JPH10139733A - New beta crystal of phenol compound and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject crystalline new compound exerting stabilization effect under specific conditions, e.g. water and useful as a stabilizer for various organic polymers such as synthetic organic polymers, natural organic polymers and cosmetics. SOLUTION: This crystalline new compound is β crystal of 1,1,3-tris(2- methyl-4-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy)-5-tert-bu tylphenyl) butane shown by formula I. The β crystal of formula I can be produced by four alternative methods; e.g. 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) butane is reacted with 3,5-di-tert-butyl-4-hydroxyphenylpropionyl chloride in the presence of triethylamine. The blending ratio of the β crystal of formula I to an organic polymer is 0.01-10 pts.wt., preferably 0.01-1 pt.wt. per 100 pts.wt. of the organic polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is useful as a stabilizer (antioxidant) for various organic polymers such as synthetic organic polymers such as polyolefins, natural organic polymers, cosmetics and oils and fats. Alternatively, the present invention relates to a novel crystalline phenol compound which exhibits a remarkable stabilizing effect when used in an environment where hot water is present, and a use thereof.

[0002]

2. Description of the Related Art Synthetic organic polymers such as polyolefins and various organic polymers such as synthetic rubbers are oxidized during molding and product use.
There is a problem that the quality is deteriorated such as a decrease in mechanical strength and a deterioration in appearance. For this reason, various antioxidants have conventionally been developed for the purpose of preventing oxidative deterioration, and are blended in the material. Among them, hindered phenol compounds (for example, JP-B-38-17164, JP-B-39-39)
Nos. 4620 and JP-B-42-9651) are particularly useful for preventing oxidative deterioration of synthetic polymer materials such as polyolefins and are widely used.

[0003] However, when a material stabilized by various conventional antioxidants is used in an environment where water or hot water is present, there is a problem that the effect of preventing oxidation deterioration is significantly reduced. Conventionally, it is thought that the reason for this is that the antioxidant is extracted by water, or that the antioxidant is extracted into water or hot water after hydrolysis. In order to prevent extraction and hydrolysis by, for example, it is common to mix an antioxidant having a high molecular weight and a rigid structure without an ester structure as in the composition described in JP-A-2-265939. It was a target. However, even the composition described in Japanese Patent Application Laid-Open No. 2-265939 cannot sufficiently satisfy the required durability, and sufficiently exhibits an antioxidant effect even in an environment where water or hot water is present. Agents and organic polymer materials were required.

Japanese Patent Application No. 7-332359 filed by the present applicants.
No. (see JP-A-8-225495),
1,3-tris (2-methyl-4- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) -5-tert-butylphenyl) butane

[0005]

Embedded image

(Hereinafter sometimes abbreviated as compound A)
It is described that such compounds exhibit a sufficient antioxidant effect even in an environment where water or hot water is present, and that the effect of preventing the oxidative deterioration has a remarkable sustaining effect.
The compound A has a melting point of 101 ° C. to 103 ° C., which is described in Japanese Patent Application No. 7-332359 (see Japanese Patent Application Laid-Open No. 8-225495). It was found that there was an infrared absorption of a hydroxyl group at 3645 cm ^-1 .

The present inventors conducted further industrialization studies on Compound A, and found that the above-mentioned melting point of 101 ° C. to 103 ° C.
° C, and found that a new crystal (hereinafter, referred to as β crystal) crystallizes different from a powder (hereinafter, referred to as α crystal) having a characteristic of having infrared absorption of a hydroxyl group at 3645 cm ^-1 . . Therefore, the present invention provides a formula [1]

[0008]

Embedded image

It is an object of the present invention to provide a novel β crystal of the compound A represented by the formula: Furthermore, the present invention relates to the above β
It is an object of the present invention to provide an organic polymer stabilizer comprising a crystal and an organic polymer material comprising the β crystal.

[0010]

That is, the present invention provides (1) an infrared absorption spectrum of 3647 cm ^-1 and 3647 cm ^-1.
Formula [1] having a hydroxyl group absorption at 29 cm ^-1

[0011]

Embedded image

1,1,3-tris (2-methyl-4- (3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxy) -5-tert-butylphenyl ) Β-crystal of butane and (2) an organic polymer, with respect to 1,1,3-tris (2-methyl-4- (3- (3,5-di-tert-butyl)- (3) Organic polymer material characterized by blending 4-hydroxyphenyl) propionyloxy) -5-tert-butylphenyl) butane β crystal, (3) The organic polymer is an olefin resin, The 1,1,3-tris (2-methyl-4- (3- (3,5,5) described in (1) above is used based on 100 parts by weight of the organic polymer material described in (2) and (4) the olefin resin.
-Di-tert-butyl-4-hydroxyphenyl) propionyloxy) -5-tert-butylphenyl) butane β crystal in an amount of 0.01 to 10 parts by weight, A polymer material, (5) the organic polymer material according to the above (3) or (4), wherein the olefin resin is an α-olefin homopolymer or an α-olefin copolymer, and (6) the above (1). Of 1,1,3-tris (2-methyl-4- (3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionyloxy) -5
The present invention relates to a stabilizer for organic polymer comprising tertiary butylphenyl) butane β crystal.

[0013]

The β crystal of the embodiment of the invention compounds A, it is characterized in that it has an absorption of hydroxyl group at 3647cm ^-1 and 3629cm ^-1 in the infrared absorption spectrum, melting point 174
It is a crystal in the range of -180 ° C. In addition, since the β crystal has lower solubility than the α crystal and has low mutual solubility with impurities generated by the reaction, the yield and purity at the time of performing the crystallization operation are high, and the compound A is industrially produced. This is a very useful crystal for

The infrared absorption spectrum of β-crystal of Compound A is shown in FIGS.
FIG. 3 is an enlarged view of the range of 00 to 3600 cm ⁻¹ ,
The X-ray diffraction pattern is as shown in FIG. Compound A
Table 1 shows the diffraction angle and relative intensity of the β crystal from the X-ray diffraction pattern.

