Diphosphite-based compound, method for producing same, and uses of same

Abstract

The present invention provides a compound that has high heat resistance and can be used for processing of an organic material, which requires a high processing temperature.　Disclosed is a diphosphite-based compound which is represented by formula (I) (wherein R1 represents an alkyl group having 1-12 carbon atoms, a cycloalkyl group having 5-8 carbon atoms, an alkylcycloalkyl group having 6-12 carbon atoms, or an aralkyl group having 7-25 carbon atoms; R2 represents an alkyl group having 1-12 carbon atoms, a cycloalkyl group having 5-8 carbon atoms, an alkylcycloalkyl group having 6-12 carbon atoms, or an aralkyl group having 7-12 carbon atoms; R3 represents a hydrogen atom, an alkyl group having 1-12 carbon atoms, a cycloalkyl group having 5-8 carbon atoms, an alkylcycloalkyl group having 6-12 carbon atoms, or an aralkyl group having 7-25 carbon atoms; and X represents a single bond, an alkylidene group having 1-4 carbon atoms, a sulfur atom, or an oxygen atom).

Description

Diphosphite compounds, their production method and uses

[0001] This patent application claims priority under the Paris Convention to Japanese Patent Application No. 2024-033944 (filing date: March 6, 2024), the entire contents of which are incorporated herein by reference. The present invention relates to novel diphosphite compounds, their production methods, and their use as stabilizers for organic materials.

[0002] Diphosphite compounds are disclosed in Patent Documents 1 and 2. Patent Document 1 describes that the compounds stabilize organic polymers.

[0003] Japanese Patent Publication No. 57-122093 Chinese Patent Application Publication No. 111320653

[0004] Organic materials such as thermoplastic resins, thermosetting resins, natural or synthetic rubber, mineral oil, lubricating oil, adhesives, and paints are subject to deterioration due to the action of heat, oxygen, and the like during production, processing, and even use, resulting in a decrease in the strength properties of the organic materials due to phenomena such as molecular scission and molecular crosslinking, changes in flowability, coloration, and deterioration in surface properties, which can significantly impair their commercial value. Therefore, it is necessary to prevent such deterioration and stabilize the organic materials, and in the case of organic materials such as engineering plastics, which require even higher processing temperatures than general thermoplastic resins, a stabilizer with high heat resistance is required.

[0005] Therefore, an object of the present invention is to provide a compound having high heat resistance that can be used in processing organic materials that require high processing temperatures.

[0006] The present inventors have conducted extensive research to solve the above problems and have completed the present invention. That is, the present invention includes the following preferred embodiments.

[0007] [1] Formula (I): [In formula (I), R １ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 25 carbon atoms; R ２represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; R ３ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 25 carbon atoms, and X represents a single bond, an alkylidene group having 1 to 4 carbon atoms, a sulfur atom, or an oxygen atom. [2] R １ is a tertiary alkyl group having 4 to 12 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or a tertiary aralkyl group having 9 to 15 carbon atoms. [3] The compound of formula (I) above is a compound of formula (I'): [In formula (I'), R １ , R ２ , R ３ and X is as defined above. [4] The compound according to any one of [1] to [3], wherein X is a single bond. [5] R ３ is a tertiary alkyl group having 4 to 12 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or a tertiary aralkyl group having 9 to 21 carbon atoms. [6] The compound according to any one of [1] to [4]. ３ [7] The compound according to [5], wherein R is a tertiary alkyl group having 5 to 10 carbon atoms. [In formula (II), R １ is as defined above] with phosphorus trihalide, to obtain a reaction product, [In formula (III), R ２ , R ３and X is as defined above. [8] A stabilizer for organic materials, comprising the compound according to any one of [1] to [6]. [9] The stabilizer according to [8], wherein the organic material is a thermoplastic resin.

[10] The stabilizer according to [9], wherein the thermoplastic resin is a polyolefin or an engineering plastic.

[11] A method for stabilizing an organic material, comprising adding the compound according to any one of [1] to [6] to an organic material.

[12] An organic material composition, comprising an organic material and the compound according to any one of [1] to [6].

[13] The composition according to

[12] , wherein the organic material is a thermoplastic resin.

[14] The composition according to

[13] , wherein the thermoplastic resin is a polyolefin or an engineering plastic.

[0008] According to the present invention, it is possible to provide a highly heat-resistant compound that can be used in processing organic materials that require high processing temperatures.

[0009] Hereinafter, embodiments of the present invention will be described in detail. Note that the scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present invention.

[0010] The present invention relates to a compound of formula (I): The present invention provides a diphosphite compound represented by the formula:

[0011] In the above formula (I), R １ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms; R ２ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; R ３ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 25 carbon atoms.

[0012] Examples of alkyl groups having 1 to 12 carbon atoms include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, tert-pentyl, n-hexyl, i-hexyl, n-octyl, i-octyl, tert-octyl, i-nonyl, tert-nonyl, 2-ethylhexyl, 1,1-diethylpropyl, 1,2-dimethylpropyl, 1,2-diethylpropyl, and 1-ethyl-1-methylpropyl.

[0013] Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a norbornyl group.

[0014] Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include a 1-methylcyclopentyl group, a 1-methylcyclohexyl group, and a 1-methyl-4-i-propylcyclohexyl group.

[0015] Examples of aralkyl groups having 7 to 25 carbon atoms include benzyl, α-methylbenzyl, cumyl (α,α-dimethylbenzyl), phenylethyl, phenylpropyl, α,α-dimethyl-4-phenylbenzyl, and α,α-dimethyl-2,4-di-tert-butylphenylbenzyl.

[0016] In a preferred embodiment of the present invention, the compound of formula (I) has the formula (I'): [In formula (I'), R １ , R ２ , R ３ and X is as defined above. That is, when one R １ The other R １ The meta position relative to the group is preferred from the viewpoint of improving the heat resistance of the diphosphite compound represented by formula (I).

[0017] In one preferred embodiment of the present invention, R １From the viewpoint of improving the heat resistance of the diphosphite compound represented by formula (I), is preferably a tertiary alkyl group having 4 to 12 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or a tertiary aralkyl group having 9 to 15 carbon atoms, more preferably a tertiary alkyl group having 4 to 12 carbon atoms, and even more preferably a tert-butyl group or a tert-pentyl group.

[0018] R ２ is preferably an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkylcycloalkyl group having 6 to 12 carbon atoms, from the viewpoint of improving the heat resistance of the diphosphite compound represented by formula (I); and is more preferably a tertiary alkyl group having 4 to 10 carbon atoms or a tertiary aralkyl group having 9 to 12 carbon atoms, since the diphosphite compound represented by formula (I) becomes less susceptible to the effects of hydrolysis, and is further preferably a methyl group, a tert-butyl group, a tert-pentyl group, or a cumyl group.

[0019] R ３ From the viewpoint of improving the heat resistance of the diphosphite compound represented by formula (I), is preferably an alkyl group having 1 to 10 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 25 carbon atoms, more preferably a tertiary alkyl group having 4 to 12 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or a tertiary aralkyl group having 9 to 21 carbon atoms, even more preferably a tertiary alkyl group having 5 to 10 carbon atoms or a tertiary aralkyl group having 9 to 15 carbon atoms, and still more preferably a tert-butyl group, a tert-pentyl group, or a cumyl group.

