TW201202328A - New compound, and method for synthesizing the same, and antioxidant, resin composition and resin molded form each including the same - Google Patents

Abstract

To provide a new compound having high heat resistance, and to provide an antioxidant, resin composition and resin molded form each including the same. The new compound is represented by formula (1) [wherein, L is H or a specific heterocyclic ring group-containing group; R<SP>3</SP>is a 1-20C monovalent (halogenated) hydrocarbon group; R<SP>4</SP>is a 1-20C bivalent (halogenated) hydrocarbon group; A is a single bond, 1-20C bivalent (halogenated) hydrocarbon group; -S-, -SO<SB>2</SB>-, -CO- or -O-; m is an integer of 0-10; n is an integer of 0-4; and at least one of a plurality of L groups is a heterocyclic ring group-containing compound group containing both oxygen atom and phosphorus atom].

Description

201202328 6. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to an antioxidant for a polymer material such as a synthetic resin, a novel compound of a mold release agent, a method for synthesizing the same, and an antioxidant containing the compound. , a release agent, a resin composition, and a resin molded body. [Prior Art] Polymer materials such as synthetic resins can be used for packaging materials, building materials, automotive parts, daily sundries, agricultural materials, medical instruments, digital camera lenses, and actions due to their excellent mechanical and chemical properties. The telephone lens is used in a wide range of applications such as a CD, a blue read lens, an optical lens typified by a microlens, a substrate such as a compact disc, a light guide plate, and a cymbal. In recent years, in the field of optical parts, a molded body made of a transparent thermoplastic resin has been used in terms of workability and degree of freedom, and in order to impart optical characteristics such as diffusion, condensing, diffraction, and reflection. A fine shape is imparted to the surface of the molded body. These molded bodies having a fine shape are obtained by a method of injection molding, thermal transfer molding by melt processing by a pressing method, or a method of transferring a fine shape formed on a metal surface by a conventional method. The molded article made of the transparent thermoplastic resin is usually used as a substrate, and the molded article may be used as a substrate, and the surface thereof is obtained by applying a method of curing a transparent resin such as ultraviolet curable resin. It is used as a transparent stamper for forming an optical element. -5- 201202328 However, 'polymer materials usually show deterioration due to discoloration caused by exposure to high temperatures during heat processing, and it is easy to lose the original function, but it is not suitable for practical use. Further, after the polymer material is used in various applications, there is a case where deterioration such as discoloration is observed over a period of time. A method of suppressing the deterioration phenomenon such as discoloration is known as a method of adding various antioxidants to a synthetic resin. The antioxidant used therein includes a primary antioxidant such as a phenol-based antioxidant or an amine-based antioxidant, or a secondary antioxidant such as a phosphorus-based antioxidant or a thioether-based antioxidant. Among these compounds, a phenolic antioxidant is known, for example, as a compound shown in Patent Document 1, and a compound represented by Patent Document 2 is known. However, these compounds have insufficient heat resistance and have problems such as decomposition due to exposure to high temperatures during heat processing. Further, when the molded article having the above-described fine shape is formed by injection molding or thermal transfer molding, it is difficult to release the mold from the mold to be used, and the resin may remain in the mold even if the mold is released. Therefore, a method of improving mold release property is known as a method of adding various mold release agents to a synthetic resin. The release agent used therein includes a fluorine-based release agent, a oxime-based release agent, and a fatty acid ester-based release agent. For the release agents, for example, a oxime-based release agent disclosed in Patent Document 3 is known. However, the release agent has insufficient heat resistance and has a problem of being decomposed by exposure to a high temperature at the time of heat treatment. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. 2002-307. Disclosure of the Invention [Problems to be Solved by the Invention] The present invention has been made in view of the above problems. That is, the object of the present invention is to provide a novel compound having high heat resistance and a method for synthesizing the same, and an antioxidant, a releasing agent, a resin composition and a resin molded body containing the compound. [Means for Solving the Problem] The inventors of the present invention actively reviewed the above problems. As a result, it has been found that the above problems can be solved by using a compound having the following structure, and thus the present invention has been completed. That is, the present invention provides the following [1] to [1〇]. Π]—a compound represented by the following formula (1) [Chemical 1]

[Chemical 2]

The base of 201202328, represented by the following formula (3) or R8CO- (R8 is a monovalent hydrocarbon group of 1 to 40 or a halogenated hydrocarbon group of 1 to 40 carbon atoms), and each of R4 is independently a carbon number of 1 to 2. a monovalent hydrocarbon group or a halogenated hydrocarbon group having 1 to 20 carbon atoms, each of which is independently a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent halogenated hydrocarbon group having a carbon number, and A is a single bond and has a carbon number of 1 to 2 0 a divalent halogenated hydrocarbon group having a valence number of 1 to 20, -S-, -S02-, -CO- or -0-, an integer of 〇~10, η is an integer of 0 to 4, but not four full In the case of a hydrogen atom, in the formula (2), R1 is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and each of R2 is independently a monoterpene CO-, and R3 is independently a divalent hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having a carbon number of 1 to 20, a base of a carbon number of 1 to 20, and a carbon m being a monovalent I or · 2 [Chemical 3]

A monovalent price of 1 to 20 201202328 A hydrocarbon group or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and each of R7 is independently a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms. [2] The compound according to [1], wherein, in the above formula (1), L is a group represented by the above formula (2). [3] The compound according to [2], wherein, in the above formula (2), R2 is a single bond. [4] The compound according to [1], wherein in the above formula (1), each L is independently a hydrogen atom or a group represented by the above formula (3), and at least one of the plurality of L is in the above formula (3) ) the basis of the statement. [5] The compound according to [1], wherein, in the above formula (1), L is each independently a hydrogen atom or a group represented by R8CO -, and at least one of the plurality of L is a group represented by R8CO-. [6] An antioxidant according to any one of [2] to [4]. [7] A mold release agent comprising the compound according to [5]. [8] A resin composition comprising the compound according to any one of [1] to [5]. [9] A resin molded body, which comprises the compound according to any one of [1] to [5]. [10] A method for synthesizing a compound represented by the following formula (1), which comprises the compound represented by the following formula (4) and the following formula (5), the following formula (6), and the following formula ( 7) A step of reacting a compound selected from the group consisting of the compounds:

201202328 【化4】

(4) [Chemical 5]

In the formula (4), each of R4 is independently a carbon number iDO, a monovalent halogenated hydrocarbon group having a valence number of 1 to 20, and each of R5 is independently a carbon number of 1 to 20 hydrocarbon groups or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a single bond, a divalent hydrocarbon group of carbon, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, -s_, · CO- or -〇-, m is an integer of 0 to 10, and n is an integer of 〇~4, ΟΗ In (5), each of R1 is independently a hydrogen atom, a carbon number of 丨~20 hydrocarbon group or a carbon number of 1 to 20 one-valent halogenated hydrocarbon group, and each of R3 is independently a divalent hydrocarbon group of carbon or a divalent halogenated hydrocarbon group having a carbon number of 1 to 20. , γ is a group represented by a hydroxyl group or a carboxyl group, but R9 is a hydrocarbon group having a carbon number of 1 to 20 or a divalent number of carbon I to 20 S 0 2 -, _ a valence of 1 to 20 R9S〇3 · Base, -10- 201202328 【化6】

— valence 1~2〇 atom or carbon formula (6), R6 is each independently a hydrogen atom, a hydrocarbon group having a carbon number of 1 to 20 or a carbon number of 1 to 20, a monovalent halogenated hydrocarbon group 'R7 each independently a carbon number a valence hydrocarbon group or a divalent halogenated hydrocarbon group having a carbon number of 1 to 20' X is a halogen [Chemical 7] r81—z (7) 0 In the formula (7), R 8 is independently a carbon number of 1 to 40 and a monovalent hydrocarbon group of 1 to 40 a valence halogenated hydrocarbon group, Z is a hydroxyl group, or a halogen atom, [Chemical 8]

It is indicated that R8 m and η are each unique -11 - 201202328 and R4, R5'A, m and η in the formula (4) are synonymous, but not all of the four L are hydrogen atoms.