[0015]

[Table 1]

On the other hand, the α-crystal of the compound A has a hydroxyl group absorption at 3645 cm ⁻¹ in an infrared absorption spectrum and is a powder having a melting point of 101 to 103 ° C. The infrared absorption spectrum of the α crystal of Compound A is shown in FIG. 5, the enlarged view of the infrared absorption spectrum in the range of 3700 cm ^{−1 to} 3600 cm ⁻¹ is shown in FIG. 6, and the X-ray diffraction pattern is shown in FIG. It is on the street. Table 2 shows the diffraction angle and relative intensity of the α-crystal of Compound A from the X-ray diffraction pattern.

[0017]

[Table 2]

The β-crystal of the compound A is obtained by converting the reaction mixture of the compound A (also referred to as reaction mixture A) or the α-crystal of the compound A with alcohols, ketones, glycols, aliphatic nitriles, aliphatic hydrocarbons, After heating and dissolving in one or more solvents selected from aromatic hydrocarbons, halogenated hydrocarbons, ethers, esters, fatty acids, phenols and amines at the boiling point or lower. It can be produced by cooling while stirring. The β crystals of the compound A thus obtained are:
After separation by a usual filtration operation, isolation and purification can be performed by appropriately combining usual means such as washing and drying. Here, if necessary, the decoloring operation may be performed using activated carbon or activated clay.

The alcohol used in the present invention preferably has 1 to 8 carbon atoms, and particularly preferably has 1 to 3 carbon atoms. Specifically, methanol, ethanol, n-
Propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tertiary butyl alcohol, n-pentyl alcohol, tertiary pentyl alcohol, 1-hexanol, 1-heptanol,
-Octanol, 2-ethyl-1-hexanol, glycerin and the like, among which methanol, ethanol and isopropyl alcohol are particularly preferred.

The ketones preferably have 3 to 6 carbon atoms, and specific examples thereof include acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone.
Of these, acetone is particularly preferred.

The glycols preferably have 2 to 6 carbon atoms, and specific examples include ethylene glycol, trimethylene glycol, diethylene glycol, and triethylene glycol.

Aliphatic nitriles are those having 2 or 3 carbon atoms.
Are preferred, and specific examples thereof include acetonitrile and propionitrile. Among them, acetonitrile is particularly preferred.

The aliphatic hydrocarbons are preferably those having 5 to 10 carbon atoms, specifically, n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-octane.
Decane, cyclohexane, cyclopentane and the like can be mentioned, among which n-hexane and n-heptane are particularly preferable.

Specific examples of the aromatic hydrocarbons include toluene, xylene, benzene, and chlorobenzene.

Halogenated hydrocarbons are those having 1 to 6 carbon atoms.
Are preferred, and specific examples include chloroform, methylene chloride, and 1,2-dichloroethane.

The ethers are preferably those having 2 to 6 carbon atoms, and specific examples include diethyl ether and diisopropyl ether.

The esters are preferably those having 2 to 6 carbon atoms, and specific examples include ethyl acetate, butyl acetate, ethyl propionate and ethyl butyrate.

The fatty acid preferably has 2 to 4 carbon atoms, and specific examples thereof include acetic acid, propionic acid and butyric acid.
Of these, acetic acid is particularly preferred.

The phenols specifically include phenol, cresol, xylenol and the like.

The amines specifically include trimethylamine, triethylamine, pyridine and the like.

The β-crystal of Compound A can be obtained by using the above-mentioned solvent alone or in a mixture of two or more.

Among the above solvents used, alcohols (preferably methanol, ethanol, isopropyl alcohol), ketones (preferably acetone),
Glycols, aliphatic nitriles (preferably acetonitrile), ethers, esters, fatty acids (preferably acetic acid), phenols and amines are from 0.01 to
It may contain 10% moisture.

The reaction mixture of the compound A (reaction mixture A) or the α-crystal of the compound A used for crystallizing the β-crystal of the compound A can be produced, for example, by the following methods 1 to 4.

Method 1: 1,1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane is converted to 3,5-di-tert-butyl-4 in the presence of triethylamine or the like. -React with hydroxyphenylpropionyl chloride.

Method 2: 1,1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and 3,5-ditert-butyl-4-hydroxyphenylpropionic acid are In the presence of an acid anhydride such as trifluoroacetic anhydride, -20 to 100 ° C, preferably -20 to 3
The reaction is carried out at 0 ° C. for 1 to 48 hours, preferably 1 to 24 hours.

Method 3: 1,1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and 3,5-ditert-butyl-4-hydroxyphenylpropionic acid are Using a mineral acid such as hydrochloric acid or sulfuric acid or a Lewis acid such as boron trifluoride ether complex, De
The reaction is performed while removing water generated by an an-Stark apparatus (water separator) or the like.

Method 4: 1,1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and 3,5-ditert-butyl-4-hydroxyphenylpropionic acid are Dicyclohexylcarbodiimide,
The reaction is carried out using a condensing agent such as carbonyldiimidazole and diethyl azodicarboxylate. Among them, in the present invention, it is preferable to produce by the above-mentioned method 1 or 2, and to synthesize by the method 1 is particularly advantageous industrially and particularly preferable.

The β crystal of the compound A of the present invention is useful as an excellent antioxidant, particularly as an antioxidant which exhibits a remarkable effect even when used in an environment where water or hot water is present.
In addition, the effect of preventing oxidative deterioration shows a remarkable sustaining effect.

The β crystal of the compound A of the present invention can be used as a stabilizer for various organic polymers, and is effective for preventing oxidative deterioration of the organic polymers. In particular, it is effective for preventing oxidative deterioration of synthetic polymers often used in an environment where water or hot water is present.

The β crystal of the compound A of the present invention has the formula [2]

[0041]

Embedded image

For all three X's, the formula [3]

[0043]

Embedded image

In the present invention, in the present invention, in addition to the β crystal, any two of X in the formula [2] are the formula [3], and the other one is a hydrogen atom A compound in which any one of X in the formula [2] is the formula [3] and the remaining two are hydrogen atoms, and a compound in the formula [2]
May be a mixture of compounds in which all three of X are hydrogen atoms. This mixture can also be obtained by synthesizing and mixing the respective compounds by the same method as that for obtaining the reaction mixture A.

By blending the β crystals of the compound A of the present invention with an organic polymer, an organic polymer material can be obtained. The compounding method is not particularly limited, and includes a conventionally known method, and the like.
The compounding ratio of β crystals is based on 100 parts by weight of the organic polymer.
It is 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.01 to 1 part by weight.