[0020] In the above formula (I), X represents a single bond, an alkylidene group having 1 to 4 carbon atoms, a sulfur atom, or an oxygen atom. The alkylidene group having 1 to 4 carbon atoms includes a methylene group (—CH ２ -), ethylene group (-CH ２ -CH ２ -), 1-methylethylene group (-CH ２ -CH(CH ３ )-), propylidene group (—CH(CH ２ -CH ３ )-), isopropylidene group (—C(CH ３ ) ２-), and butylidene groups (-CH(CH ２ -CH ２ -CH ３ From the viewpoint of improving the heat resistance of the diphosphite compound represented by formula (I), X is preferably a single bond, a methylene group, an ethylene group or a sulfur atom, more preferably a single bond.

[0021] The diphosphite compound represented by the formula (I) above is, for example, a compound represented by the formula (II): [In formula (II), R １ is as defined above] with phosphorus trihalide, to obtain a reaction product, [In formula (III), R ２ , R ３ and X is as defined above].

[0022] Examples of phosphorus trihalides include phosphorus trichloride, phosphorus tribromide, etc. From the viewpoint of ease of handling, phosphorus trichloride is preferably used.

[0023] The reaction can be accelerated by the coexistence of a dehydrohalogenating agent such as an amine, pyridine, pyrrolidine, or amide, or a hydroxide of an alkali metal or alkaline earth metal. To accelerate the reaction, one type of dehydrohalogenating agent or hydroxide of an alkali metal or alkaline earth metal may be used, or two or more types of these may be used in combination.

[0024] As the amines, any of primary amines, secondary amines, and tertiary amines may be used. Examples of amines include t-butylamine, t-pentylamine, t-hexylamine, t-octylamine, di-t-butylamine, di-t-pentylamine, di-t-hexylamine, di-t-octylamine, trimethylamine, triethylamine, N,N-diisopropylethylamine, N,N-dimethylaniline, and N,N-diethylaniline. Triethylamine and / or N,N-diisopropylethylamine are preferably used as amines from the viewpoint of facilitating the reaction. Examples of pyridines include pyridine and picoline, with pyridine being preferred. Examples of pyrrolidines include 1-methyl-2-pyrrolidine. Examples of amides include N,N-dimethylformamide and N,N-dimethylacetamide, with N,N-dimethylformamide being preferred.

[0025] Examples of the hydroxide of an alkali metal or alkaline earth metal include sodium hydroxide and calcium hydroxide, with sodium hydroxide being preferred.

[0026] The reaction is usually carried out in an organic solvent. The organic solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include aromatic hydrocarbons, aliphatic hydrocarbons, oxygenated hydrocarbons, and halogenated hydrocarbons. The reaction may be carried out in one type of organic solvent, in a mixed solvent of two or more types of organic solvents, or in a mixed solvent of the organic solvent and another solvent.

[0027] Examples of aromatic hydrocarbons include benzene, toluene, xylene, and ethylbenzene. Examples of aliphatic hydrocarbons include n-hexane, n-heptane, and n-octane. Examples of oxygen-containing hydrocarbons include diethyl ether, dibutyl ether, tetrahydrofuran, and 1,4-dioxane. Examples of halogenated hydrocarbons include chloroform, carbon tetrachloride, monochlorobenzene, dichloromethane, 1,2-dichloroethane, and dichlorobenzene. From the viewpoint of improving yield, it is preferable to use toluene, xylene, n-hexane, n-heptane, diethyl ether, tetrahydrofuran, 1,4-dioxane, chloroform, or dichloromethane as the organic solvent.

[0028] The reaction method employed is a two-stage reaction method in which a compound represented by formula (II) is reacted with phosphorus trihalide to obtain a reaction product, and then a compound represented by formula (III) is reacted with the resulting product. In this method, the phosphorus trihalide is preferably used in an amount of about 1.6 to 2.6 times by mole, more preferably about 1.8 to 2.4 times by mole, and even more preferably about 2.0 to 2.2 times by mole, relative to the compound represented by formula (II). When a dehydrohalogenating agent is used, the dehydrohalogenating agent is preferably used in an amount of about 0.05 to 5.0 times by mole, more preferably about 1.5 to 4.5 times by mole, and even more preferably about 2.0 to 4.0 times by mole, relative to the compound represented by formula (II).

[0029] The reaction of the compound represented by formula (II) with phosphorus trihalide is typically carried out at a temperature of about −60 to 100° C. The reaction time may typically be about 0.5 to 12 hours. The reaction may be carried out in air or in an inert gas atmosphere such as nitrogen gas or argon gas. However, from the viewpoint of easily suppressing decomposition of the phosphorus trihalide and intermediates, it is preferable to carry out the reaction in an inert gas atmosphere. The reaction may be carried out under normal pressure, elevated pressure, or reduced pressure. It is believed that this reaction produces an intermediate halogenophosphite. The resulting reaction product may be isolated and subjected to the next reaction, but typically the reaction mixture is directly subjected to the reaction with the compound represented by formula (III).

[0030] The method for reacting the compound represented by formula (II) with the phosphorus trihalide is not particularly limited as long as it allows the two to be mixed uniformly. However, from the viewpoint of easy control of the heat of reaction, it is preferable to carry out the reaction by a method in which the phosphorus trihalide is added dropwise to a mixture containing the compound represented by formula (II) and, optionally, a dehydrohalogenating agent, or a method in which the compound represented by formula (II) is added dropwise to a mixture containing the phosphorus trihalide and, optionally, a dehydrohalogenating agent. Furthermore, when a dehydrohalogenating agent is used, the reaction may be carried out by a method in which the dehydrohalogenating agent is added dropwise to a mixture containing the compound represented by formula (II) and the phosphorus trihalide. The dropwise addition time is also not particularly limited, and may be, for example, about 0.5 to 3 hours.

[0031] In the subsequent second-stage reaction, the compound represented by formula (III) is typically used in an amount of about 1.5 to 3.5 molar times, more preferably about 1.7 to 2.8 molar times, and even more preferably about 1.9 to 2.3 molar times, relative to the compound represented by formula (II). A dehydrohalogenating agent can also be used in this reaction. In this case, the amount of the dehydrohalogenating agent is preferably about 0.1 to 15 molar times, more preferably about 4.0 to 13.5 molar times, and even more preferably about 6.0 to 12.0 molar times, relative to the compound represented by formula (II) used in the first-stage reaction. The amount of the dehydrohalogenating agent used in the second-stage reaction is typically calculated as the total amount of the dehydrohalogenating agent used in the initial reaction and the additional dehydrohalogenating agent. The reaction with the compound represented by formula (III) is typically carried out at a temperature of about −60 to 100° C. The reaction time may typically be about 1 to 30 hours. The reaction may be carried out in air or in an inert gas atmosphere such as nitrogen gas or argon gas, but is preferably carried out in an inert gas atmosphere from the viewpoint of easily suppressing the generation of by-products. The reaction may be carried out under normal pressure, elevated pressure, or reduced pressure.

[0032] The method for reacting the compound represented by formula (II) with the compound represented by formula (III) is not particularly limited as long as the two can be mixed uniformly, but from the viewpoint of easy control of the reaction heat, it is preferable to carry out the reaction by a method in which the compound represented by formula (III) is added dropwise to a reaction product obtained by reacting the compound represented by formula (II) with phosphorus trihalide. The dropwise addition time is also not particularly limited, and may be carried out for, for example, about 10 minutes to 2 hours.

