl-4-monomethylphenyl) pentaerythritol diphosphate

2, 2'-methylenebis (4,6-di-tert-butylphenyl)-2-ethylhexylphosphite,

Bis [2-methyl-4,6-bis (di-dimethylethyl) phenyl] ethylphosphite, and

2, 2 ', 2 "-from the two-mouth [Trietiltris (3, 3', 5, 5 '-tetra-tertiary tertiary butyl, 1, 1'-biphenyl 2, 2 '-diyl) phosphite] The stabilized organic polymer material according to any one of claims 7 to 9, wherein the organic polymer material is at least one selected from the group consisting of:

1 1. The stabilized organic polymer material according to any one of claims 7 to 10, wherein the organic polymer is a synthetic resin.

12. The stabilized organic polymer material according to any one of claims 7 to 10, wherein the organic polymer is a polyolefin-based resin.

1 3. The organic polymer is a polyethylene-based resin, a polypropylene-based resin, a mixture or a compatible polymer of a polyethylene-based resin and a polypropylene-based resin, a compatible polymer containing a polyethylene-based resin and / or a polypropylene-based resin, Claims 7 to 7 which are an ethylene-vinyl acetate copolymer or an ethylene-propylene copolymer.

10. The stabilized organic polymer material according to any of 10.

1 4. Claims that further contain a sulfur-based antioxidant and / or light stabilizer? The stabilized organic polymer material according to any one of items 1 to 10.