The organic polymer includes a synthetic organic polymer and a natural organic polymer. As synthetic organic polymers,
Resins such as thermoplastic resins and thermosetting resins are exemplified.
As the thermoplastic resin, for example, an olefin resin, a halogen-containing polymer, a styrene resin, an acrylic resin,
Thermoplastic polyester resin, polyamide resin, aromatic polycarbonate resin, polyacetal resin, polyethylene oxide resin, polyphenylene ether resin, polysulfone resin, polyurethane resin, petroleum resin, polyvinyl acetate resin, vinyl acetal resin, cellulose (cellulose) resin, Polyether sulfone resin, polyphenylene sulfide resin, polyether ketone resin, polyetherimide resin, polyoxybenzoyl resin, polyimide resin, polymaleimide resin, polyamideimide resin, polyarylate resin, fluororesin, ionomer,
Examples thereof include a thermoplastic elastomer, and a mixture thereof can also be used.

As the olefin resin, for example,
Α-olefins having 2 to 8 carbon atoms, such as low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-high-molecular-weight polyethylene, polypropylene, polybutene-1, polypentene and poly-3-methylbutylene Polymer; α- such as ethylene / propylene random copolymer, ethylene / propylene block copolymer, ethylene / butene-1 random copolymer, propylene / ethylene / butene-1 random copolymer
Olefin copolymers; maleic anhydride-modified polypropylene, copolymers of α-olefins such as ethylene-vinyl acetate copolymer and other monomers, and the like, and two or more of these, or other Mixtures with compatible polymers can also be used. After polymerization, these olefin-based resins have been subjected to a slight purification treatment including a step of removing catalyst residues, and those having a relatively high degree of purification, as well as using a highly active catalyst and not undergoing a catalyst removal step. Or
Or an olefin-based resin containing a catalyst residue obtained by simplification, in particular, a crystallinity obtained using a Ziegler-type catalyst or a chromium-based catalyst using a halogen-containing magnesium compound as a catalyst carrier and not yet subjected to a catalyst residue removal step. An olefin resin may be used (Japanese Patent Publication No. 62-4418).
Gazette, Japanese Patent Publication No. 3-56245, U.S. Pat.
No. 5639). Further, an olefin resin having a very narrow molecular weight distribution obtained by a metallocene single-site catalyst may be used (Journal of
Polymer Science. Polymer Chemistry Edition (Journal of Polymer S
science. Polymer Chemistry
Edition, Vol. 23, p. 2151 (1985)
Year)).

Examples of the halogen-containing polymer include polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, vinyl chloride / alkyl acrylate copolymer, and chlorinated polyethylene. As the styrene resin, for example,
Polystyrene, high impact polystyrene, styrene / acrylonitrile copolymer, styrene / MMA copolymer, A
BS resin, AES resin, ACS resin, AAS resin, EE
S resins and the like, and mixtures thereof.
Examples of the acrylic 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, Aramid, and the like, and mixtures thereof.

As the thermosetting resin, unsaturated polyester resin, phenol resin, urea resin, melamine resin, epoxy resin, polyimide resin, silicone resin,
Examples include diallyl phthalate resin, polyurethane resin, and furan resin.

Examples of the natural organic polymer include natural rubber, proteins, derivatives such as cellulose, mineral oil, animal and vegetable oils, waxes, oils and fats, and the like.

The β crystal of the compound A of the present invention has excellent antioxidant properties when it is blended with an olefin resin, especially an α-olefin homopolymer or α-olefin copolymer, among these organic polymers. Show the effect. The most preferred α-olefin is propylene.

Further, the β crystals of the compound A of the present invention exhibit more excellent effects, especially when used in combination with a phenolic antioxidant. That is, when the β crystal of Compound A and a phenolic antioxidant are used as a stabilizer and incorporated into an organic polymer, an organic polymer material having more excellent stability can be obtained. Phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6-tert-butylphenol, and 2,6-di-tert-butyl-4-hydroxymethylphenol 2,6-di-tert-butyl-4-ethylphenol, 2,4,6-tri-tert-butylphenol, butylated hydroxyanisole, n-octadecyl-3-
(4-hydroxy-3,5-di-tert-butylphenyl)
Propionate, isooctyl-3- (4-hydroxy-3,5-ditert-butylphenyl) propionate,
Distearyl / (4-hydroxy-3-methyl-5-tert-butyl) benzylmalonate, propyl gallate,
Octyl gallate, dodecyl gallate, tocopherol (vitamin E), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) ),
4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-butylidenebis (4-ethyl-6
-Tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,
2'-thiobis (4-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), styrenated phenol, N, N '
-Hexamethylenebis (3,5-di-tert-butyl-4-
Hydroxyhydrocinnamide), bis (3,5-dithird)
Ethyl butyl-4-hydroxybenzylphosphonate)
Calcium, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane,
3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyloxymethyl] methane;
1,6-hexanediol-bis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2 '-Methylenebis [6
-(1-methylcyclohexyl) -4-methylphenol], 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 1,3,5-tris (3,5-di-tert-butyl-4
-Hydroxybenzyl) isocyanuric acid, triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], ethylene glycol-bis (3,3-bis (3-third Tert-butyl-4-hydroxyphenyl) butyrate), 2-tert.
Tert-butyl-6- (3-tert-butyl-5-methyl-2-
(Hydroxybenzyl) -4-methylphenyl acrylate, 2,2′-oxamide-bis [ethyl-3- (3,
5-di-tert-butyl-4-hydroxyphenyl) propionate], 6- (4-hydroxy-3,5-di-tert-butylanilino) -2,4-dioctylthio-1,3,3.
5-triazine, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 3,9-bis [2- [3 -(3-tert-butyl-4-hydroxy-5
-Methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [2- [3-
(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionyloxy] -1,1-dimethylethyl]-
2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5-tris [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanate, 2,2-thiodiethylene-
Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl]-
4,6-ditertiary pentylphenyl acrylate, 2,
Examples include, but are not limited to, 4-di-octylthiomethyl-6-methylphenol.