[0033] After the reaction is completed, in the case where a dehydrohalogenating agent has been used, the hydrohalide salt of the dehydrohalogenating agent produced by the reaction is removed, and the solvent is then removed. Thereafter, an appropriate post-treatment such as crystallization or column chromatography can be carried out to obtain the diphosphite compound of the present invention represented by formula (I).

[0034] The compounds represented by formula (II) and (III) that can be used in the production method of the present invention can be produced by known methods. For example, the compound represented by formula (II) can be produced according to the method described in Chinese Patent Application Publication No. 112341494. The compound represented by formula (III) can be produced according to the method described in Japanese Patent Application Laid-Open No. 2003-171325. If the compounds represented by formula (II) and (III) are commercially available, they can also be used.

[0035] Examples of the compound represented by formula (II) include resorcinol, 4,6-di-tert-butylresorcinol, 4,6-di-tert-pentylresorcinol, 4,6-di-α-cumylresorcinol, 4,6-dimethylresorcinol, 4,6-diethylresorcinol, and 4,6-di-tert-octylresorcinol.

[0036] Examples of the compound represented by formula (III) include 3,3',5,5'-tetra-tert-butyl-2,2'-dihydroxybiphenyl, 3,3',5,5'-tetra-tert-pentyl-2,2'-dihydroxybiphenyl, 3,3',5,5'-tetra-α-cumyl-2,2'-dihydroxybiphenyl, 3,3',5,5'-tert-pentyl-2,2'-dihydroxybiphenyl, 6,6'-methylenebis(2,4-tert-dibutylphenol), 3,3',5,5'-tetramethyl-2,2'-dihydroxybiphenyl, 6,6 '-thiobis(2,2'-di-tert-butyl-4,4'-dimethylphenol), 6,6'-methylenebis(2,2',4,4'-tetra-tert-butylphenol), 6,6'-oxybis(2,2',4,4'-tetra-tert-butylphenol), 6,6'-thiobis(2,2',4,4'-tetra-tert-butylphenol), 6,6'-methylenebis(2,2',4,4'-tetra-tert-pentylphenol), 6,6'-oxybis(2,2',4,4'-tetra-tert-pentylphenol), 6,6'- Thiobis(2,2',4,4'-tetra-tert-pentylphenol), 6,6'-methylenebis(2,2'-di-tert-butyl-4,4'-dimethylphenol), 6,6'-oxybis(2,2'-di-tert-butyl-4,4'-dimethylphenol), 3,3'-di-tert-butyl-5,5'-dimethyl-2,2'-dihydroxybiphenyl, 6,6'-thiobis(2,2',4,4'-tetramethylphenol), 6,6'-methylenebis(2,2',4,4'-tetramethylphenol), 6,6'-oxybis(2, 2',4,4'-tetramethylphenol), 6,6'-methylenebis(2,2',4,4'-tetra-α-cumylphenol), 6,6'-thiobis(2,2',4,4'-tetra-α-cumylphenol), 6,6'-oxybis(2,2',4,4'-tetra-α-cumylphenol), 3,3'-di-tert-butyl-5,5'-di-tert-pentyl-2,2'-dihydroxybiphenyl, 3,3'-di-tert-butyl-5,5'-di-α-cumyl-2,2'-dihydroxybiphenyl, 3,3'-di-tert-pentyl-5,5'-di-tert-butyl-2,2'-dihydroxybiphenyl, 3,3'-di-tert-pentyl-5,5'-dimethyl-2,2'-dihydroxybiphenyl, 3,3'-di-tert-pentyl-5,5'-α-cumyl-2,2'-dihydroxybiphenyl, 3,3'-dimethyl-5,5'-di-tert-butyl-2,2'-dihydroxybiphenyl, 3,3'-dimethyl-5,5'-di-tert-pentyl-2,2 '-dihydroxybiphenyl, 3,3'-dimethyl-5,5'-di-α-cumyl-2,2'-dihydroxybiphenyl, 3,3'-di-α-cumyl-5,5'-di-tert-butyl-2,2'-dihydroxybiphenyl, 3,3'-di-α-cumyl-5,5'-di-tert-pentyl-2,2'-dihydroxybiphenyl, 3,3'-di-α-cumyl-5,5'-dimethyl-2,2'-dihydroxybiphenyl, etc.

[0037] Addition of the diphosphite compound of the present invention represented by formula (I) to an organic material reduces thermal and oxidative degradation of the organic material, thereby stabilizing the organic material. Furthermore, the diphosphite compound of the present invention has high heat resistance. Therefore, the diphosphite compound of the present invention is particularly suitable as an active ingredient in stabilizers for organic materials that require high processing temperatures. From the viewpoint of exhibiting excellent heat resistance, the temperature at which the diphosphite compound of the present invention reaches a mass loss of 1% is preferably 340°C or higher, and more preferably 342°C or higher, 343°C or higher, 350°C or higher, 360°C or higher, 380°C or higher, or 400°C or higher. The temperature at which the mass loss reaches 1% is usually 440°C or lower.

[0038] Therefore, the present invention also provides a stabilizer for organic materials containing the diphosphite compound of the present invention represented by formula (I), a method for stabilizing organic materials by adding the diphosphite compound of the present invention represented by formula (I) to an organic material, and an organic material composition containing an organic material and the diphosphite compound of the present invention represented by formula (I). In these embodiments, as the diphosphite compound of the present invention represented by formula (I), one type of diphosphite compound represented by formula (I) may be used, or two or more types of diphosphite compounds represented by formula (I) may be used in combination.

[0039] Examples of organic materials that can be stabilized by the diphosphite compound of the present invention include, but are not limited to, the following: The organic material may be one type of organic material or a mixture of two or more types of organic materials.

[0040] (1) polyethylene, such as high density polyethylene (HD-PE), low density polyethylene (LD-PE), linear low density polyethylene (LLDPE), (2) polypropylene, (3) methylpentene polymer, (4) EEA (ethylene / ethyl acrylate copolymer) resin, (5) ethylene / vinyl acetate copolymer resin, (6) polystyrenes, such as polystyrene, poly(p-methylstyrene), poly(α-methylstyrene), (7) AS (acrylonitrile / styrene copolymer) resin, (8) ABS (acrylonitrile / butadiene / styrene copolymer) resin, (9) AAS (special acrylic rubber / acrylonitrile / styrene copolymer) resin, (10) ACS (acrylonitrile / chlorinated polyethylene / styrene copolymer) resin,

[0041] (11) chlorinated polyethylene, polychloroprene, chlorinated rubber, (12) polyvinyl chloride, polyvinylidene chloride, (13) methacrylic resin, (14) ethylene / vinyl alcohol copolymer resin, (15) fluororesin, (16) polyacetal, (17) grafted polyphenylene ether resin and polyphenylene sulfide resin, (18) polyurethane, (19) polyamide, (20) polyester resin, for example, polyethylene terephthalate, polybutylene terephthalate,

[0042] (21) polycarbonate, (22) polyacrylate, (23) polysulfone, polyether ether ketone, polyether sulfone, (24) thermoplastic resin such as aromatic polyester resin, (25) epoxy resin, (26) diallyl phthalate prepolymer, (27) silicone resin, (28) unsaturated polyester resin, (29) acrylic-modified benzoguanamine resin, (30) benzoguanamine / melamine resin, (31) thermosetting resin such as urea resin,

[0043] (32) polybutadiene, (33) 1,2-polybutadiene, (34) polyisoprene, (35) styrene / butadiene copolymer, (36) butadiene / acrylonitrile copolymer, (37) ethylene / propylene copolymer, (38) silicone rubber, (39) epichlorohydrin rubber, (40) acrylic rubber, (41) natural rubber,

[0044] (42) Chlorinated rubber paint, (43) polyester resin paint, (44) urethane resin paint, (45) epoxy resin paint, (46) acrylic resin paint, (47) vinyl resin paint, (48) amino alkyd resin paint, (49) alkyd resin paint, (50) nitrocellulose resin paint, (51) oil-based paint, (52) wax, (53) lubricating oil, etc.