ΟΗ In formula (2), R1 and R3 are each independently synonymous with R1 and R3 in formula (5), and R2 is independently a single bond or -CO-, [Chemical 1 0]

In the formula (3), R6 and R7 are each independently synonymous with R6 and R7 in the formula (6). [Effect of the Invention] The novel compound of the present invention has high heat resistance. Therefore, the compound can be used as an antioxidant or a mold release agent for a polymer material such as a synthetic resin, and it is possible to provide a resin composition and a resin molded body which are less likely to cause deterioration such as discoloration and have excellent mold release property. Further, the synthesis method of the present invention can synthesize a novel compound of high purity in a good yield and easily. [Embodiment] Hereinafter, the novel compound of the present invention and a method for producing the same, and an antioxidant, a releasing agent, a resin composition and a resin molded body containing the compound will be described in detail. [Compound] The novel compound of the present invention is a compound represented by the following formula (1). Further, the compound represented by the following formula (1) is also referred to as "compound (1)". [1 1]

In the formula (1), each L is independently a hydrogen atom, a group represented by the following formula (2), a group represented by the following formula (3) or a R8CO- (R8 is a hydrocarbon number of 1 to 40 carbon atoms or a carbon number of 1 to 40% of a halogenated hydrocarbon group), R4 is independently a carbon number of 1 to 20 one-valent hydrocarbon group or a carbon number of 1 to 20 one-valent halogenated hydrocarbon group, and R5 is independently a carbon number of 1 to 20 a divalent hydrocarbon group or a divalent halogenated hydrocarbon group having a carbon number of 1 to 20 201202328, A being a single bond, a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, -S-, -S02- , -CO - or - 0-, m is an integer of 〇~10, and η is an integer of 0 to 4, but not four hydrogen atoms of all horses, [1 2]

式 In the formula (2), each of R1 is independently a hydrogen atom, a hydrazine group having a carbon number of 1 to 2 Å or a valence halogenated hydrocarbon group having a carbon number of 1 to 20, and each of R 2 is independently a single bond or · CO-, and R 3 is independently a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, [Chem. 1 3]

In the formula (3), each of R6 is independently a hydrogen atom, a carbon number of 1 to 2 fluorene, or a carbon number of 1 to 20, and the valence of the hydrocarbon group 'r7 is independently a divalent hydrocarbon group having 1 to 20 carbon atoms or A divalent-hydrocarbon group having 1 to 20 carbon atoms. The ones having a carbon number of from 1 to 20 in the above R1, R4 and R6 are exemplified by methyl, ethyl, propyl, isopropyl, butyl 'isobutyl, tert-butyl, -14-201202328 pentyl. And an alkyl group having a carbon number of 1 to 20 such as a hexyl group; a cycloalkyl group having a number of 3 to 20 such as a cyclopentyl group and a cyclohexyl group; a carbon number of 6 to 2 0 aromatic groups such as a phenyl group, a naphthyl group, and a biphenyl group; Hydrocarbyl group; alkenyl group having 2 to 20 carbon atoms such as a vinyl group and an allyl group. The one-valent halogenated hydrocarbon group having 1 to 20 carbon atoms in the above R1, R4 and R6 is a halogenated alkyl group having 1 to 20 carbon atoms, a halogenated cycloalkyl group having 3 to 20 carbon atoms, and a halogenated aromatic group having 6 to 20 carbon atoms. A hydrocarbon group. The halogenated alkyl group is exemplified by a trichloro group, a trifluoromethyl group, a tribromomethyl group, a pentachloroethyl group, a pentafluoroethyl group, a pentabromo group or the like, and the halogenated cycloalkyl group is exemplified by a chlorocyclopentyl group and a chlorocyclohexyl group. The halogenated aromatic hydrocarbon group is exemplified by a chlorophenyl group and a chloronaphthyl group. The divalent hydrocarbon group having 1 to 20 carbon atoms in the above R3, R5, R7 and fluorene is classified into a divalent linear or branched hydrocarbon group having 1 to 20 carbon atoms, a dialicyclic hydrocarbon group having 3 to 20 carbon atoms, and A divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. The divalent straight-chain or branched hydrocarbon group having 1 to 20 carbon atoms in the above R3, R5, R7 and A is exemplified by methyl, ethyl, trimethyl, tetramethyl, and methyl. Methyl and heptamethyl are the alkyl groups; propylene, propylene, butylene, isobutylene, pentylene, isoamyl and hexylene branched alkylene; alkenyl; Alkynyl and the like. Among these, it is preferred to extend the base. The divalent alicyclic group having 3 to 20 carbon atoms in the above R3, R5, R7 and A is exemplified by a cycloalkyl group such as a cyclopropyl group, a cyclopentene group, a cyclopentyl group and a cyclohexylene group; An alkenyl group, a cyclopentenyl group, a cyclohexene group, and the like. The bonding site of the above alicyclic hydrocarbon group may be any carbon on the alicyclic ring. The above-mentioned R3, R5, R7 and A in the above-mentioned R3, R5, R7 and A have a carbon number of 6 to 2 〇 of the divalent aromatic carbon. The hydrocarbons of the isopropene hydrocarbons are listed as hydrocarbons, such as phenylene, phenylene and naphthyl. The divalent halogenated hydrocarbon having 1 to 20 carbon atoms in the above R3, R5, R7 and A is exemplified by at least one of hydrogen atoms of the divalent hydrocarbon group having the carbon number i-20 exemplified above via a halogen atom (for example, a fluorine atom) , chlorine atom, bromine, iodine atom) substituted. The one-valent hydrocarbon group having 1 to 40 carbon atoms in the above R8 is exemplified by methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, second butyl group, tert-butyl group, pentylhexyl group, heptyl group and octyl group. , anthracenyl, fluorenyl, undecyl, lauryl, myristyl, palmityl, stearyl and other alkyl groups having 1 to 40 carbon atoms; cyclopropylcyclobutyl, cyclopentyl, cyclohexyl, cycloheptane a cycloalkylphenyl group having a carbon number of 3 to 40 such as a cyclooctyl group, a cyclodecyl group, a fluorenyl group, a cyclodecyl group or a cyclododecyl group, a tolyl group, a xylyl group, a naphthyl group or a benzyl group. Aromatic hydrocarbon group having a carbon number of 6 to 40; vinyl 'allyl, 1-propenyl, 1,3-butadienylisopropenyl, 1-butenyl, 2-butenyl, 2- An alkenyl group having a carbon number of 2 to 12 such as a pentenyl group. The one-valent halogenated hydrocarbon group having 1 to 40 carbon atoms in the above R8 is exemplified by a halogenated alkyl group having 1 to 4 carbon atoms, a halogenated cycloalkyl group having 3 to 40 carbon atoms, and a halogenated aromatic hydrocarbon group having 6 to 40 carbon atoms. The above halogenated alkyl groups are exemplified by trichloromethyl, trimethyl, tribromomethyl, pentachloroethyl, pentafluoroethyl, pentabromoethyl, heptapropyl, heptabromyl, nonafluorobutyl and Examples of the bromobutyl group include a chlorocyclopentyl group and a chlorocyclohexyl group, and the halogenated aromatic hydrocarbon group is a chlorophenyl group or a chloronaphthyl group. In the above formula (1), A is preferably an isopropylidene group, an -S-, -S〇2_, -CO- or -Ο-based subunit, a meat &gt; a ring » an aromatic 40-number fluorohalane. Column-16- 201202328 η is preferably 0. Further, the compound (1) is a compound in which all of L is a group represented by the above formula (2) (hereinafter also referred to as "compound (1 _η", heat resistance of the compound, compatibility with the resin, and inhibition of the resin) In the case of the deterioration phenomenon, in the compound (1 -1 ), R1 is preferably each independently a hydrogen atom or a hydrocarbon having 3 to 20 carbon atoms, and at least one R1 bonded to any one of the aromatic rings is preferably. The carbon number of 3 to 20 is bonded to the aromatic ring and the one adjacent to the -0 fluorenyl group or the two R1 groups are more preferably a hydrocarbon having 3 to 20 carbon atoms, and the carbon number is 3 to 20 The one-valent hydrocarbon group is preferably a third butyl group, and R 2 is preferably each independently a single bond, and R 3 is preferably each independently a divalent straight-chain or branched-chain hydrocarbon group having 1 to 20 carbon atoms, more preferably a methyl group. Ethyl or trimethyl, m is preferably 0 or 1, more preferably 0. In the above formula (2), when R2 is a single bond, it has an oxidation preventing effect, a higher heat resistance and a phase with a resin. Further, the compound (1-1) is a compound represented by the following formula (1) (hereinafter also referred to as "compound (1 ')" Composition may be preferably used as the antioxidant. 201202328 [Chemical 14]