As preferred phenolic antioxidants,
2,6-di-tert-butyl-4-methylphenol, 2,
6-di-tert-butyl-4-ethylphenol, n-octadecyl-3- (4-hydroxy-3,5-di-tert-butylphenyl) propionate, 2,2′-methylenebis (4-methyl-6 Tertiary butyl phenol), 2,
2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-
6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 1,
1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl- 4-
Hydroxybenzyl) benzene, tetrakis [3-
(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionyloxymethyl] methane, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanuric acid, triethyleneglycol-bis [3- (3-tert-butyl-4-) Hydroxy-5-methylphenyl) propionate], 3,9-bis [2-
[3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2-thiodiethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2- [1- (2-hydroxy-3,5-di-tert-pentyl) Phenyl) ethyl]-
4,6-ditertiary-pentylphenyl acrylate,
2,4-di-octylthiomethyl-6-methylphenol and the like. Among them, particularly preferred is
2,6-di-tert-butyl-4-methylphenol.

In the present invention, one or more of these phenolic antioxidants can be used as a stabilizer for organic polymers in combination. The phenolic antioxidant is preferably 0.01 to 10 parts by weight, more preferably 0.0 to 10 parts by weight, based on 100 parts by weight of the organic polymer.
It is good to mix in 1 to 5 parts by weight, particularly preferably 0.01 to 1 part by weight. When the compound of the present invention and a phenolic antioxidant are used in combination, they may be added separately or as a premixed compounding agent. The mixing ratio at the time of use is 0.1 to the compound of the present invention.
A range of 1 to 10 times is preferable. In order to facilitate the addition operation, an organic polymer composition (generally referred to as a masterbatch) containing the compound of the present invention in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the organic polymer is previously provided. It can be produced and added to an organic polymer to produce an organic polymer material having the above-mentioned preferable mixing ratio at the time of use.

Further, the β crystals of the compound A of the present invention exhibit more excellent effects, especially when used in combination with a phosphorus-based antioxidant. That is, when the β crystal of the compound A and the phosphorus-based antioxidant are used as a stabilizer and incorporated into an organic polymer, an organic polymer material having more excellent stability can be obtained. Tris (2,4-di-tert-butylphenyl) phosphite, tris (2,4-di-tert-butyl-6-methylphenyl) as a phosphorus-based antioxidant
Phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4′- Biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-
4-methylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis (4,6-ditert-butylphenyl) -2-ethylhexyl phosphite,
(2,4,6-tritert-butylphenyl) -2-butyl-2-ethyl-1,3-propanediol phosphite, 2,2 ′, 2 ″ -nitrilo [triethyltris (3,3 ′, 5,5′-tetra-tert-butyl-1,
1′-biphenyl-2,2′-diyl) phosphite], distearylpentaerythritol diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) ) Butanetriphosphite and the like.

Preferred phosphorus antioxidants include tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,
4'-biphenylenediphosphonite, tetrakis (2,
4-ditert-butyl-5-methylphenyl) -4,4 '
-Biphenylenediphosphonite, bis (2,4-dithird
Tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite and the like.

In the present invention, one or more of these phosphorus antioxidants can be used as a stabilizer for organic polymers. Phosphorus antioxidants
It is preferable that each of the organic polymers is blended in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, particularly preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the organic polymer. When the compound of the present invention and a phosphorus-based antioxidant are used in combination, they may be added separately or as a premixed compounding agent. The mixing ratio at the time of use is preferably in the range of 0.1 to 10 times the amount of the compound of the present invention. Also, to make the addition work easy,
The compound of the present invention is 1 to 100 parts by weight of the organic polymer.
An organic polymer composition containing 50 parts by weight (usually,
It is called a master batch. ) Can be prepared in advance and added to an organic polymer to produce an organic polymer material having the above-mentioned preferred mixing ratio at the time of use.

Further, the β crystal of the compound A of the present invention can be used in combination with a sulfur-based antioxidant. The sulfur-based antioxidant is not particularly limited, but is preferably dilaurylthiodipropionate, laurylstearylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, ditridecylthiodipropionate, tetrakis. [(3-Laurylthiopropionyloxy) methyl] methane, tetrakis [(3-stearylthiopropionyloxy) methyl]
Methane, bis [2-methyl-4- (3-n-alkyl (C12-C14) thiopropionyloxy) -5-tert-butylphenyl] sulfide and the like can be mentioned.

In the present invention, one or a combination of two or more of these sulfur-based antioxidants can be used as a stabilizer for organic polymers. Sulfur-based antioxidants
It is preferable that each of the organic polymers is blended in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, particularly preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the organic polymer. When the compound of the present invention and a sulfur-based antioxidant are used in combination, they may be added separately or as a premixed compounding agent. The mixing ratio at the time of use is preferably in the range of 0.1 to 10 times the amount of the compound of the present invention. Also, to make the addition work easy,
The compound of the present invention is 1 to 100 parts by weight of the organic polymer.
An organic polymer composition containing 50 parts by weight (usually,
It is called a master batch. ) Can be prepared in advance and added to an organic polymer to produce an organic polymer material having the above-mentioned preferred mixing ratio at the time of use.

Further, the β crystal of the compound A of the present invention can be used in combination with an ultraviolet absorber or a light stabilizer. Examples of these ultraviolet absorbers and light stabilizers include salicylic acid compounds, benzophenone compounds, benzotriazole compounds, benzoate compounds, cyanoacrylate compounds, nickel compounds, and piperidine compounds.

Examples of salicylic acid-based compounds that can be used as an ultraviolet absorber and a light stabilizer include phenyl salicylate, p-tertiary butyl phenyl salicylate,
p-octylphenyl salicylate and the like.

As benzophenone-based compounds which can be used as an ultraviolet absorber and a light stabilizer, 2,4-
Dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,
4'-dimethoxybenzophenone, 2-hydroxy-4
-N-octyloxybenzophenone, 2-hydroxy-4-isooctyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxy Benzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate,
Compounds such as 2,2 ′, 4,4′-tetrahydroxybenzophenone and 2-hydroxy-4-benzoyloxybenzophenone are exemplified.

As the benzotriazole compound which can be used as an ultraviolet absorber and a light stabilizer, 2-benzotriazole compounds
(2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5- Methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,
5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- [2-hydroxy-5- (1,1,3,3)
3-tetramethylbutyl) phenyl] benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, methyl-3- [3-tertiary butyl Condensation product of -5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol, 2- (2-hydroxy-3,5-ditert-amylphenyl) benzotriazole , 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6
-(2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- [2-hydroxy-3
-(3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole.