[0045] Among these, thermoplastic resins, particularly polyolefins such as polyethylene, for example, HD-PE, LD-PE, LLDPE and polypropylene, polyamides, engineering plastics such as polyethylene terephthalate, polybutylene terephthalate and polycarbonate are preferably used.

[0046] The polyolefin is not particularly limited, and may be, for example, one obtained by radical polymerization or one produced by polymerization using a catalyst containing a metal of Group IVb, Vb, VIb, or VIII of the periodic table. Examples of such metal-containing catalysts include metal complexes having one or more ligands, such as oxides, halides, alcoholates, esters, and aryls, coordinated by π or σ bonds. These complexes may be in the form of metal complexes themselves, or may be supported on a substrate such as magnesium chloride, titanium chloride, alumina, or silicon oxide. Preferred polyolefins are those produced using, for example, Ziegler-Natta catalysts, TNZ catalysts, metallocene catalysts, or Phillips catalysts.

[0047] Engineering plastics are also not particularly limited. Polyamide resins may be any resins that have amide bonds in the polymer chain and can be melted by heating. Polyamide resins may be produced by any method, including those produced by the condensation reaction of diamines and dicarboxylic acids, the condensation reaction of aminocarboxylic acids, and the ring-opening polymerization of lactams. Examples of polyamide resins include nylon 66, nylon 69, nylon 610, nylon 612, poly-bis-(p-aminocyclohexyl)methandodecamide, nylon 46, nylon 6, nylon 12, and copolymers such as nylon 66 / 6 and nylon 6 / 12, which are copolymers of nylon 66 and nylon 6. Polyester resins may be any resins that have ester bonds in the polymer chain and can be melted by heating, including, for example, polyesters obtained by polycondensation of dicarboxylic acids and dihydroxy compounds. Polyester resins may be either homopolyesters or copolyesters. The polycarbonate resin may be any resin having a carbonate bond in the polymer chain and capable of being melted by heating, such as a polycarbonate obtained by reacting an aromatic hydroxy compound or a small amount of a polyhydroxy compound with a carbonate precursor such as phosgene or diphenyl carbonate in the presence of a solvent, an acid acceptor, and a molecular weight modifier. The polycarbonate resin may be linear or branched, or may be a copolymer.

[0048] When the diphosphite compound of the present invention represented by formula (I) is added to an organic material to stabilize the organic material, the content of the diphosphite compound of the present invention is usually 0.0001 part by mass or more, preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and even more preferably 0.05 part by mass or more, per 100 parts by mass of the organic material, from the viewpoint of stabilizing the organic material. Furthermore, the content of the diphosphite compound of the present invention is usually 5 parts by mass or less, preferably 3 parts by mass or less, and more preferably 1 part by mass or less, per 100 parts by mass of the organic material, from the viewpoint of efficiently stabilizing the organic material and being economical.

[0049] When the diphosphite compound of the present invention represented by formula (I) is added to an organic material, other additives may be added to the organic material as needed, such as phenolic antioxidants, sulfur-based antioxidants, phosphite-based antioxidants other than the diphosphite compound of the present invention, ultraviolet absorbers, light stabilizers, peroxide scavengers, polyamide stabilizers, hydroxyamines, lubricants, plasticizers, flame retardants, nucleating agents, metal deactivators, antistatic agents, pigments, fillers, pigments, antiblocking agents, surfactants, processing aids, foaming agents, emulsifiers, gloss agents, calcium stearate, etc. Neutralizing agents such as sodium or hydrotalcite, color improvers such as 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, and co-stabilizers such as benzofurans and indolines described in U.S. Patent Nos. 4,325,853, 4,338,244, 5,175,312, 5,216,053, 5,252,643, 4,316,611, DE-A-4,316,622, 4,316,876, EP-A-589,839, and EP-A-591,102 can also be added. These additives can be added to the organic material simultaneously with the diphosphite compound of the present invention, or can be added to the organic material at a stage separate from the diphosphite compound of the present invention. One type of additive can be used, or two or more types of additives can be used in combination. The amount of these additives to be added is not particularly limited as long as it does not affect the desired properties of the organic material, but may be usually about 0.001 to 5 parts by mass, preferably about 0.005 to 3 parts by mass, and more preferably about 0.01 to 1 part by mass, per 100 parts by mass of the organic material.

[0050] Examples of the phenolic antioxidant include the following: As the phenolic antioxidant, the following compounds may be used alone or in combination of two or more.

[0051] (1) Examples of alkylated monophenols: 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,6-di-t-butylphenol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2 ,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundecyl-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadecyl-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridecyl-1'-yl)phenol and mixtures thereof.

[0052] (2) Examples of alkylthiomethylphenols include 2,4-dioctylthiomethyl-6-t-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol, and mixtures thereof. (3) Examples of hydroquinone and alkylated hydroquinones include 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyphenyl stearate, bis(3,5-di-t-butyl-4-hydroxyphenyl)adipate, and mixtures thereof.

[0053] (4) Examples of tocopherols: α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, and mixtures thereof. (5) Examples of hydroxylated thiodiphenyl ethers: 2,2'-thiobis(6-t-butylphenol), 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), 4,4'-thiobis(3,6-di-t-amylphenol), 4,4'-(2,6-dimethyl-4-hydroxyphenyl)disulfide, and the like.

[0054] (6) Examples of alkylidene bisphenols and derivatives thereof 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol)], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(4-methyl-6-nonylphenol), 2,2'-methylenebis(4,6-di-t-butylphenol), 2,2'-ethylidenebis(4,6-di-t-butylphenol), 2,2'-ethylidenebis(4-isobutyl-6-t-butylphenol), 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[4,6-(α,α- dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(6-t-butyl-2-methylphenol), 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol Bis[3,3-bis-3'-t-butyl-4'-hydroxyphenyl)butyrate], bis(3-t-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3'-t-butyl-2'-hydroxy-5'-methylbenzyl)-6-t-butyl-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-t-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra(5-t-butyl-4-hydroxy-2-methylphenyl)pentane, 2-t-butyl-6-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,4-di-t-pentyl-6-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]phenyl acrylate, and mixtures thereof.

[0055] (7) Examples of O-, N- and S-benzyl derivatives: 3,5,3',5'-tetra-t-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tris(3,5-di-t-butyl-4-hydroxybenzyl)amine, bis(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-t-butyl-4-hydroxybenzyl mercaptoacetate, and mixtures thereof. (8) Examples of hydroxybenzylated malonate derivatives include dioctadecyl-2,2-bis(3,5-di-t-butyl-2-hydroxybenzyl)malonate, dioctadecyl-2-(3-t-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecylmercaptoethyl-2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate, and mixtures thereof. (9) Examples of aromatic hydroxybenzyl derivatives: 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,4-bis(3,5-di-t-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-t-butyl-4-hydroxybenzyl)phenol, and mixtures thereof.