In the formula (1'), 'R1 to R5, A, m and η are synonymous with R1 to R5, A, m and η in the above formula (1) or (2). The compound (1) is preferably a compound having a hydrogen atom or a group represented by the above formula (3) from the viewpoints of heat resistance of the compound, compatibility with the resin, and deterioration of the resin. At least one of the plurality of l is represented by the above formula (3) 'hereinafter, also referred to as "compound (1-2)"). More preferably, all four L are represented by the above formula (3). Compound. In the compound (1 - 2 ), R6 is preferably each independently a hydrogen atom or a monovalent hydrocarbon group having 3 to 20 carbon atoms, more preferably at least one R6 bonded to any one of the aromatic rings is a hydrocarbon having 3 to 20 carbon atoms. And preferably bonded to one or both of the ortho and R6 of the carbon atom bonded to the oxygen atom to the oxygen atom, or one of the carbon atoms of 3 to 20, and more preferably a bond The two ortho to R6 of the carbon atom bonded to the oxygen atom bonded to the oxygen atom is a hydrocarbon having a carbon number of 3 to 20, and the carbon number of 3 to 20 is preferably the lowest. It is a third butyl group. R7 is preferably independently a divalent straight or branched chain hydrocarbon group having 1 to 20 carbon atoms, more preferably a methyl group, an ethyl group or a trimethyl group. -18- 201202328 m is preferably 〇 or 1, more preferably i. The compound (1) is preferably a hydrogen atom or a ruthenium in terms of the heat resistance of the compound, the compatibility with the resin, the reproducibility of the resin composition containing the compound, and the resin molded body. ~ indicates the basis (but 'at least one of the plurality of L is a group represented by R8CO-, hereinafter also referred to as "compound 1-3"). More preferably, the four compounds of L are all represented by r8c〇- Further, in the R8 system and the r8 synonym compound (1 - 3) in the above compound (1), R8 is preferably each independently a carbon number of 5 to 40, more preferably one of 10 to 30 carbon atoms. Price base. R5 is preferably each independently a divalent straight or branched chain hydrocarbon group having 1 to 20 carbon atoms, more preferably a methyl group, an ethyl group or a methyl group. m is preferably 0 or 1, more preferably 0. [Synthesis Method of Compound (1)] The compound (1) of the present invention can contain a compound represented by the following formula (4) (hereinafter also referred to as "compound (4)"), and the following formula (5) a compound (hereinafter also referred to as "compound (5)"), a compound represented by the following formula (6) (hereinafter also referred to as "compound (6)"), and a compound represented by the following formula (7) (hereinafter) It is also synthesized by a method of the step of reacting a compound (i) selected from the group consisting of "compound (7)"). By reacting the compound (4) with the compound (i), a novel compound of high purity can be easily synthesized in a good yield (1) -19-201202328 [Chemical Formula 1]

Among them, R4, R5, A, m and η are synonymous. 【化1 6】

R—Υ (5) ΟΗ In the formula (5), R1 and R3 are each independently the same as R1 and R3 in the above formula (2), and Υ is a group represented by R9S03-, a hydroxyl group or a carboxyl group, but R9 is a carbon number. a hydrocarbon group of 1 to 20. The hydrocarbon group having 1 to 20 carbon atoms in the above R9 may be the same as the one having a carbon number of 1 to 20 in the above R1. -20- 201202328 【化1 7】

In the formula (6), R6 and R7 are independently synonymous with R6 and R7 in the above formula (3), and X is a halogen atom. Further, the compound (6) can be synthesized by the method described in Phosphorus and Sulfur, 1984, Vol 19, pp 285-293. R81 —z (7) 0 In the formula (7), R 8 is a one-valent hydrocarbon group having a carbon number of 1 to 40 or a carbon number 丨~cut. One-valent halogenated hydrocarbon group 'Z is a hydroxyl group or a halogen atom. Further, R8 is synonymous with R8 in the above compound (1). The temperature and time of the above reaction are not particularly limited, and the reaction temperature is usually -30 to 120 ° C, preferably -20 to 90 ° C, preferably -10 to 80. (:; The reaction time is usually from 0.1 to 48 hours, preferably from 0.5 to 24 hours, preferably from the hour. "Synthesis method of the compound (1-1)" The method for synthesizing the above compound (1 - 1) is not particularly limited. , but the step of reacting the compound (4) with the compound (5) is better than that of the reaction of the compound (4) and the compound (5), and the molar ratio of the compound (4) to the compound (5) ( The compound (5) / the compound (4)) is usually 4 to 20, preferably 4.05 to 5. When the compound (4) is reacted with the compound (5) in the same amount, it can be synthesized in a higher yield and easily. Novel compound (1-1) of purity. <Synthesis method of compound wherein R2 is -C 0 - in compound (1 -1 )> Compound (1) wherein R2 is -CO- can make compound (4) It is obtained by reacting a compound in which compound Y is a carboxyl group in the compound (5) (hereinafter also referred to as "reaction (I)"). The reaction (I) can be carried out in the presence of a carbodiimide and/or a base catalyst or the like. The carbodiimide may, for example, be dicyclohexylcarbodiimide or diisopropylcarbodiimide. 5) The molar ratio to the carbodiimide (carbodiimide/compound (5)) is usually from 1 to 20, preferably from 1.05 to 5. Further, the base catalyst is Ν, Ν- Dimethylaminopyridine, triethylamine, pyridine, sodium carbonate, etc. The molar ratio of the compound (5) to the base catalyst (base catalyst/compound (5)) is usually 〇.〇1~1, preferably Further, in the above reaction (I), an organic solvent such as dichloromethane, chloroform, carbon tetrachloride or/or 1,2-dichloroethane or water or the like can be used as the solvent. Each compound of lg (5), usually, preferably from 1 to 20 ml, preferably from 2 to 10 ml. • 22-201202328, in the reaction (I), the molar ratio of the compound (Ο to the compound (5), and The temperature and time of the reaction are the same as above. <Synthesis method of a compound in which R2 is a single bond in the compound (1-1)> Further, in the compound (1-1), a compound in which R2 is a single bond can make the compound (4) It is obtained by reacting a compound in which the hydrazine in the compound (5) is a hydroxyl group or a group represented by R9S03- (wherein R9 is a hydrocarbon group having 1 to 20 carbon atoms) (hereinafter also referred to as "reaction (II)"). (II) can be carried out in the presence of a catalyst or the like. The catalyst is exemplified by sodium hydride, etc. The molar ratio of the compound (4) to the catalyst (catalyst/compound (4)) is usually 〇.〇1 ~20, preferably 0.1~10. Also in the reaction (II), N,N-dimethylacetamide, dimethylformamidine, chloroform, carbon tetrachloride and/or 1,2 may also be used. An organic solvent such as dichloroethane or water, or the like is used as a solvent. The solvent is used in an amount of usually 0.1 to 50 ml, preferably 1 to 20 nU, more preferably 2 to 10 ml or less per 1 g of the compound (5). The molar ratio of the compound (4) to the compound (5) in the reaction (II) and the temperature and time of the reaction are the same as described above. <Synthesis method of the compound (Γ)> When the compound (1) is synthesized, the compound represented by the following formula (5 ') may be replaced with the compound (5). -23- 201202328 【化1 9】