Benzoate compounds which can be used as an ultraviolet absorber and a light stabilizer include n-hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate and 2,4-di-tert-butylphenyl. 3,5-
Compounds such as di-tert-butyl-4-hydroxybenzoate are exemplified.

Examples of cyanoacrylate compounds that can be used as an ultraviolet absorber and a light stabilizer include ethyl-2-cyano-3,3-diphenylacrylate, octyl-2-cyano-3,3-diphenylacrylate and the like. .

Nickel compounds that can be used as an ultraviolet absorber and a light stabilizer include 2-ethylhexylamine nickel, nickel dimethyldithiocarbamate, and [2,2′-thiobis [4- (1,1,3,3
-Tetramethylbutyl) phenolate]]-n-butylamine nickel, [2,2′-thiobis [4- (1,
1,3,3-tetramethylbutyl) phenolate]] and nickel.

As a piperidine compound which can be used as an ultraviolet absorber and a light stabilizer, bis (2,2)
2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,
2,2,6,6-pentamethyl-4-piperidyl) -2
-(3,5-ditert-butyl-4-hydroxybenzyl) -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-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [(6-morpholino-s-triazine-2,4-diyl) [(2
2,6,6-tetramethyl-4-piperidyl) imino]
Hexamethylene [(2,2,6,6-tetramethyl-4
-Piperidyl) imino]] (cyanuric chloride / tertiary octylamine / 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane condensate), 1-
Hydroxyethyl-2,2,6,6-tetramethyl-4
-Piperidinol / succinic acid condensate, N, N'-bis (3-aminopropyl) ethyldiamine / 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4- Piperidyl) amino] -6-chloro-1,3,3
Compounds such as a 5-triazine condensate are exemplified.

Preferred compounds that can be used as ultraviolet absorbers and light stabilizers are 2-hydroxy-
4-n-octyloxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole,
2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2
-Hydroxy-3,5-ditert-butylphenyl) -5
-Chlorobenzotriazole, bis (2,2,6,6-
Tetramethyl-4-piperidyl) sebacate, poly [[6- (1,1,3,3-tetramethylbutyl) imino-s-triazine-2,4-diyl] [(2,2
6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] (cyanuric chloride / tertiary octylamine / 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane condensate) and the like.

In the present invention, one or more of these ultraviolet absorbers and light stabilizers can be used as a stabilizer for organic polymers. The ultraviolet absorber and the light stabilizer are based on 100 parts by weight of the organic polymer.
Preferably each is 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, particularly preferably 0.01 to 1 part by weight.
It is preferable to mix them in parts by weight. When the compound of the present invention and an ultraviolet absorber and a light stabilizer are used in combination, they may be added separately or as a premixed compounding agent. The mixing ratio at the time of use is preferably in the range of 0.1 to 10 times the amount of the compound of the present invention. In order to facilitate the addition operation, an organic polymer composition (generally referred to as a masterbatch) containing the compound of the present invention in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the organic polymer is previously provided. It can be produced and added to an organic polymer to produce an organic polymer material having the above-mentioned preferable mixing ratio at the time of use.

[0070] Any two or more of these phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, ultraviolet absorbers and light stabilizers, and β crystals of compound A are blended in an organic polymer. Thereby, further effects can be obtained.

The β-crystal of the compound A of the present invention, when used as a stabilizer, may further contain, if necessary, other additives such as hydrotalcite which do not significantly impair the effect of the β-crystal of the compound A of the present invention. , Metal soaps such as calcium stearate, heavy metal deactivators such as hydrazine compounds, monoalkyltin tris (octyl thioglycolate), dialkyltin tris (octyl thioglycolate), monoalkyltin tris (maleic acid) Organic tin stabilizers such as monoalkyl esters) or dialkyltin tris (monoalkyl maleate), epoxy compounds such as epoxidized soybean oil or epoxy octyl stearate, various organic pigments, flame retardants such as phosphate esters, cations Antistatic of non-ionic or anionic surfactants Lubricants such as lower alcohol esters of aliphatic amides or fatty acids; acrylic polymer processing aids; plasticizers such as di-2-ethylhexyl phthalate or di-2-ethylhexyl adipate; fillers such as aluminum oxide; It can be used in combination with one or more kinds of foaming agents such as sodium carbonate and azodicarbonamide.

The β crystals of the compound A of the present invention can be used in combination with a nucleating agent, a clarifying agent, and the like, if necessary.
As a crystal nucleating agent and a clarifying agent, hydroxyaluminum bis (p-tert-butylbenzoate), sodium bis (4-tert-butylphenyl) phosphate, 2,2′-methylenebis (4,6-ditert-butyl) Butylphenyl) phosphate sodium salt, dibenzylidene sorbitol, bis (p-methylbenzylidene) sorbitol, bis (p
-Ethylbenzylidene) sorbitol, bis (p-chlorobenzylidene) sorbitol and the like.

The method for incorporating the stabilizer into the organic polymer is not particularly limited, and may be a conventionally known method.
For example, after mixing an organic polymer and a stabilizer, kneading,
Examples include a method of processing through a process such as extrusion.

To prepare the organic polymer material according to the present invention, the β crystal of Compound A is optionally replaced with a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, an ultraviolet absorber, The light stabilizer or other additives may be weighed to a predetermined amount and mixed with the organic polymer, and may be mixed and kneaded. When mixing, a mixing machine conventionally used when mixing an additive with an organic polymer,
For example, ball mill, pebble mill, tumble mixer,
For example, a mixing mixer, a super mixer (Henschel mixer), and the like. When kneading, a kneading machine conventionally used when kneading an additive to an organic polymer, for example, a mixing roll, a Banbury mixer,
ΣA blade-type mixer, a high-speed twin-screw continuous mixer, an extruder-type kneader, and the like.

The organic polymer material according to the present invention can be obtained by molding various conventionally known organic polymer materials, for example, injection molding, extrusion molding, calender molding, blow molding, compression molding. For example, it can be formed into a target product. The product is 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 the like. More specifically, a coating layer of a steel pipe for transporting heavy oil at a high temperature, a heating pipe (for hot water supply, for underfloor heating, etc.), a jar, a pot, a part of a home appliance such as a washing machine, and the like can be given.