[0056] (10) Examples of triazine derivatives: 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2-n-octylthio-4,6-bis(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2-n-octylthio-4,6-bis(4-hydroxy-3,5-di-t-butylphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-t-butyl-4-phenoxy)-1,3,5-triazine, tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)iso cyanurate, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 2,4,6-tris(3,5-di-t-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 2,4,6-tris(3,5-di-t-butyl-4-hydroxyphenylpropyl)-1,3,5-triazine, tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, tris[2-(3',5'-di-t-butyl-4'-hydroxycinnamoyloxy)ethyl]isocyanurate, and mixtures thereof.

[0057] (11) Examples of benzylphosphonate derivatives include dimethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoester, and mixtures thereof. (12) Examples of acylaminophenol derivatives include 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide, octyl-N-(3,5-di-t-butyl-4-hydroxyphenyl)carbamate, and mixtures thereof. (13) Examples of esters of β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid with the following monohydric or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, and mixtures thereof.

[0058] (14) Examples of esters of β-(5-t-butyl-4-hydroxy-3-methylphenyl)propionic acid with the following monohydric or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, and mixtures thereof. (15) Examples of esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with the following monohydric or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, and mixtures thereof.

[0059] (16) Examples of esters of 3,5-di-t-butyl-4-hydroxyphenylacetic acid with the following monohydric or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, and mixtures thereof. (17) Examples of amides of β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid include N,N'-bis[3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionyl]hydrazine, N,N'-bis[3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionyl]hexamethylenediamine, N,N'-bis[3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionyl]trimethylenediamine, and mixtures thereof.

[0060] Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, neopentanetetrayltetrakis (3-laurylthiopropionate), and the like.

[0061] Examples of phosphite-based antioxidants other than the diphosphite-based compounds of the present invention include the following: As the phosphite-based antioxidants other than the diphosphite-based compounds of the present invention, the following compounds may be used alone or in combination of two or more: triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-t-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-t-butylphenyl)pentaerythritol Diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-diphenylene diphosphonite, 2,2'-methylenebis(4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, 2,2'-ethylidenebis(4,6-di-t-butylphenyl) fluorophosphite, bis(2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, bis(2,4-di-t-butyl-6-methylphenyl) methyl phosphite, 2-(2,4,6-tri-t-butylphenyl)-5-ethyl-5-butyl-1,3,2-oxaphosphorinane, 2,2',2''-nitrilo[triethyl-tris(3,3',5,5'-tetra-t-butyl-1,1'-biphenyl-2,2'-diyl] phosphite, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1,3,2]dioxaphosphepine, and mixtures thereof.

[0062] Examples of ultraviolet absorbers include the following. As the ultraviolet absorber, the following compounds may be used alone or in combination of two or more. (1) Examples of salicylate derivatives: phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3',5'-di-t-butyl-4'-hydroxybenzoate, 4-t-octylphenyl salicylate, bis(4-t-butylbenzoyl)resorcinol, benzoylresorcinol, hexadecyl 3',5'-di-t-butyl-4'-hydroxybenzoate, octadecyl 3',5'-di-t-butyl-4'-hydroxybenzoate, 2-methyl-4,6-di-t-butylphenyl 3',5'-di-t-butyl-4'-hydroxybenzoate, and mixtures thereof. (2) Examples of 2-hydroxybenzophenone derivatives include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2′,4,4′-tetrahydroxybenzophenone, and mixtures thereof.

[0063] (3) Examples of 2-(2'-hydroxyphenyl)benzotriazole: 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(3',5'-di-t-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-t-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(3'-s-butyl-2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'- 2-(3',5'-di-t-amyl-2'-hydroxyphenyl)benzotriazole, 2-[2'-hydroxy-3',3'-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-[(3'-t-butyl-2'-hydroxyphenyl)-5'-(2-octyloxycarbonylethyl)phenyl]-5-chlorobenzotriazole, 2-[3'-t-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2' -hydroxyphenyl]-5-chlorobenzotriazole, 2-[3'-t-butyl-3'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl]-5-chlorobenzotriazole, 2-[3'-t-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl]benzotriazole, 2-[3'-t-butyl-2'-hydroxy-5-(2-octyloxycarbonylethyl)phenyl]benzotriazole, 2-[3'-t-butyl-2'-hydroxy-5'-[2-(2-ethylhexyl) a mixture of 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole and 2-[3'-t-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenyl]benzotriazole, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[4-t-butyl-6-(2H-benzotriazol-2-yl)phenol], condensation products of poly(3-11)(ethylene glycol) and 2-[3'-t-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl]benzotriazole, condensation products of poly(3-11)(ethylene glycol) and methyl 3-[3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl]propionate, 2-ethylhexyl 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, octyl 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, methyl 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionic acid, and mixtures thereof.

[0064] Examples of light stabilizers include the following. As the light stabilizer, the following compounds may be used alone or in combination of two or more. (1) Examples of hindered amine light stabilizers: bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(N-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-cyclohexyloxy-2,2,6,6-tetramethyl-4- piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1-acroyl-2,2,6,6-tetramethyl-4-piperidyl) 2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate, 2,2,6,6-tetramethyl-4-piperidyl Methacrylate, 4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-1-[2-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)ethyl]-2,2,6,6-tetramethylpiperidine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionyl Pionamide, 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, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol,

[0065] Mixed esters of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, dimethyl Polycondensation copolymer of succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[(6-morpholino-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)], poly[(6-(1,1,3,3-tetramethyl- N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)imino-1,3,5-triazine-2,4-diyl((2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)], polycondensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 1,2-dibromoethane, N,N',4,7-tetramethylbutyl Rakis[4,6-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, N,N',4-tris[4,6-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine 1,10-diamine, N,N',4,7-tetrakis[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, N,N',4-tris[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine and mixtures thereof.

[0066] (2) Examples of acrylate-based light stabilizers include ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, and mixtures thereof. (3) Examples of nickel-based light stabilizers include nickel complexes of 2,2'-thiobis-[4-(1,1,3,3-tetramethylbutyl)phenol], nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, nickel complexes of ketoximes, and mixtures thereof.

[0067] (4) Examples of oxamide-based light stabilizers: 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-t-butylanilide, 2,2'-didodecyloxy-5,5'-di-t-butylanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-t-butyl-2'-ethoxyanilide, 2-ethoxy-5,4'-di-t-butyl-2'-ethyloxanilide, and mixtures thereof. (5) Examples of 2-(2-hydroxyphenyl)-1,3,5-triazine-based light stabilizers: 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2,4-dihydroxyphenyl-4,6-bis(2,4-dimethylphenyl]-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis (4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and mixtures thereof.

[0068] Examples of metal deactivators include N,N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide, and mixtures thereof.

[0069] Examples of peroxide scavengers include esters of β-thiodipropionic acid, mercaptobenzimidazole, zinc salts of 2-mercaptobenzimidazole, zinc salts of dibutyldithiocarbamic acid, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate, and mixtures thereof. Examples of polyamide stabilizers include copper or divalent manganese salts of iodides or phosphorus compounds, and mixtures thereof.

[0070] Examples of hydroxyamines include N,N-dibenzylhydroxyamine, N,N-diethylhydroxyamine, N,N-dioctylhydroxyamine, N,N-dilaurylhydroxyamine, N,N-ditetradecylhydroxyamine, N,N-dihexadecylhydroxyamine, N,N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl-N-octadecylhydroxyamine, and mixtures thereof.