In the formula (5,), the 'Ri'R:» and γ are synonymous with R^R3 and γ in the formula (5). <<Synthesis Method of Compound (1-2)>> The method for synthesizing the compound (1-2) is not particularly limited, but preferably comprises reacting the compound (4) with the compound (6) (hereinafter also referred to as "reaction (111) Step). In the reaction (III), the molar ratio of the compound (4) to the compound (6) (the compound (6) / the compound (4)) is usually from 1 to 20, preferably from 4 to 20, more preferably from 4.05 to 6. When the compound (4) is reacted with the compound (6) in the same amount, the high-purity novel compound (1-2) can be synthesized more easily and easily. In the above reaction (III), the reaction temperature and time are the same as described above. Further, the above reaction (ΙΠ) can be carried out in the presence of a base catalyst. The base catalysts are exemplified by hydrazine, hydrazine-dimethylaminopyridine, triethylamine, pyridine, and sodium carbonate. The molar ratio of the compound (6) to the base catalyst (base catalyst/compound (6)) is usually 0.05 to 5, preferably 0.5 to 2. Further, in the above reaction (ΙΠ), an organic solvent such as dichloromethane, chloroform-24-201202328, carbon tetrachloride or/or 1,2-dichloroethane or water or the like can be used as the solvent. The solvent is usually used in an amount of from 0.1 to 50 ml, preferably from 1 to 20 ml', preferably from 2 to 10 ml, per lg of the compound (6). <<Synthesis Method of Compound (1-3)>> The method for synthesizing the compound (1-3) is not particularly limited, but preferably comprises reacting the compound (4) with the compound (7) (hereinafter also referred to as "reaction (IV)" Step). In the reaction (IV), the molar ratio of the compound (4) to the compound (7) (the compound (7) / the compound (4)) is usually from 1 to 20, preferably from 4 to 20, more preferably from 4.05 to 5. When the compound (4) is reacted with the compound (7) in the same amount, the high-purity novel compound (1-3) can be synthesized more easily and easily. In the above reaction (IV), the reaction temperature and time are the same as described above. As the compound (7), for example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, and tetradecanoic acid can be cited. Alkanoic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, tetracosanoic acid, cerotic acid, hexadecane Acid, brown acid (Μ 〇 ntan acid), melisic acid, Lacceric acid, isobutyric acid, isovaleric acid, isobutyric acid, 2-methylbutyric acid, ring Propanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cycloheptanecarboxylic acid, cyclooctanecarboxylic acid, cyclopropylacetic acid, cyclobutylacetic acid, cyclopentyl acetic acid, ring Hexyl acetic acid, cycloheptyl acetic acid, cyclooctyl acetic acid, raw borneol carboxylic acid-25-201202328, di-norbornanecarboxylic acid, norbornaneacetic acid, di-n-methylcyclohexanecarboxylic acid, 4-ethylcyclo Hexanecarboxylic acid, 4-, 4-butylcyclohexanecarboxylic acid, 4-propylcyclohexanecarboxylic acid alkanecarboxylic acid, 4-ethyldicyclohexanecarboxylic acid, 4-propyldibutyl Cyclohexanecarboxylic acid, 4-propyl dicyclohexyl Carboxy cholestranoic acid), trifluoroacetic acid, pentafluorocarbon (propionate, hexafluoropentanoic acid, and halides of such acids, etc.) The reaction (IV) can be carried out in carbodiimide and/or carbodiimide. It is exemplified by dicyclohexylcarbodicarbodiimide, etc. The molar ratio of the compound (7) to the carbodiimide (7)) is usually from 1 to 20, preferably from 1.05 to 5, in addition to the base. The catalyst is exemplified by N,N-dimethylamine, pyridine, sodium carbonate and the like. The molar ratio (base) of the compound (7) to the base catalyst is usually 0.01 to 1, preferably 0.03 to 0.5» and the above reaction can also be carried out using dichloromethane 'chlorine/ or 1,2-dichlorohexyl An organic solvent such as an alkane or water or the like is used in an amount of usually 1 to 20 ml, preferably 2 to 15 ml, per 1 g of the compound (7). <<Synthesis method of compound (4)>> The above compound (4) can be obtained by a conventional method as a production method comprising the steps of the following steps: a flavonoid acetic acid, a tetrapropylcyclohexanecarboxylic acid, a 4-methyl group Cyclohexylcyclohexanecarboxylic acid, 4-acid, cholesterol acid (acid, heptafluorobutyric acid, alkali catalyst in the presence of quinone imine and diisopropyl (carbodiimide / decyl pyridine, triethylamine) Catalyst/compound (7 imitation, carbon tetrachloride, and solvent. The solvent is 1 to 50 ml). Preferably, the method is as follows: hydrogenation of the compound represented by the following formula (8) Table-26-201202328 is obtained by the following formula (9) The step (i) of the compound (in the form of τ, also referred to as the compound (9)), the compound (9) is oxidized to obtain a compound represented by the following formula (1 〇) (hereinafter also referred to as a compound (1 〇)) Step (π) 'Step (iii) of reacting the compound (1 〇) with a compound represented by the following formula (丨) (hereinafter also referred to as the compound (11)), and obtaining the step (ii) a compound (hereinafter also referred to as compound (11')) and a carbonate diester or by the following formula (12) The step (iv) of the reaction of the compound (hereinafter also referred to as the compound (I2)). Further, when the compound of the compound (4) wherein m is 0, the above step (iv) is not required. [Chemical 2 0] ho_hO~a ^O^oh (8) (In equation (8), 'A is synonymous with A in equation (1)). (Chemical 2 1) ηο^3_α_{Ζ)_οη (9) (in equation (9) 'Α系与式( 1) Zhongzhiyi is synonymous.) [Chem. 2 2] (1〇) (In the formula (10), 'Α is synonymous with α in the formula (1)) -27. (11) 201202328 [Chem. 2 3] ( R4)n

(In the formula (1 1 ), R4 and η are synonymous with R4 and n in the formula (1)) Further, in the compound (1 1 ), the compound in which R4 is bonded to the para position of the phenol is less preferable. [Chem. 2 4]

(In the formula (1 2 ), R5 and m are synonymous with R5 and m in the formula (1), and X' is a halogen atom). The above conventional method can be used in the above step (i). The above step (ii) can be carried out by a conventional method, for example, by reacting the above compound (9) in the presence of an oxidizing agent and a solvent. Examples of the oxidizing agent include a hypohalous acid such as hypochlorous acid and hypobromous acid, a salt thereof, and a halogen such as chlorine. The molar ratio of the compound (9) to the oxidizing agent (oxidizing agent/compound (9)) is preferably from 2 to 3, more preferably from 2.1 to 2.3.