[0076]

EXAMPLES Next, the present invention will be described more specifically with reference to Reference Examples and Examples, but the present invention is not limited thereto. In the reference examples and examples, the infrared absorption spectrum was measured by JASCO FT / IR.
It was measured using -350 (manufacturer: JASCO).
The resolution is 4 cm ^-1 .

Reference Example 1 (Production example 1 of α-crystal of compound A) 1,1,3-tris (2-methyl-4-hydroxy-5
-Tert-butylphenyl) butane

[0078]

Embedded image

52.5 g, 3- (3,5-ditert-butyl-4-hydroxyphenyl) propionic acid

[0080]

Embedded image

A mixture of 85 g and 300 ml of toluene was stirred under ice cooling (−5 to 0 ° C.), and 79 g of trifluoroacetic anhydride was gradually added dropwise using a dropping funnel. After completion of the dropwise addition, the ice bath was removed, and the reaction was stirred at room temperature for 24 hours. This reaction solution was separated and washed several times with a 10% aqueous solution of sodium carbonate, and after neutralizing the solution, the toluene layer was concentrated. The residue was purified by a column chromatography method using silica gel to obtain a white powder having a melting point of 101 to 103 ° C. When the infrared absorption spectrum of the obtained white powder by the KBr method was measured, FIG. 5 and FIG.
This white powder had an absorption of hydroxyl groups at 3645 cm ^-1 as shown in FIG.

Nuclear magnetic resonance spectrum analysis result ¹ H-NMR (CDCl ₃ , ppm) δ: 1.16
(S, 9H), 1.22 (d, 3H), 1.29 (s,
9H), 1.31 (s, 9H), 1.42 (s, 18
H), 1.43 (s, 18H), 1.44 (s, 18
H), 1.65 (s, 3H), 1.82 (s, 3H),
2.00-2.10 (m, 1H), 2.10 (s, 3
H), 2.14-2.24 (m, 1H), 2.83-
2.93 (m, 6H), 2.93-3.08 (m, 7
H), 3.90-3.95 (m, 1H), 5.05.
(S, 1H), 5.06 (s, 1H), 5.07 (s, 1H)
1H), 6.60 (s, 1H), 6.61 (s, 1
H), 6.62 (s, 1H), 7.04 (s, 1H),
7.06 (s, 3H), 7.07 (s, 3H), 7.2
1 (s, 1H), 7.39 (s, 1H)

From the above analysis results and the results of elemental analysis, mass spectrum analysis and the like, the obtained compound was 1,
1,3-tris (2-methyl-4- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) -5-tert-butylphenyl) butane

[0084]

Embedded image

It was confirmed that it was an α-crystal of (Compound A).

Example 1 (Production Example 1 of β Crystal of Compound A) 1,1,3-Tris (2-methyl-4-hydroxy-5
-Tert-butylphenyl) butane

[0087]

Embedded image

52.5 g, 3- (3,5-ditert-butyl-4-hydroxyphenyl) propionic acid

[0089]

Embedded image

A mixture of 85 g and 300 ml of toluene was stirred under ice cooling (−5 to 0 ° C.), and 79 g of trifluoroacetic anhydride was gradually added dropwise using a dropping funnel. After completion of the dropwise addition, the ice bath was removed, and the reaction was stirred at room temperature for 24 hours. This reaction solution was separated and washed several times with a 10% aqueous solution of sodium carbonate, and after neutralizing the solution, the toluene layer was concentrated. 500 g of methanol was added to the toluene concentrated residue, and the mixture was dissolved by heating, and then stirred at room temperature for 5 hours. The obtained crystals are filtered and sufficiently dried, and the melting point is 174 to 176 ° C.
Was obtained as white crystals. The infrared absorption spectrum of the obtained white crystal measured by the KBr method was, as shown in FIG. 1, to have hydroxyl group absorptions at 3647 cm ^-1 and 3629 cm ^-1 . The crystal was subjected to instrumental analysis such as elemental analysis, nuclear magnetic resonance spectrum, and mass spectrum. The same results as in Reference Example 1 were obtained. The crystal obtained from these results is 1,1,3-tris (2-
Methyl-4- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) -5-tert-butylphenyl) butane

[0091]

Embedded image

It was confirmed that it was a β crystal of (Compound A).

Example 2 (Production Example 2 of β Crystal of Compound A) 1,1,3-Tris (2-methyl-4-hydroxy-5)
-Tert-butylphenyl) butane

[0094]

Embedded image

30 g, and 18.1 triethylamine
To 100 g of toluene, 100 g of toluene was added and heated to dissolve. Under stirring, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propynyl chloride

[0096]

Embedded image

55 g was dissolved in 50 g of toluene and added dropwise. After the addition, the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was washed with water and filtered. The filtrate was concentrated, and methanol was added to the obtained residue to cause crystallization, whereby 65 g of white crystals were obtained. The melting point of the obtained crystals is 174-17.
6 ° C. Further, the infrared absorption spectrum of the obtained crystal measured by the KBr method was, as shown in FIG. 1, to have a hydroxyl group absorption at 3647 cm ^-1 and 3629 cm ^-1 . The crystal was subjected to instrumental analysis such as elemental analysis, nuclear magnetic resonance spectrum, and mass spectrum. The same results as in Reference Example 1 were obtained. The crystals obtained from these results were obtained in the presence of 1,1,3-tris (2-methyl-4- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) -5- Tertiary butylphenyl) butane

[0098]

Embedded image

It was confirmed that it was a β crystal of (Compound A).

Example 3 The procedure of Example 1 was repeated, except that acetonitrile was used instead of methanol as a crystallization solvent. The melting point of the obtained crystals was 176 to 177 ° C. Further, the result of measurement of the infrared absorption spectrum (KBr method) was the same as that of Example 1.

Example 4 The procedure of Example 1 was repeated, except that hexane was used instead of methanol as a crystallization solvent. The melting point of the obtained crystal is 1
74-178 ° C. Further, the result of measurement of the infrared absorption spectrum (KBr method) was the same as that of Example 1.

Example 5 The procedure of Example 1 was repeated, except that acetone was used instead of methanol as a crystallization solvent. The melting point of the obtained crystal is 1
76-180 ° C. Further, the result of measurement of the infrared absorption spectrum (KBr method) was the same as that of Example 1.