[0071] Examples of the neutralizing agent include calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (basic magnesium aluminum hydroxy carbonate hydrate), melamine, amine, polyamide, polyurethane, and mixtures thereof.

[0072] Examples of lubricants include aliphatic hydrocarbons such as paraffin and wax, higher fatty acids having 8 to 22 carbon atoms, metal (Al, Ca, Mg, Zn) salts of higher fatty acids having 8 to 22 carbon atoms, aliphatic alcohols having 8 to 22 carbon atoms, polyglycols, esters of higher fatty acids having 4 to 22 carbon atoms and aliphatic monohydric alcohols having 4 to 18 carbon atoms, higher aliphatic amides having 8 to 22 carbon atoms, silicone oils, and rosin derivatives.

[0073] Examples of nucleating agents include sodium 2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate, [2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate]dihydroxyaluminum, bis[2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate]hydroxyaluminum, tris[2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate]aluminum, sodium Bis(4-t-butylphenyl)phosphate, metal salts of benzoic acid such as sodium benzoate, aluminum p-t-butylbenzoate, 1,3:2,4-bis(O-benzylidene)sorbitol, 1,3:2,4-bis(O-methylbenzylidene)sorbitol, 1,3:2,4-bis(O-ethylbenzylidene)sorbitol, 1,3-O-3,4-dimethylbenzylidene-2,4-O-benzylidene sorbitol, 1,3-O-benzylidene and mixtures thereof.

[0074] Examples of fillers include calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, carbon black, carbon fibers, zeolites, and mixtures thereof.

[0075] Among these additives, those that are preferably used are phenol-based antioxidants, phosphite-based antioxidants other than the diphosphite-based compounds of the present invention, ultraviolet absorbers, hindered amine-based light stabilizers, peroxide scavengers and neutralizing agents.

[0076] Particularly preferred phenolic antioxidants include the following compounds: 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,2'-thiobis(6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol)], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2 '-Methylenebis(4,6-di-t-butylphenol), 2,2'-ethylidenebis(4,6-di-t-butylphenol), 4,4'-methylenebis(6-t-butyl-2-methylphenol), 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 1,1,3-tris(5-t-butyl-4-hydroxy-2-methylphenyl)butane, ethylene glycol bis[3,3-bis-3'-t-butyl-4'-hydroxyphenyl)butyrate], 2-t-butyl-6-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,4-di-t-pentyl-6-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]phenyl acrylate,

[0077] 2,4,6-tris(3,5-di-t-butyl-4-phenoxy)-1,3,5-triazine, tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, bis(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, tris[2-(3',5'-di-t-butyl-4'-hydroxycinnamoyloxy)ethyl]isocyanurate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, di-n-octadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoester, n-octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, neopentanetetrayltetrakis(3,5-di-t-butyl-4-hydroxycinnamate), thiodiethylenebis(3,5-di-t-butyl-4-hydroxycinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 3,6-dioxaoctamethylenebis(3,5-di-t-butyl-4-hydroxycinnamate), hexamethylenebis(3,5-di-t-butyl-4-hydroxycinnamate), triethylene glycol Bis(5-t-butyl-4-hydroxy-3-methylcinnamate), 3,9-bis[2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl]-2,4,4,10-tetraoxaspiro[5.5]undecane, N,N'-bis[3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionyl]hydrazine, N,N'-bis[3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionyl]hexamethylenediamine, and the like.

[0078] Particularly preferred phosphite-based antioxidants other than the diphosphite-based compounds of the present invention include the following compounds. Tris(nonylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-t-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-diphenylenediphosphonite, 2,2'-methylenebis(4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, 2,2'-ethylidenebis(4,6-di-t-butylphenyl) fluorophosphite, bis(2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, 2-(2,4,6-tri-t-butylphenyl)-5-ethyl-5-butyl-1,3,2-oxaphosphorinane, 2,2',2''-nitrilo[triethyl-tris(3,3',5,5'-tetra-t-butyl-1,1'-biphenyl-2,2'-diyl)phosphite, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1,3,2]dioxaphosphepine, and the like.

[0079] Particularly preferred ultraviolet absorbers include the following compounds: phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3',5'-di-t-butyl-4'-hydroxybenzoate, 4-t-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2',4,4'-tetrahydroxybenzophenone, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(3',5'-di-t-butyl-2'-hydroxyphenyl)benzotriazole, and 2-(5'-t-butyl-2'-hydroxyphenyl)benzotriazo. 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(3'-s-butyl-2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-t-amyl-2'-hydroxyphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, and the like.

[0080] Particularly preferred light stabilizers include the following compounds: bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(N-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, and bis(1-acroyl-2,2,6,6-tetramethyl-4-piperidyl). 2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-1-[2-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)ethyl]-2,2,6,6-tetramethylpiperidine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,

[0081] Tetrakis(1,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl- Mixed esters of 4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, dimethyl Polycondensation products of succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[(6-morpholino-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)], poly[(6-(1,1,3,3-tetramethylbutyl)-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)], and the like.

[0082] The diphosphite compound of the present invention represented by formula (I) and / or other optional additives can be added to an organic material using any known method and apparatus for obtaining a homogeneous mixture. For example, when the organic material is a solid polymer, the diphosphite compound of the present invention and / or other optional additives can be dry-blended directly with the solid polymer, or the diphosphite compound and / or other optional additives can be added to the solid polymer in the form of a masterbatch. When the organic material is a liquid polymer, in addition to the above-mentioned addition method, the diphosphite compound of the present invention and / or other optional additives can be blended in the form of a solution or dispersion into the polymer solution during or immediately after polymerization. On the other hand, when the organic material is a liquid other than a solid polymer (e.g., oil), in addition to the above-mentioned addition method, the diphosphite compound of the present invention and / or other optional additives can be directly added to the organic material to dissolve it, or the diphosphite compound of the present invention and / or other optional additives can be added in the form of a solution or suspension in a liquid medium.

[0083] The diphosphite compound of the present invention represented by formula (I) has excellent performance as a stabilizer for various organic materials, including thermoplastic resins such as polyolefins. Organic materials to which the diphosphite compound of the present invention has been added are stable against thermal and oxidative degradation during production, processing, and use, resulting in high-quality products. Furthermore, because the diphosphite compound of the present invention has high heat resistance, it can be suitably used in the processing of organic materials that require high processing temperatures.

[0084] The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples.

[0085] Example 1 15.0 g (67.5 mmol) of 4,6-di-tert-butylresorcinol, 19.5 g (141.7 mmol, 2.1 equivalents relative to 4,6-di-tert-butylresorcinol (the same applies hereinafter)) of phosphorus trichloride, and 150 mL of toluene were placed in a four-neck flask and then cooled to −40° C. under a nitrogen atmosphere. A mixed solution of 20.5 g (202.4 mmol, 3.0 equivalents) of triethylamine and 150 mL of toluene was added dropwise thereto over 1 hour and 30 minutes. The temperature was then raised to room temperature and maintained at that temperature for 1 hour, and further raised to 60° C. and maintained at that temperature for 2.5 hours. After confirming by LC analysis that no raw materials remained, the mixture was cooled to -40°C, and a mixture of 55.4 g (135.0 mmol, 2.0 equivalents) of 3,3',5,5'-tetra-tert-butyl-2,2'-dihydroxybiphenyl, 41.0 g (404.8 mmol, 6.0 equivalents, a total of 9.0 equivalents including the amount used in the first-step reaction), and 150 mL of toluene was added dropwise over 30 minutes. The mixture was then stirred at room temperature for 15 hours, heated to 80°C, and stirred for an additional 4 hours. After completion of the reaction, the reaction mixture was returned to room temperature and quenched by adding water. The organic layer obtained by a separation operation using toluene was then washed twice with saturated saline solution. The obtained organic layer was dried over magnesium sulfate, filtered, and concentrated to obtain a crude product, which was purified by silica gel chromatography (ethyl acetate:hexane=1:30 (volume ratio)) and reverse-phase silica gel chromatography (acetonitrile:ethyl acetate=4:1 to 2:1 (volume ratio)), and then repulped and washed with an ethyl acetate / acetonitrile mixed solvent to obtain 47.2 g of diphosphite compound A-1 represented by formula (A-1) in a yield of 63.7% and a purity of 99.6%.