-28- 201202328 The solvent is usually used in an amount of 0.1 to 50 ml per compound (9). Further, the conditions of the step (Π) are not particularly limited, but the reaction temperature is usually from 0 ° C to the temperature below the boiling point of the solvent. Preferably, it is 1 〇~40 °c; the reaction time is usually 0.1 to 10 hours. The above step (iii) can be produced by a conventional method. For example, it is preferred to react the above compound (1?) with the above compound (11) in the presence of an acid catalyst. The molar ratio of the compound (1 〇 ) to the compound (11) (the compound (1 1 ) / the compound (10 )) is usually 4 to 50, preferably 4 to 10. Examples of the acid catalyst include inorganic acids such as hydrogen chloride gas, hydrochloric acid 'sulfuric acid and phosphoric acid, and organic acids such as p-toluenesulfonic acid, oxalic acid and methanesulfonic acid. The weight ratio of the compound (1 〇 ) to the acid catalyst (acid catalyst/compound (10)) is preferably from 0.05 to 1, more preferably from 0.3 to 0.7. Further, in the step (iii), a suitable auxiliary catalyst such as methyl mercaptan, ethyl mercaptan, dodecyl mercaptan and/or octyl mercaptan may be added together with the above acid catalyst. Alcohols and the like to promote the reaction. The weight ratio of the compound (10) to the auxiliary catalyst (auxiliary catalyst/compound (10)) is preferably from 0.01 to 0.1, more preferably from 0.02 to 0.06. In the step (iii), a solvent may be used as needed. For example, an aromatic compound such as benzene, toluene or xylene, a saturated hydrocarbon such as n-hexane, cyclohexane or n-pentane, methanol or tert-butanol may be used singly or in combination. Alcohols, etc. The weight ratio of the compound (1 1 ) to the solvent (solvent/compound (1 i )) is preferably from 0.01 to 10, more preferably from 0.1 to 2. -29-201202328 In addition, the conditions of the step (iii) are not particularly limited, but the reaction temperature is usually from 0 ° C to 60 ° C, preferably from 1 Torr to 40 ° C; and the reaction time is usually from 1 to 10 hours. Preferably, it is 1 to 5 hours. The above step (iv) can be produced by a conventional method, for example, by subjecting the compound (11') (the compound of m = 0 in the above compound (4)) to a carbonic acid diester or the above compound in the presence of a base catalyst (〗 2) The reaction can be. The molar ratio of the compound (1Γ) to the alkylene carbonate (the alkylene carbonate/compound (11,)) is usually 4 to 20, preferably 4 to 10, and the compound (1 1 ') and the compound (1 2) The molar ratio (compound (1 2 ) / compound (1 1 ')) is usually 4 to 20, preferably 4 to 10. Among them, examples of the alkylene carbonate include, for example, ethylene carbonate, propylene carbonate, and butylene carbonate. The base catalyst may, for example, be a carbonate such as potassium carbonate or sodium carbonate, a tetra-ammonium salt such as tetrabutylammonium bromide, tetrabutylammonium chloride, tetramethylammonium bromide or tetramethylammonium chloride. The weight ratio of the compound (11') to the base catalyst (base catalyst/compound (11')) is preferably 〇.〇1 to 1, more preferably 〇·〇5 to 0.5. In the step (iv), a solvent may be further used as needed. For example, a polar aprotic solvent such as N,N-dimethylformamide, acetonitrile or/or dimethylhydrazine may be used singly or in combination. The weight ratio of the compound (1 1 ') to the solvent (solvent/compound (1 1 ')) is preferably from 0.01 to 10, more preferably from 0.1 to 2. In addition, the condition of the step (iv) is not particularly limited, but the reaction temperature is -30-201202328 degrees, usually 〇°C~200°c', preferably 30-160°C; the reaction time is 1~10 hours, It is preferably from 1 to 5 hours. <Method of Compound (5) wherein Y is a group represented by R9S〇3_> In the compound (5), Y is a group represented by r9S〇3_, and R9 is a carbon number of 1 to 20. The compound of the hydrocarbon group can be obtained by reacting a compound in which γ is a hydroxyl group in the compound 5) with a compound represented by the following formula (13) (hereinafter also referred to as "the compound (13)") (hereinafter also referred to as "reaction (V)". ). [Chemical Formula 2 5] R9S02X (13) In the formula (13), R9 is a hydrocarbon group having a carbon number of 1 to 20' X is a halogen. The hydrocarbon group having 1 to 20 carbon atoms in R9 may be the same as the one having a hydrocarbon group of 1 to 20 in the above R1. In the above reaction (V), 'compound (5) and compound (1 3 molar ratio (compound (1 3 ) / compound (5)) are usually 2 to 5, and the reaction (V) can be used in the alkali catalyst. In the presence of a base catalyst N, N-dimethylaminopyridine, triethylamine, pyridine, sodium carbonate, etc. The molar ratio of (13) to the base catalyst (base catalyst / compound (13) ) is 〇.〇1~1〇, preferably 〇”~5. Also, in reaction (V), N,N-dimethylacetamide-31 can also be used for synthesis (the The substance is called the atomic carbon number), and the compound is usually used as a solvent, such as methyl chloride, chloroform, carbon tetrachloride, and/or 1,2-dichloroethane or water. The amount of solvent used is 丨g. The compounding ί is 〇_1~50ml' is preferably 1~20ml, preferably 2~10ml. The condition of the above reaction (V) is not particularly limited, but is usually -3 0° (:~120. 〇:, compared Preferably, it is -20 to 90. (:, preferably -1 should be usually 0.1 to 48 hours, preferably 0.5 to 24 hours and 1 to 10 hours. [Antioxidant] The antioxidant of the present invention contains the above compound. (1 is preferably only from the above compounds 1) The composition further preferably contains 1-1) or the compound (1-2). The above compound (1 _ 1 ) and the compound (1 - 2 ) are excellent in compatibility with a resin, etc., and can be preferably used as a shape. Prevention of resin or resin molded body exposed to high temperature [Release agent] The release agent of the present invention contains the above compound (1), which is essentially composed only of the above compound (1), more preferably 1-3) The above compound (1-3) is excellent in heat resistance and resin, and can be preferably used as a release agent for a resin or a resin molded body which is to be processed or formed. Such an organic solvent (5) usually has a hydrazine reaction. The temperature is 0~80〇C; when it is reversed, it is best to be), the compound (heat resistance and processing or oxidizing agent. It is better, there are compounds (the compatibility is exposed to high temperature -32- 201202328 [Resin composition] The resin composition of the present invention contains the above compound (1). The resin composition of the present invention preferably contains a resin and the above compound (1). The resin may be a cyclic olefin polymer or an acrylic resin. (PMMA), polycarbonate resin PC), polyarylate (par), poly selenide resin (PSF), polyether maple resin (PES), polyparaphenylene resin (PPP), poly(arylene ether oxide phosphine oxide resin (PEOP), polyimine resin (PPI), a polyether phthalimide resin (PEI), a polyamidimide resin (PAI), etc. Among these resins, it is preferred from the viewpoint of compatibility with the above compound (1) and the like. A cyclic olefin polymer is used. Further, in the resin composition, the compound (1) is preferably added in an amount of 0.05 to 20 parts by mass, more preferably 0.1 to 1 part by mass, per 100 parts by mass of the resin. [Resin Molded Body] The resin molded body of the present invention contains the above compound (1). The resin molded body of the present invention is preferably one in which the above resin composition is molded. The resin molded body is not particularly limited, and specific examples thereof include packaging materials, building materials, and automotive parts, 'daily miscellaneous goods, agricultural materials, medical instruments, digital camera lenses, mobile phone lenses, and CDs. The above-mentioned compound (1 -1 ) and compound (1 -2 ) are particularly heat-resistant, and the resin used for a wide range of applications such as a blue lens, an optical lens represented by a microlens, a substrate such as a compact disc, a light guide plate, and a ruthenium sheet. -33-201202328 Excellent compatibility with resins. The resin composition containing the compound (1 - η and (1 - 2) and the resin molded body are excellent in storage stability, and in particular, even when exposed to a high temperature, deterioration of discoloration or the like is hard to occur. The above compound (1 - 3) The resin composition and the resin molded article containing the compound (1-3) are excellent in mold release property, and are excellent in process formability particularly when exposed to high temperatures. [Examples] The present invention is not limited to the following examples. (Synthesis Example 1) A 1-liter three-necked flask equipped with a dropping funnel and a thermometer is weighed and expressed by the following formula (3-Α). 3-(3',5,-di-t-butyl- 4,-hydroxy-phenyl)-propyl alcohol 〇 〇 5.8 g (〇. 4 mol), 500 ml of dichloromethane was added and dissolved under a nitrogen atmosphere. The flask was cooled in an ice bath. 121 g of triethylamine (1.2 m〇i) was added to the solution, and then the temperature of the solution was maintained below 5 ° C. 'Methanesulfonate was added dropwise over 90 minutes through a dropping funnel. Chlorine 105.4g (0.92mol). Then, remove the ice bath, then heat up to 2 (TC, stir at 20 ° C After 1 hour, ice water was added to the reaction solution, and the dichloromethane layer was separated by a liquid separation operation. The dichloromethane layer was washed with 200 ml of distilled water. The mixture was dried over magnesium sulfate, filtered, and the solvent was evaporated. , obtaining 1 3 7g of crude product (methanesulfonate) ^ -34- 201202328 I 2 6]

A sodium hydride solution of 3.84 g (1 60 mmol) purified from a suspension of sodium hydride mineral oil was weighed into a 1-liter three-necked flask equipped with a dropping funnel and a thermometer. 100 ml of hydrazine, hydrazine-dimethylacetamide was added thereto under a nitrogen atmosphere to prepare a suspension, followed by cooling in an ice bath. Next, 4,4',4",4"'-[(1-methylethylidene)di-4-cyclohexan-1-ylidene-indolylphenol represented by the following formula (2_A) was 18.5 g ( 32 mmol) was dissolved in hydrazine, hydrazine-dimethylacetamide 100 ml, and added dropwise to the suspension over 30 minutes. The solution was stirred under ice cooling for 30 minutes, and then 54.8 g (160 mmol) of the above-mentioned synthesized methanesulfonate was dissolved in N,N-dimethylacetamide 200 ml in 30 minutes. The solution was added dropwise to the solution. After 30 minutes, the solution was allowed to warm to room temperature, and after 30 minutes, it was warmed to 7 (TC. After 5 hours, the reaction solution was cooled to room temperature, and ammonium chloride was poured into the reaction mixture to terminate the reaction. After extracting the reaction solution three times with ethyl acetate (3 ml), the organic layer was collected, washed with distilled water, and evaporated to give a crude product. The crude product was purified by silica gel column chromatography to ethyl acetate. The hexane was dissolved to obtain a white solid (35. lg.), and the white solid was recrystallized from a mixture of diethyl ether and hexane to obtain 30.3 g (yield: 61%) of the following formula (1-A). ) indicates the target. -35- 201202328 [Chem. 2 7]

[化2 8]

1H-NMR measurement of the compound (AVANCE500 type manufactured by Bruker Co., Ltd.), MS analysis (ACQUITY UPLC &amp; reg system manufactured by Japan WATERS Co., Ltd., and SYNAPT HDMS (High Definition Mass Spectrometry) system) and utilization of TG-DTA The analysis (manufactured by Rigaku Electric Co., Ltd., TG8120) confirmed that the objective compound was obtained. The analysis results are as follows: ° j-NMR (solvent: CDC13) chemical shift σ: 7.23 ppm (aromatic ring hydrogen, 4H), 7-30 ppm (aromatic ring hydrogen, 4H), 6.99 ppm (aromatic ring hydrogen, 4H), 6.96 ppm (aromatic ring) Hydrogen, 4H), 6.83ppm (aromatic ring hydrogen, 4H), 6.72ppm (aromatic ring hydrogen, 4H), 5.〇lppm. (phenolic hydroxyl group, 4H), 3.95ppm (aromatic ring - 0-CH_2-, 4H ), 3.89ppm (aromatic ring-Ο-CHjz-, 4H), 2.73ppm~2.65ppm (12H), 2.03ppm (aromatic ring-CH2-Cii2-CH2-,8H), 1.84ppm (cyclohexane cyclic hydrogen) , 4H), 1.58ppm~].21ppm(14H), 1.41ppm(-36-201202328 third butyl, 72H), 0.52ppm (methyl, 6H). LC-MS: [M + + Na] = 1 5 8 5 1 1 5 0 (calculated 値1 1 8 5 1 1 06 ), [M + + K] = 1 60 1 1 073 (calculated 値1 60 1 0846 )