Example 6 The procedure of Example 1 was repeated, except that isopropyl alcohol was used instead of methanol as a crystallization solvent. The melting point of the obtained crystals was 174 to 177 ° C. Further, the result of measurement of the infrared absorption spectrum (KBr method) was the same as that of Example 1.

Example 7 The procedure of Example 1 was repeated, except that a mixed solvent of chloroform and hexane was used instead of methanol as a crystallization solvent. The melting point of the obtained crystals was 174 to 178 ° C.
Further, the result of measurement of the infrared absorption spectrum (KBr method) was the same as that of Example 1.

Example 8 In the same manner as in Example 1 except that 95% aqueous ethanol was used instead of methanol as a crystallization solvent. The melting point of the obtained crystals was 176 to 178 ° C. Further, the result of measurement of the infrared absorption spectrum (KBr method) was the same as that of Example 1.

Example 9 The procedure of Example 1 was repeated, except that acetic acid was used instead of methanol as a crystallization solvent. The melting point of the obtained crystal was 176.
179 ° C. In addition, the infrared absorption spectrum (KB
As a result of measurement of r method), it was the same as that of Example 1.

Example 10 (Production Example of Reaction Mixture A) 1,1,3-Tris (2-methyl-4-hydroxy-5
-Tert-butylphenyl) butane

[0108]

Embedded image

16.3 g, 3- (3,5-ditert-butyl-4-hydroxyphenyl) propionic acid

[0110]

Embedded image

A mixture of 25.1 g and 100 ml of toluene was cooled to -10 ° C., and 18.9 g of trifluoroacetic anhydride was gradually added dropwise to the mixture with a dropping funnel. After completion of the dropwise addition, the ice bath was removed, and the mixture was stirred at room temperature for 3 hours. This reaction solution was separated and washed several times with a 10% aqueous sodium carbonate solution, the toluene layer was filtered, and the toluene layer was concentrated. Methanol was added to the toluene-concentrated residue, and the mixture was heated and dissolved, and then crystallized to give white crystals 3 having a melting point of 177 to 180 ° C.
2.7 g were obtained. Further, when the crystals were analyzed by liquid chromatography, the formula [2] was obtained.

[0112]

Embedded image

In all three X's, the formula [3]

[0114]

Embedded image

89% of the compound (compound A), which is a group represented by the formula, is a compound in which two of X in the formula [2] are a group represented by the formula [3] and one is a hydrogen atom. 7%, Formula [2]
1% of the compounds in which one of X is a group represented by the formula [3] and two of them are hydrogen atoms, and 3% of the compounds in which all three of X in the formula [2] are hydrogen atoms And a mixture consisting of When the infrared absorption spectrum of the obtained crystal was measured by the KBr method, it was 3647 cm 3 as shown in FIG.
^-1 and 3629 cm ^-1 have absorption of hydroxyl groups,
Although the details were different, they were almost the same as in Example 2. Therefore, it was inferred that the obtained white crystals were a mixture containing the β crystal of the compound A as a main component.

Efficacy Test Example 1 (Examples 11 to 12, Comparative Examples 1 to 4) Propylene alone having an intrinsic viscosity of 1.9 (measured in tetralin at 135 ° C.) and an isotactic component of 98% by weight The compounds shown in Table 3 were blended with 100 parts by weight of the polymer powder in the proportions shown in the same table, and mixed well with a mixer. L / D = 20, discharge diameter 20 mm
Was melt-kneaded at a cylinder temperature of 255 ° C., extruded from a die into a strand shape, and cut to obtain pellets. From the obtained pellets, a thickness of 0.5 mm and a length of 100
A square sheet having a length of 50 mm and a width of 25 mm was cut out from the sheet.
The obtained test pieces were subjected to a hot water test in the following manner. A test piece and 12 ml of distilled water are sealed in a stainless steel pressure-resistant container with a lid having an inner diameter of 38 mm and a depth of 55 mm, which is then sealed. The container is placed in an oven at a temperature of 140 ° C. and the container is deteriorated. Promoted. Every 24 hours, distilled water was replaced, the test piece was taken out, the appearance was visually observed, and the time required for embrittlement was measured by a test method in which the test piece was touched with a finger. The time required until embrittlement means the time required for the surface of the test piece to turn brown and to become brittle to such an extent that the test piece easily collapses when touched with a finger. In this test, the same test was performed for each of three test pieces, and the average time was calculated and indicated as hot water resistance (time). The larger the value, the better the hot water resistance.

The abbreviations of the compounds in Table 3 are as follows. A-1: 1,1,3-tris (2-methyl-4- (3-
(3,5-di-tert-butyl-4-hydroxyphenyl)
Β-crystal of propionyloxy) -5-tert-butylphenyl) butane (compound A) (synthesized in Example 2) B-1: Tetrakis (3- (3,5-di-tert-butyl-)
4-hydroxyphenyl) propionyloxymethyl)
Methane (trade name "Tominox TT" manufactured by Yoshitomi Fine Chemical Co., Ltd.) B-2: 1,3,5-trimethyl-2,4,6-tris (3,5-ditert-butyl-4-hydroxybenzyl)
Benzene (trade name "IRGANO" manufactured by Ciba Geigy)
X1330 ") C-1: Dimyristylthiodipropionate (trade name" DMTP "Yoshitomi""manufactured by Yoshitomi Fine Chemical Co., Ltd.) D-1: Bis (2,4-di-tert-butylphenyl) pentaerythritol diphos Fight (manufactured by GE Specialty Chemicals, trade name "Ultra Knox 626") E-1: Calcium stearate

[0118]

[Table 3]

The following is clear from Table 3. (1) The organic polymer material containing the compound of the present invention (Example 11) together with the antioxidant D-1 commonly used in organic polymers is mixed with the same amount of the antioxidant D-1 used in general. It is excellent in hot water resistance as compared with organic polymer materials (Comparative Examples 1 and 2) blended with general-purpose antioxidants B-1 or B-2 which have good hot water resistance. (2) An organic polymer material containing the compound of the present invention together with the antioxidants C-1 and D-1 commonly used in organic polymers (Example 12) has the same amount of commonly used antioxidants. Compared to C-1 and D-1, the organic polymer material (Comparative Examples 3 and 4) blended with a general-purpose antioxidant B-1 or B-2, which has good hot water resistance, has a higher hot water resistance. Are better.