[0086]

[0087] １ H-NMR (CD ２ Cl ２ , 400MHz): δ1.23 (s, 18H), δ1.36 (s, 36H), δ1.40 (s, 36H), δ7.24-7.26 (m, 5H), δ7.28 (s, 1H), δ7.45-7.46 (m, 4H)

[0088] Example 2 In the method shown in Example 1, 15.0 g of 4,6-di-tert-pentylresorcinol was used instead of 4,6-di-tert-butylresorcinol to obtain 44.8 g of diphosphite compound A-2 represented by formula (A-2) in a yield of 66.3% and a purity of 99.0%.

[0089]

[0090] １ H-NMR (CDCl ３ , 400MHz): δ0.61 (t, J=7.2Hz, 6H), δ1.30 (s, 12H), δ1.76 (q, J=7.6Hz, 4H), δ2.33 (s, 12H), δ2.34 (s, 1 2H), δ7.01 (d, J=1.6Hz, 4H), δ7.10 (d, J=1.6Hz, 4H), δ7.19 (s, 1H), δ7.37 (t, J=1.2Hz, 1H)

[0091] Example 3 In the method shown in Example 1, 168 g of 3,3',5,5'-tetra-tert-pentyl-2,2'-dihydroxybiphenyl was used instead of 3,3',5,5'-tetra-tert-butyl-2,2'-dihydroxybiphenyl, to obtain 118.4 g of diphosphite compound A-3 represented by formula (A-3) in a yield of 54.3% and a purity of 99.3%.

[0092]

[0093] １ H-NMR (CD ２ Cl ２ , 400MHz): δ0.65 (t, J=7.4Hz, 12H), δ0.75 (t, J=7.4Hz, 12H), δ1.26 (s, 18H), δ1.32 (s, 24H), δ1.36 (s, 12H), δ1.40 (s, 12H), δ1.65- 1.79 (m, 12H), δ1.88-1.91 (m, 4H), δ7.18 (d, J=2.2Hz, 4H), δ7.27 (t, J=2.5Hz, 1H), δ7.29 (s, 1H), δ7.32 (d, J=2.2Hz, 4H)

[0094] Example 4 In the method shown in Example 1, 2.10 g of 4,6-di-tert-pentylresorcinol was used instead of 4,6-di-tert-butylresorcinol, and 8.03 g of 3,3',5,5'-tert-pentyl-2,2'-dihydroxybiphenyl was used instead of 3,3',5,5'-tetra-tert-butyl-2,2'-dihydroxybiphenyl, to obtain 6.96 g of diphosphite compound A-4 represented by formula (A-4) in a yield of 66.9% and a purity of 99.9%.

[0095]

[0096] １ H-NMR (CD ２ Cl ２ , 400MHz): δ0.53 (t, J=7.5Hz, 6H), δ0.64 (t, J=7.4Hz, 12H), δ0.75 (t, J=7.4H z, 12H), δ1.22 (s, 12H), δ1.31 (s, 24H), δ1.36 (s, 12H), δ1.39 (s, 1 2H), δ1.61-1.77 (m, 16H), δ1.88-1.92 (m, 4H), δ7.12 (s, 1H), δ7.1 7 (d, J=2.5Hz, 4H), δ7.24 (t, J=2.7Hz, 1H), δ7.31 (d, J=2.5Hz, 4H)

[0097] Example 5 In the method shown in Example 1, 1.50 g of 4,6-di-tert-pentylresorcinol was used instead of 4,6-di-tert-butylresorcinol, and 4.34 g of 6,6'-thiobis(2,2'-di-tert-butyl-4,4'-dimethylphenol) was used instead of 3,3',5,5'-tetra-tert-butyl-2,2'-dihydroxybiphenyl, to obtain 2.57 g of diphosphite compound A-5 represented by formula (A-5) in a yield of 33.0% and a purity of 97.4%.

[0098]

[0099] １ H-NMR (CDCl ３, 400MHz): δ0.68 (t, J=7.5Hz, 6H), δ1.30 (s, 36H), δ1.44 (s, 12H), δ1.99 (m, 4H), δ2.21 (s, 12H), δ6.97 (d, J=2.2Hz, 4H), δ7.16 (t, J=2.1Hz, 1H), δ7.19 (d, J=1.7Hz, 4H), δ7.21 (s, 1H)

[0100] Example 6 In the method shown in Example 1, 3.0 g of 4,6-di-tert-pentylresorcinol was used instead of 4,6-di-tert-butylresorcinol, and 5.99 g of 3,3',5,5'-tetramethyl-2,2'-dihydroxybiphenyl was used instead of 3,3',5,5'-tetra-tert-butyl-2,2'-dihydroxybiphenyl, to obtain 4.99 g of diphosphite compound A-5 represented by formula (A-6) in a yield of 52.7% and a purity of 99.8%.

[0101]

[0102] １ H-NMR (CDCl ３ , 400MHz): δ0.61 (t, J=7.5Hz, 6H), δ1.30 (s, 12H), δ1.75-1.77 (m, 4H), δ2.33 (s, 12H), δ2.34 (s, 12 H), δ7.01 (d, J=1.7Hz, 4H), δ7.10 (d, J=1.7Hz, 4H), δ7.19 (s, 1H), δ7.37 (t, J=1.2Hz, 1H)

[0103] Example 7 In the method shown in Example 1, 2.7 g of 4,6-di-tert-pentylresorcinol was used instead of 4,6-di-tert-butylresorcinol, and 13.9 g of 3,3',5,5'-tetra-α-cumyl-2,2'-dihydroxybiphenyl was used instead of 3,3',5,5'-tetra-tert-butyl-2,2'-dihydroxybiphenyl, to obtain 6.38 g of diphosphite compound A-7 represented by formula (A-7) in a yield of 36.4% and a purity of 98.6%.

[0104]

[0105] １ H-NMR (CD２ Cl ２ , 400MHz): δ0.57 (t, J=7.4Hz, 6H), δ1.12 (s, 12H), δ1.56 (s, 16H), δ1.68 (s, 36H) ), δ6.79 (t, J=2.7Hz, 1H), δ6.99-7.03 (m, 24H), δ7.14-7.33 (m, 25H)

[0106] Comparative Example 1: 4.66 g (11.4 mmol) of 3,3',5,5'-tetra-tert-butyl-2,2'-dihydroxybiphenyl and 12 mL of toluene were placed in a three-necked flask and heated to 60°C under a nitrogen atmosphere. 1.80 g (13.1 mmol) of phosphorus trichloride was added, followed by dropwise addition of 7.34 g (56.8 mmol) of N,N-diisopropylethylamine over 1 hour and 30 minutes. After maintaining the temperature at the same temperature for 2 hours, 0.5 g (4.54 mmol) of resorcinol was added, and the mixture was maintained at the same temperature for an additional 6 hours. After confirming no change in the reaction by LC analysis, the reaction mixture was returned to room temperature and quenched by adding 10 mL of water. The organic layer obtained by a separation operation using toluene was then washed twice with saturated saline. The obtained organic layer was dried over magnesium sulfate, filtered, and concentrated to obtain a crude product, which was purified by silica gel chromatography (ethyl acetate:hexane=1:30 (volume ratio)) to obtain 1.50 g of diphosphite compound B-1 represented by formula (B-1) in a yield of 33.5% and a purity of 98.6%.