TG-DTA: melting point = 170 ° C (Synthesis Example 2) 4,4',4",4"'-[(1-methylethylidene)--4 represented by the above formula (2-A) -cyclohex-1-ylidene] 25.9 g (45 mmol), and 3-(3,5'-di-tert-butyl-4'-hydroxy-phenyl group represented by the following formula (3-B) - Propionic acid 56.2 g (202.5 mm 〇l) was weighed into a 2-liter three-necked flask, dissolved in a chlorinated plant at 800 m 1 , and cooled in an ice bath. After cooling, 44.5 g (216 mmol) of dicyclohexylcarbodiimide and 2.7 g (25 mmol) of N,N-dimethylaminopyridine were added to the solution under a nitrogen atmosphere and stirred. After 3 minutes, the reaction solution was allowed to warm to room temperature, and stirred at room temperature at 25 ° C for 4 hours. After 4 hours, the solvent-insoluble matter precipitated in the reaction liquid was removed by suction filtration to collect the solvent-soluble fraction and distilled under reduced pressure. When the residual solution became about 500 ml in total, the residual solution was transferred to a separatory funnel, washed with 100 ml of dilute hydrochloric acid, and then washed with a saturated aqueous solution of sodium hydrogencarbonate (i?0mi) with distilled water of 100 ml. After washing twice, it was dried over magnesium sulfate. The dried solution was dried under reduced pressure to give a crude product of a white solid. This white solid was recrystallized with n-hexane to obtain 5 2 · 6 g (yield 72%) of the object represented by the following formula (1 - B). -37- 201202328 【化2 9】

(3-B)

[Chemical 3 Ο I

1H_NMR measurement of the compound (AVANCE500 type manufactured by Bruker Co., Ltd.), MS analysis (ACQUITY UPLC &amp; reg system manufactured by Sakamoto WATERS Co., Ltd., and SYNAPT HDMS (High Definition Mass Spectrometry) system) and analysis using TG_DTA (science) Electric Co., Ltd. manufactures TG8120) and confirms that the target compound is obtained. The analysis results are as follows. H-NMR (solvent: CDC13) chemical shift σ: 7_32ppm (aromatic ring gas, 4H), 7.12ppm (fragrance ring nitrogen, 4H), 7.04ppm (aromatic ring hydrogen, 4H), 7.02ppm (aromatic ring hydrogen, 4H), 6.99ppm (aromatic ring gas, 4H), 6.85ppm (aromatic ring hydrogen, 4H.), 5.08ppm (hydrazine hydroxyl group, 4H), 2.97ppm (aromatic ring-〇CO-CH_2-, 4H), 2.82ppm (fragrance Ring-OCO-Cii_2-, 4H), 2.66ppm (cyclohexyl ring hydrogen, 2H), 1.90ppm~1.21ppm (16H), 1.43ppm (third-38-201202328 butyl, 72H), 0,51ppm (methyl, 6H). LC-MS: [M + + Na] = 1641 0172 (calculation 値 1641 0277), [M + + K] = 1657 0240 (calculation 値 1657 0016)

TG-DTA: melting point = 1 8 1 ° C (Synthesis Example 3) 4,4',4,',4,''-[(1-methylethylene) represented by the above formula (2-A) ) a cyclohex-1-ylidene] 肆酣i〇〇g (i73mmol), ethylene carbonate 122g (1384mmol), tetrabutylammonium bromide ii.ig (35mmol) and N,N-dimethylformamide 100ml was added to the 500mm 1 three-necked flask with the serpentine condenser and thermometer installed! 5 加热 Heat and stir for 4 hours. The reaction solution was cooled, N,N-dimethylformamide was distilled off under reduced pressure, and then chloroform (500 m) was added and transferred to a separating funnel. The organic layer was separated by adding 100 ml of a 5% potassium hydroxide aqueous solution thereto. Further, 100 ml of a 5% potassium hydroxide aqueous solution was added to the organic layer, and the organic layer was separated. Subsequently, the solution was washed twice with 100 ml of distilled water. The thus obtained chloroform solution was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to give crude crystals. The crude crystals were recrystallized from ethyl acetate to obtain 11.1 g (yield 85 %) of the compound represented by the following formula (2 - B). [化3 1]

(2-B) -39-201202328 This compound was measured by 1H-NMR (AVANCE 500 model manufactured by Bruker Co., Ltd.), and it was confirmed that the objective compound was obtained. The results of the analysis are as follows: 】 H-NMR (solvent: CDC13) Chemical shift σ: 7.25ppm (aromatic ring hydrogen, 4H), 7.05ppm (aromatic ring argon, 4H), 6.86ppm (aromatic ring gas, 4H), 6.75ppm ( Aromatic ring argon, 4H), 4.07ppm (aromatic ring-Ο · C Hjz -, 4 Η ), 4.0 1 ppm (aromatic ring-Ο - C H_2 -, 4 Η ), 3.95ppm (aromatic ring -O-CH2- CiL2-0H, 4H), 3.90ppm (aromatic ring - 0-CH2-Cii2-0H, 4H), 2.63 ppm (cyclohexane cyclic hydrogen, 4H), 1.99ppm (hydroxyl hydrogen, 2H), 1.94ppm (hydroxyl Hydrogen, 2H), 1.84ppm (cyclohexane cyclic hydrogen, 4H), 1.60 ppm (cyclohexane cyclic hydrogen, 4H), 1.38ppm (cyclohexane cyclic hydrogen, 2H), 1.20 Ppm (cyclohexane cyclic hydrogen, 4H), 0.52 ppm (methyl, 6H). 3.07 g (4.09 mmol) of the compound represented by the above formula (2-B) synthesized in the above step, and 3-(3',5,-di-t-butyl-4 represented by the above formula (3-B). 5.0 g (18.0 mmol) of '-hydroxy-phenyl)-propionic acid was weighed into a 100 ml three-necked flask, and dissolved in 40 ml of dichloromethane. 4.05 g (19.6 mmol) of dicyclohexylcarbodiimide and 0.25 g (2.0 mmol) of N,N-dimethylaminopyridine were added to the solution under a nitrogen atmosphere and stirred. After stirring for 4 hours, the solvent which was precipitated in the reaction liquid was removed by suction filtration, and the solvent-soluble fraction was collected and distilled under reduced pressure. The residue solution was dissolved in 100 ml of dichloromethane, transferred to a separatory funnel, and washed with 20 ml of 10% diluted hydrochloric acid, and then washed with 20 ml of a saturated aqueous solution of sodium hydrogencarbonate, and then washed twice with 20 ml of distilled water. , dried over magnesium sulfate. The solution after drying and drying -40 - 201202328 was distilled off under reduced pressure to give a crude product as a white solid. The white solid was purified by silica gel column chromatography eluting with ethyl acetate: n-hexane to obtain the title compound (yield: 58%).