Efficacy Test Example 2 (Examples 13 and 14, Comparative Examples 5 and 6) Polymerization was carried out by a slurry method using a Ziegler-Natta catalyst. The compound shown in Table 4 was blended with 100 parts by weight of a propylene homopolymer powder having 98% by weight of a tic component in the concentration shown in Table 4 and thoroughly mixed by a mixer. = 28, melt-kneading with an extruder having a discharge diameter of 20 mm, extruded from a die in a strand shape, and cut to obtain pellets. The obtained pellets were crushed at 200 ° C. and 50 kg / cm ² by a vertical screw type injection molding machine manufactured by Yamashiro Seiki Co., Ltd.
A test piece having a thickness of 0 mm, a width of 50 mm, and a thickness of 3 mm was prepared.
The obtained test piece was subjected to a hot water test. That is, the degree of coloring after the test piece was immersed in boiling distilled water for two months was determined by yellowness (YI) using a color tester SM-7 manufactured by Suga Test Instruments. The smaller the value, the better the hot water coloring property.

The abbreviations of the compounds in Table 4 are as follows. A-1: 1,1,3-tris (2-methyl-4- (3-
(3,5-di-tert-butyl-4-hydroxyphenyl)
Β-crystal of propionyloxy) -5-tert-butylphenyl) butane (compound A) (compound synthesized according to Example 2) B-1: tetrakis (3- (3,5-di-tert-butyl-)
4-hydroxyphenyl) propionyloxymethyl)
Methane (trade name "Tominox TT" manufactured by Yoshitomi Fine Chemical Co., Ltd.) D-2: Tris (2,4-di-tert-butylphenyl) phosphite (trade name "Irgaphos 168" manufactured by Ciba-Geigy) D- 3: Tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite (manufactured by Clariant, trade name “Sandstub P-EPQ”) E-1: Calcium stearate

[0122]

[Table 4]

From Table 4, the following is clear. (1) Antioxidant D-2 commonly used in organic polymers
In addition, the organic polymer material containing the β crystal of the compound of the present invention (Example 13) is the same amount of a widely used antioxidant D-2 as well as a widely used antioxidant having good hot water resistance. Organic polymer material containing B-1 (Comparative Example 5)
Compared with, it is excellent in hot water coloring. (2) Antioxidant D-3 commonly used in organic polymers
In addition, the organic polymer material containing the β crystal of the compound of the present invention (Example 14) is the same amount of a widely used antioxidant D-3 as well as a widely used antioxidant having good hot water resistance. Organic polymer material containing B-1 (Comparative Example 6)
Compared with, it is excellent in hot water coloring. From the above examples, it was revealed that the organic polymer material containing the compound of the present invention has stable and excellent hot water resistance.

[0124]

The present invention has the following particularly effective effects, and its industrial utility is extremely large. 1. The β crystal of Compound A is an excellent antioxidant for various organic polymers including synthetic polymers such as polyolefins, and exhibits a remarkable effect even when used in an environment where water or hot water is present. Useful as an antioxidant,
In addition, the effect of preventing oxidative deterioration shows a remarkable sustaining effect. 2. INDUSTRIAL APPLICABILITY According to the present invention, 1,1,3-tris (2-methyl-4-yl) useful as an excellent antioxidant, particularly an antioxidant which exhibits a remarkable effect even when used in an environment where water or hot water is present. A novel β crystal of (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) -5-tert-butylphenyl) butane (compound A) can be produced industrially with high purity and high yield. Can be manufactured on a scale. 3. The organic polymer material using the phenolic compound of the present invention retains its excellent durability, especially its hot water life and low colorability, even after repeating the resin molding process.

[Brief description of the drawings]

FIG. 1 is a view showing an infrared absorption spectrum of a β crystal obtained by the present invention using methanol as a crystallization solvent.

FIG. 2 is a view showing an infrared absorption spectrum of a β crystal obtained by the present invention using acetone as a crystallization solvent.

FIG. 3 shows a range of 3700 to 36 in the infrared absorption spectrum of β crystal obtained by the present invention using acetone as a crystallization solvent.
It is an enlarged view of the range of 00 cm- ¹ .

FIG. 4 is an X-ray diffraction pattern of β crystal obtained by the present invention using acetone as a crystallization solvent.

FIG. 5 is a diagram showing an infrared absorption spectrum of α-crystal.

FIG. 6 shows the infrared absorption spectrum of α-crystal at 3700 to
It is an enlarged view of the range of 3600cm < ^-1 >.

FIG. 7 is an X-ray diffraction pattern of α-crystal.

FIG. 8 is an enlarged view of an infrared absorption spectrum of a reaction mixture synthesized in Example 10 in a range of 3700 to 3600 cm ⁻¹ .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09K 15/08 C09K 15/08

Claims (6)

[Claims] 1. In an infrared absorption spectrum, 3647
wherein an absorption of hydroxyl group in cm ^-1 and 3629cm ^-1 [1] [Formula 1] 1,1,3-tris (2-methyl-4- (3
Β-crystal of-(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxy) -5-tert-butylphenyl) butane. 2. The organic polymer according to claim 1, wherein the 1,1,3-tris (2-methyl-4- (3- (3,5
An organic polymer material comprising -di-tert-butyl-4-hydroxyphenyl) propionyloxy) -5-tert-butylphenyl) butane β crystal. 3. The organic polymer material according to claim 2, wherein the organic polymer is an olefin resin. 4. An amount of 100 parts by weight of the olefin resin,
The 1,1,3-tris (2-methyl-4- according to claim 1,
(3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxy) -5-tert-butylphenyl) butane β crystal in an amount of 0.01 to 10 parts by weight. 4. The organic polymer material according to claim 3, wherein 5. The organic polymer material according to claim 3, wherein the olefin resin is an α-olefin homopolymer or an α-olefin copolymer. 6. The 1,1,3-tris (2) according to claim 1,
-Methyl-4- (3- (3,5-ditert-butyl-4-)
(Hydroxyphenyl) propionyloxy) -5-third
Grade butylphenyl) butane β-crystal stabilizer for organic polymers.