[0107]

[0108] １ H-NMR (CDCl ３ , 400MHz): δ1.35 (s, 36H), δ1.47 (s, 36H), δ6.80 (dd, J=8.2, 2.2Hz, 2H), δ6.91 (m, 1H ), δ7.15 (t, J=8.3Hz, 1H), δ7.19 (d, J=2.4Hz, 4H), δ7.45 (d, J=2.4Hz, 4H)

[0109] Comparative Example 2 In the method shown in Example 1, 18.0 g of 2,4-tert-butylphenol was used instead of 3,3′,5,5′-tetra-tert-butyl-2,2′-dihydroxybiphenyl, to obtain 45.3 g of diphosphite compound B-2 represented by formula (B-2) in a yield of 46.9% and a purity of 97.8%.

[0110]

[0111] １ H-NMR (CD ２ Cl ２ , 400MHz): δ1.26 (s, 36H), δ1.31 (s, 54H), δ7.04 (dd, J=8.4, 2.5Hz, 4H), δ7.16 (dd, J=8 .4, 2.0Hz, 4H), δ7.31 (s, 1H), δ7.33 (d, J=2.5Hz, 4H), δ7.51 (t, J=3.3Hz, 1H)

[0112] Reference Example 1 In the method of Comparative Example 1, A-1 was synthesized using 0.21 g of 4,6-di-tert-butylresorcinol instead of resorcinol. As a result, 0.15 g of A-1 was obtained in a yield of 14.3%, and 0.17 g of compound A-1′ represented by formula (A-1′) was obtained in a yield of 20.4%.

[0113] １ H-NMR (CDCl ３ , 400MHz): δ1.33 (s, 72H), δ7.14 (d, J=2.5Hz, 4H), δ7.36 (m4H)

[0114] [Analysis conditions for diphosphite compounds] The purity of the compounds in the examples and comparative examples was measured under the following conditions. Purity (LC) Model: LC-20A (Shimadzu Corporation) Column: SUMIPAX ODS A-212 (5 μm, 6 mmφ, 150 mm) (Sumika Chemical Analysis Center Co., Ltd.) Injection volume: 1 μL (each methanol / chloroform = 1 / 1 (v / v) solution) Mobile phase: Solution A: acetonitrile Solution B: 2-propanol Gradient: B conc. (%) 80% → (20 min) → 100% → (30 min) → 100% Flow rate: 1.0 mL / min Column temperature: 40°C Measurement wavelength: UV, 280 nm

[0115] Structural analysis of the compounds of Examples and Comparative Examples ( １ H-NMR measurement was carried out using the following equipment: Equipment: Varian 400MR (manufactured by Agilent)

[0116] [Evaluation of Heat Resistance (TG-DTA)] The diphosphite compounds A-1 to A-7 and B-1 to B-2 obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were each heated from 23-25°C to 200°C at a rate of 20°C / min in a nitrogen atmosphere using a thermogravimetric differential thermal analyzer (Shimadzu Corporation, "DTG-60H"), held for 10 minutes, cooled to 100°C, and then heated to 600°C at a rate of 20°C / min to measure the temperature at which a mass loss of 1% was reached. The results are shown in Table 1. A higher temperature indicates better heat resistance. Based on the obtained results, evaluation was performed according to the following evaluation criteria. A: 340°C or higher, B: less than 340°C

[0117] [Evaluation of Processing Stability (MFR)] Pellets were prepared using the diphosphite compounds A-1 to A-7 and B-1 to B-2 obtained in Examples 1 to 7 and Comparative Examples 1 and 2, respectively, according to the following procedure. 100 parts by mass of homopolypropylene (manufactured by Sumitomo Chemical, MFR = 17 to 21) was dry-blended with 0.05 parts by mass of calcium stearate (manufactured by Nitto Kasei Kogyo Co., Ltd.), 0.05 parts by mass of Irganox 1010 (manufactured by BASF Japan Ltd.), and 0.1 parts by mass of the diphosphite compound. The resulting mixture was kneaded in a twin-screw extruder (BTN-32, PLABORA) with a cylinder diameter of 32 mm under nitrogen atmosphere at 230°C and a screw rotation speed of 50 rpm to obtain pellets. The MFR of the resulting pellets was measured according to the following method.

[0118] The MFR was measured using a melt flow index tester (Model No. 120-LABOT-50, manufactured by Yasuda Seiki Seisakusho Co., Ltd.) according to the method specified in JIS K7210-2014 under conditions of a temperature of 230°C and a load of 21.18 N. Resin compositions containing thermoplastic resins primarily composed of polypropylene resins undergo thermal processing, resulting in an increase in MFR. Therefore, the smaller the MFR, the better the processing stability. The homopolypropylene used in this evaluation had an MFR of approximately 17 to 21 before processing. The MFR of pellets containing the compound of Example 2 was 17.2, and the MFR of pellets containing the compound of Comparative Example 2 was 17.6. Furthermore, the compounds of Examples 1 and 3 to 7 all exhibited good processing stability.

[0119]

[0120] It was confirmed that the diphosphite compounds of the examples had high heat resistance.

[0121] The diphosphite compound of the present invention has high heat resistance and can therefore be suitably used in the processing of organic materials which require high processing temperatures.

Claims

1. Formula (I): [In formula (I), R １ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 25 carbon atoms; R ２ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; R ３ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 25 carbon atoms; and X represents a single bond, an alkylidene group having 1 to 4 carbon atoms, a sulfur atom, or an oxygen atom.

2. R １ is a tertiary alkyl group having 4 to 12 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or a tertiary aralkyl group having 9 to 15 carbon atoms.

3. The compound of formula (I) above has the formula (I'): [In formula (I'), R １ , R ２ , R ３ and X is as defined above.

4. The compound of claim 1, wherein X is a single bond.

5. R ３ is a tertiary alkyl group having 4 to 12 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or a tertiary aralkyl group having 9 to 21 carbon atoms.

6. R ３ is a tertiary alkyl group having 5 to 10 carbon atoms.

7. Formula (II): [In formula (II), R １ is as defined above] with phosphorus trihalide, to obtain a reaction product, [In formula (III), R ２ , R ３ and X is as defined above.

8. A stabilizer for organic materials comprising the compound of claim 1.

9. The stabilizer of claim 8, wherein the organic material is a thermoplastic resin.

10. The stabilizer according to claim 9, wherein the thermoplastic resin is a polyolefin or an engineering plastic.

11. A method for stabilizing an organic material, which comprises adding the compound according to claim 1 to the organic material.

12. An organic material composition comprising an organic material and the compound of claim 1.

13. The composition of claim 12, wherein the organic material is a thermoplastic resin.

14. The composition of claim 13, wherein the thermoplastic resin is a polyolefin or an engineering plastic.

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