The compound was subjected to 1H-NMR measurement (AVANCE model 5.00 manufactured by Bruker Co., Ltd.), and analyzed by TG-DTA (TG8 120 manufactured by Rigaku Denki Co., Ltd.) to confirm the desired compound. The analysis results are as follows. W-NMR (solvent: CDC13) chemical shift σ: 7.2 5 ppm (aromatic ring hydrogen, 4H), 7.05ppm (aromatic ring hydrogen, 4H), 6.98ppm (aromatic ring hydrogen, 8H), 6.84ppm (aromatic ring hydrogen, 4H), 6.73ppm (aromatic ring hydrogen, 4H), 5.05ppm (酣H, 4H), 4.43ppm (aromatic ring-0-CH2-CH_2-0C = 0,4H), 4.3 8ppm (aromatic ring-O -CH2· C|^2-0C = Ο ), 4.14ppm (square ring-0-CJJ_2-, 4Η), 4.08ppm (aromatic ring-〇-CiL2-, 4H), 2.87ppm (aromatic ring-CH2-CH? - C = 0,4H), 2.63ppm (aromatic ring-Cg_2-CH2-C = 〇, cyclohexane cyclic hydrogen, 12H), 1.84 ppm (cyclohexane cyclic hydrogen, 4H), l_60ppm Cyclic hydrogen, 4H), 1.38~1.20 ppm (t-butyl, cyclohexyl-41 - 201202328 alkane-ring hydrogen, 78H), 0.52 ppm (methyl, 6H). (Synthesis Example 4) 4,4',4'',4'''-[(1-methylethylidene)di-4-cyclohexan-1-ene represented by the above formula (2-A) 5.0 g of indole phenol (8.67 mmol), 5.27 g of potassium carbonate (2.2 mmol) and 75 ml of dimethyl decyl decylamine were added to a 500-neck three-necked flask equipped with a serpentine condenser tube and a thermometer at 140 ° C. The mixture was stirred under heating for 1 hour. Next, the reaction liquid was allowed to stand to cool to room temperature, and then 5.58 g (69.35 mm 〇l) of 2-chloroethanol and 0.28 g (0.87 mmol) of tetrabutylammonium bromide were added, and the mixture was stirred under heating at 140 ° C for 2 hours. Subsequently, the reaction vessel was cooled to room temperature, 1 ml of distilled water was added, and then the organic layer was extracted with 100 ml of ethyl acetate. After repeating the extraction twice, the organic layer obtained at this point was collected, and the washing operation was carried out twice with distilled water. After distilling off the organic layer under reduced pressure, a crude product of title compound was obtained. The crude product obtained here was purified by silica gel column chromatography eluting with ethyl acetate-hexane to afford 5.67 g (yield: 87%) of the compound of formula (2-B). The compound was subjected to 1H-NMR measurement (AVANCE 00 type manufactured by Bruker Co., Ltd.), and it was confirmed that the objective compound was obtained. The analysis results are as follows. H-NMR (solvent: CDC13) chemical shift σ: 7_26pj3m (aromatic ring hydrogen, 4H), 7.05ppm (aromatic ring hydrogen, 4H), 6.86ppm (aromatic ring hydrogen, 4H), 6_75ppm (aromatic ring gas, 4H), 4.07ppm (aromatic ring-OCHj!-CH2-OH, 4H), 4.01ppm (aromatic ring-OCH2-CH2--42-201202328 OH, 4H), 3.95ppm (aromatic ring-〇CH2-CiL2-OH, 4H) 3.90ppm (aromatic ring-〇CH2-CiL2-〇H, 4H), 2.63ppm (hydrogen on cyclohexane ring, 4H), 1.98ppm (aromatic ring-OCH2_-CH2-〇iL 4H), 1.84ppm (ring Hydrogen on the hexane ring, 4H), 1.59 ppm (hydrogen on the cyclohexane ring, 4H), 1.38 ppm (hydrogen on the cyclohexyl ring, 2H), 1.20 ppm (hydrogen on the cyclohexane ring, 4H), 0.52 ppm (methyl, 6H). 1.85 g (2.458 mmol) of the compound represented by the above formula (2-B) synthesized in the above step was weighed into a 100 ml three-necked flask equipped with a dropping funnel and a thermometer, and dissolved in 15 ml of dichloromethane under a nitrogen atmosphere to dissolve Ice cooling. To the solution was added 1.49 g (14.7 mmol) of triethylamine. Next, 2,4,8,10·tetra-tert-butyl-6-chloro-12H-dibenzo[(1,§][1,3,2]dioxa squalane (£1)丨〇\3卩11〇5卩11〇£^11)5.77§ (11.8mmol) After dissolving in 40ml of dichloromethane, the dropping funnel was opened and added dropwise to the reaction solution for 1 hour. After 0 minutes, the ice container was removed from the reaction vessel, and stirred at room temperature for 23 hours at 23 ° C. Then, the reaction vessel was transferred to a separatory funnel, 100 ml of distilled water was added, and the organic layer was extracted with chloroform (1 ml). After repeating the extraction operation three times, the organic layer was collected, and the organic layer was washed with distilled water, and then the organic layer was dried over magnesium sulfate and evaporated under reduced pressure to obtain crude crystals of the desired product. The crude crystals were determined by W-NMR (Bruker) Co., Ltd. manufactures AVANCE500 type), GPC analysis (manufactured by TOSHO Co., Ltd., HLC-8 020). After confirming the structure, it is confirmed that the above compound (丨-D) is represented by the above formula (2-B). 1~3 of the base of the compound and 2,4,8,10-tetrabutyl-3-butyl-6-chloro-1211-dibenzo[〇14][1,3,2]di-43-201202328 Oxygen The compound obtained by the reaction of the phosphorus heterocyclooctane was subjected to a recrystallization operation of the crude crystals in isopropyl alcohol three times to obtain a white crystal of the target compound represented by the following formula (1-D): 4.59 g (yield: 73%). The 1H-NMR measurement of this compound (AVANCE500 model manufactured by Bruker Co., Ltd.) and the analysis of 31 P-NMR measurement (AVAN CE 5 00 manufactured by Bruker Co., Ltd.) confirmed that the objective compound was obtained. The analysis results are as follows. j-NMR (solvent) : CDC13) Chemical shift σ: 7.30ppm (aromatic ring hydrogen, 8H), 7.26ppm (aromatic ring hydrogen, 12H), 7.08ppm (aromatic ring, 4H), 6.92ppm (aromatic ring hydrogen, 4H), 6.81ppm ( Aromatic ring hydrogen, 4H), 4.78??!11 (aromatic ring-0 (^2-(: over ^-0?, 4H), 4.72ppm (aromatic ring-OCHz-CiirOP, 4H), 4.35ppm (aromatic ring) - OCii2-CH2-OP and Ph-C Ph, 8H), 4.29ppm (aromatic ring-OCU^-CHyOP, 4H), 3.44ppm (Ph-CH^-Ph, 4H), 2.66ppm (hydrogen on cyclohexane) , 4H), 1.8 7ppm (hydrogen on cyclohexane ring, 4H), 1.60ppm (hydrogen on cyclohexane ring, 4H), 1.45ppm~1.14ppm (t-butyl, 144H, hydrogen on the cyclohexyl ring, 6H), 0.52ppm ( Yl, 6H). 3IP-NMR (solvent: CDC13) chemical shift σ : 1 30_22 ppm, 13 0.10 ppm (phosphite, CH 2-0-P (aromatic) 2). -44 - 201202328 【化3 3】

(Evaluation Example 1) Antioxidation effect 10% (wt/wt) toluene solution lkg of ARTON resin (ARTON R5 3 00, manufactured by JSR Co., Ltd.) was prepared, and then 〇.3 g (0.3% relative to ARTON resin) was added, respectively. The compound synthesized in the above Synthesis Example 1, 2 or 4 or the commercially available representative phenol-based antioxidant IrganoxlOlO (manufactured by Nippon Ciba Specialty Chemical Co., Ltd.) was dissolved. After filtering with a PTFE filter, the toluene solution was distilled off under reduced pressure, and solidified by concentration. The solid matter was heated at 330 ° C for 3 hours in an argon atmosphere, and then dissolved in toluene to adjust to a 10% (w/w) toluene solution, and then the yellowness was measured. The results are shown in Table 1. [Table 1] Yellowness ARTON + Synthesis Example Compound 0.3 ARTON + Synthesis Example 2 Compound 0.3 ARTON + Synthesis Example 4 Compound 0.3 ARTON + Irganox 1 0 1 0 0.3 (Evaluation Example 2) Thermal Analysis (TG-DTA) -45-201202328 For the synthesis of the compound IrganoxlOlO synthesized in the above Synthesis Examples 1 to 4 (Irgafosl68 manufactured by Japan Cibajiaji Co., Ltd. (Sumitomo Chemical Co., Ltd. manufactured by Japan Ciba Jiaji Co., Ltd.), using DTA (Technology Electric Co., Ltd. manufactures TG8120) Measured the weight reduction rate at 300 ° C for 1 hour. Measurement conditions: nitrogen atmosphere, temperature rise to 300 ° C at 40 ° C / min, hold at 300 t for 1 hour, calculate its The weight reduction rate is shown in Table 2. [Table 2] Weight reduction rate Compound of Synthesis Example 1 3.7% Compound 1 of Synthesis Example 2 3 . 1 % Compound of Synthesis Example 3 5. 1 % Compound of Synthesis Example 3 3.3 % IrganoxlOlO 1 6.1 % Irgafos168 8 3.0 % Sumilizer GP 9 9.5 % Regarding the compounds synthesized in the above Synthesis Examples 1 to 4, the weight reduction is smaller than that of IrganoxlOlO, Irgafosl68, and Sumilizer GP, and Synthetic Example 1 and The weight reduction rate of the compound synthesized in Example 4 (Evaluation Example 3) Preservation stability and II TG-determination, and the results of the results are all in particular -46-201202328 Mixed ARTON resin (aRTON R5300, manufactured by JSR Co., Ltd.) 9. 9g and the compound 〇.lg synthesized in the above Synthesis Example 1, the mixture was dissolved in 9 g of dichloromethane to prepare a solution having a solid concentration of 1% by weight. The solution was applied to a culture dish and dried. Thereafter, the film was allowed to stand overnight to form a film. Subsequently, the obtained film was peeled off from the Petri dish, and dried in a vacuum dryer at 100 ° C for 24 hours. The obtained film was chopped and placed in a test tube. The tank was heated at 3 001 for 18 hours. 3 〇mg of the film before and after heating was dissolved in 5 ml of tetrahydrofuran (Thf), and the solution was used for GPC measurement. The peak area (polymer portion) of the RI detection region was determined. The area before and after self-heating was calculated according to the following formula: The composition of the compound synthesized in Synthesis Example 1 was replaced with IrganoxlOlO (manufactured by Nippon Ciba Specialty Chemical Co., Ltd.), and the gel fraction was also measured. It is not shown in Table 3. Gel fraction (%) = (1 - Peak area of RI detection area of heated resin / Peak area of RI detection area of resin before and after heating) X1 〇〇

Compound name Gel fraction Synthesis Example 1 0% IrganoxlOlO 2 5% (Synthesis Example 5) 4,4',4",4"'-[(1-methyl ia) represented by the above formula (2-A) Ethyl)--4-cyclohex-1-ylidene] decanoic acid 〇g ( 17.3 mmol), stearic acid-47-201202328 acid 20.2 g (70.9 mmol) was weighed into a 500 ml three-necked flask, adding two Methyl chloride 200 ml dissolved. After cooling the solution in an ice bath, 15.7 g (76.1 mmol) of monocyclohexylcarbenium imine and N,N-dimethylaminopyridinium.42 g (3.5 mmol) were added to the solution under a nitrogen atmosphere. Stir. After 30 minutes, the reaction solution was allowed to warm to room temperature, and stirred at room temperature at 25 ° C for 4 hours. The solvent-insoluble matter in the reaction liquid was removed by suction filtration, and the solvent-soluble fraction was collected and distilled off under reduced pressure. When the organic portion is about 100 ml in total, the residual solution is transferred to a separatory funnel, washed with 10% diluted hydrochloric acid 50 m 1 , and then washed with saturated aqueous sodium carbonate solution 50 m 1 to distilled water. After washing twice with 100 ml, it was dried over magnesium sulfate, filtered through a filter paper, and distilled under reduced pressure to obtain a crude product of white crystals. After confirming the structure of the crude crystals by W-NMR (AVANCE500 type manufactured by Bruker Co., Ltd.) and GPC analysis (HLC-8020, manufactured by Ο Ο S Η Ο Co., Ltd.), it was confirmed that the above compound (1-Α) was excluded. 'There are 1 to 3 phenolic hydroxyl groups of the compound represented by the above formula (2-Α) which are reacted with stearic acid. Then, the white solid was recrystallized from ethyl acetate-n-hexane to obtain 23.6 g (yield: 83%) of the object compound represented by the following formula (1-?). The 1 Η - N M R measurement of the compound (AVANCE 5 00 type manufactured by B r u k e r Co., Ltd.) was carried out, and the analysis of TG-DTA (TG8 120 manufactured by Rigaku Electric Co., Ltd.) was carried out, and it was confirmed that the objective compound was obtained. The analysis results are as follows. j-NMR (solvent: CDC13) chemical shift σ: 7.32Ppm (aromatic-48-201202328 aromatic ring hydrogen, 4H), 7.l3ppm (aromatic ring hydrogen, 4H), 7.03 ppm (aromatic ring hydrogen, 4H), 6.8 91 13111 (aromatic ring hydrogen, 4 magic, 2.68ppm (cyclohexane cyclic hydrogen, 2H), 2 52ppm ( cOO-Cib-, 4H ), l_90PPm~1.20PPm ( ι36Η ), 〇. 8 8 ppm (hard fat) Acid methyl, l 2 Η ), 〇·5 1 ppm (CH3 base, 6h) TG _ DTA : decomposition point = 4 2 3 It. [Chemical 3 4]

(Evaluation Example 4) A 10% (wt/wt) toluene solution lkg of ARTON resin (ARTON R53 00, manufactured by JSR Co., Ltd.) was prepared, and then 〇.5 g (0.5% relative to ARTON resin) was added to the above synthesis example. 5 synthesized compound, and dissolved. Then, the resulting mixture was solidified with a large amount of methanol and separated, and then granulated by a twin-screw extruder to obtain granules. The pellets obtained here were injection molded using a wire injection molding machine (solid mold force 75 ton, cylinder diameter 28 mm). The injection molding conditions were a cylinder temperature of 3 3 0 ° C, an injection speed of 200 mm/s, and the mold temperature was raised to 150 ° C at the surface measured temperature. After the mold was cooled, the molded body was taken out from the mold, and 10 positions of any lOmm x 10 mm area on the surface thereof were observed with a 1 〇〇 microscope, and no peeling (shedding) was observed in all the areas. -49-

Claims (1)

201202328 VII. Patent application scope: 1 · A compound represented by the following formula (1), [Chemical 1] (In the formula (1), each L is independently a hydrogen atom, a group represented by the following formula (2), a group represented by the following formula (3) or a R8C〇- (R8 is a hydrocarbon having a carbon number of 1 to 40) Or a carbon number of 1 to 40 one-valent halogenated hydrocarbon group), R4 is independently a carbon number of 1 to 20 one-valent hydrocarbon group or a carbon number of 1 to 20 one-valent halogenated hydrocarbon group, and R5 is independently a carbon number of 1 to 20 a divalent hydrocarbon group or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, A being a single bond, a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, -S-, -S02-, -CO- or -0-, m is an integer of 〇~10, and η is an integer of 0 to 4, but not all of the four Ls are hydrogen atoms), [Chemical 2] ΟΗ 1 to 2 0 of a monovalent hydrocarbon (in the formula (2), R1 is independently a hydrogen atom, a carbon number of -50 - 201202328 or a carbon number of 1 to 20 - a valence halogenated hydrocarbon group 'r2 each independently a single bond or - Co-, R3 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms)] [Chemical 3] (In the formula (3), R6 each independently represents a hydrogen atom, a carbon number of 1 to 20, a monovalent hydrocarbon group or a carbon number of 1 to 20, a valence halogenated hydrocarbon group 'R7 each independently a divalent hydrocarbon group having 1 to 20 carbon atoms or carbon A divalent halogenated hydrocarbon group of 1 to 2 Å). 2. The compound of claim 1, wherein in the above formula (1), L is a group represented by the above formula (2). 3. The compound of claim 2, wherein in the above formula (2), R2 is a single bond. 4. The compound of claim 1, wherein in the above formula (1), each L is independently a hydrogen atom or a group represented by the above formula (3), and at least one of the plurality of L is the above formula (3) ) the basis of the statement. 5. The compound of claim 1, wherein in the above formula (1), each L is independently a hydrogen atom or a group represented by R8CO-, and at least one of the plurality of L is a group represented by R8CO-. An antioxidant comprising a compound according to any one of claims 2 to 4. 7 _ - a release agent containing the compound 201202328 as claimed in claim 5 of the scope of the patent application. A resin composition which contains a compound according to any one of claims 1 to 5 of the patent application. A resin molded body which contains a compound according to any one of claims 1 to 5. 10. A method for synthesizing a compound represented by the following formula (1), which comprises the compound represented by the following formula (4) and the following formula (5), the following formula (6), and the following formula (7) a step of reacting a compound selected from the group consisting of compounds: [Chemical 4] 1 to 20, a one-valent halogenated hydrocarbon group, each of which is independently a divalent hydrocarbon group of carbon number U0 or a divalent halogenated hydrocarbon group having a carbon number of 1 to 20, A is a single bond, a divalent hydrocarbon group having a carbon number U0, and a carbon number of 1 to 20 The divalent halogenated hydrocarbon group, -s-, -S02-, -CO- or -m is an integer of 0 to 10, and η is an integer of 0 to 4), -52-201202328 [Chemical 5] R—Y (5) OH 1 to 20 monovalent hydrocarbons R9S03-hydrocarbyl) (In the formula (5), R1 is independently a hydrogen atom, a carbon number of 1 to 20 or a carbon number of 1 to 2 0. a hydrocarbon group, R 3 each independently a carbon | divalent hydrocarbon group or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, Y is a group represented by a hydroxyl group or a carboxyl group, wherein R 9 is a carbon number of 1 to 20 a monovalent halogenated hydrocarbon group of 1 to 20 carbon atoms or 1 to 20 carbon atoms of the monovalent hydrocarbon, and each of R 7 is independently a divalent hydrocarbon group of carbon or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and X is a halogen. 】 r81 —Z (7) 〇-53 - 201202328 (In the formula (7), R8 is independently a carbon number of 1 to 40, a hydrocarbon group having a carbon number of 1 to 40, a halogenated hydrocarbon group having 1 to 40 carbon atoms, or a hydroxyl group or a halogen atom. ), 【化8】 (1) In the formula (1), each of L is independently a hydrogen atom, a group represented by the following formula (2), a group represented by the following formula (3) or a group represented by R8CO-, and each of R8 is independently of the formula (7) In the case of R8, R' R is synonymous with IT RA, m and, A, m and η in formula (4), but not in the case where all four L are hydrogen atoms. (2) ΟΗ (In equation (2), R1 and R3 are each independently the same as R1 and R3 in formula (5), and R2 is independently a single bond or -C0-) -54- 201202328 [Chemical 1 0] (In the formula (3), R6 and R7 are each independently the same as R6 and R7 in the formula (6). -55- 201202328 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 201202328 V If there is a chemical formula in this case, please disclose the chemical formula 1 that best shows the characteristics of the invention.