JP5167600B2 - Crystals of phosphites - Google Patents

Description

  The present invention relates to crystals of phosphites.

  Crystals of phosphites are used as antioxidants in thermoplastic resins. As a method for producing phosphites, crystals have been conventionally obtained by concentrating the reaction solution and purifying the obtained concentrated residue by silica gel column chromatography (see Patent Document 1).

JP-A-10-273494 ([Example])

However, the method of crystallization by purification by column chromatography has a high crystal recovery rate, but the production equipment is complicated, the production capacity per unit time is low, and is not suitable for industrial production.
The inventors of the present invention tried cooling crystallization using n-decane, and although wet crystals (wet cakes) containing crystals with satisfactory yield and purity were obtained, the wet crystals obtained by crystallization were obtained. In order to remove residual n-decane in the crystal, if the dryer body is left standing, the n-decane remains after drying and may block when stored in a warehouse or the like. It was revealed. Further, it has been clarified that, when a wet crystal containing n-decane is sufficiently dried over a long period of time and is blended with a thermoplastic resin, the thermoplastic resin is colored.
The object of the present invention is to provide crystals of phosphites that have sufficient yield and purity, do not block during storage, and do not cause coloring of the thermoplastic resin even when blended with the thermoplastic resin. That is.

Under such circumstances, the present inventors have found that crystals of phosphites containing a specific amount of a specific organic solvent can solve such problems, and have completed the present invention.
That is, the present invention includes the following formula (I) containing at least one hydrocarbon selected from the group consisting of an aliphatic hydrocarbon having a boiling point of 150 ° C. or less and an alicyclic hydrocarbon having a boiling point of 150 ° C. or less. A phosphite ester represented by the following formula (I) having a hydrocarbon content of 0.005 to 0.3 part by weight per 100 parts by weight of the crystal: It is a crystal.

［式中、Ｒ¹、Ｒ²、Ｒ⁴及びＲ⁵は、それぞれ独立に、水素原子、炭素数１〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表し、Ｒ³は水素原子又は炭素数１〜８のアルキル基を表し、Ｘは単結合、硫黄原子又は−ＣＨＲ⁶−基を表す。ここでＲ⁶は水素原子、炭素数１〜８のアルキル基又は炭素数５〜８のシクロアルキル基を表し、Ａは炭素数２〜８のアルキレン基又は＊−ＣＯＲ⁷−基を表し、ここでＲ⁷は単結合又は炭素数１〜８のアルキレン基を表し、＊は酸素原子側に結合していることを表す。Ｙ及びＺは、いずれか一方がヒドロキシル基、炭素数１〜８のアルコキシ基又は炭素数７〜１２のアラルキルオキシ基を表し、他方が水素原子又は炭素数１〜８のアルキル基を表す。］

[Wherein R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkyl having 6 to 12 carbon atoms. A cycloalkyl group, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X represents a single bond, a sulfur atom or a —CHR ⁶ — group. . Here, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, A represents an alkylene group having 2 to 8 carbon atoms or a * —COR ⁷ — group, and R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond to the oxygen atom side. One of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

  The crystals of the phosphites (I) of the present invention have sufficient yield and purity, do not block during storage, and do not cause coloring of the thermoplastic resin even when blended with the thermoplastic resin.

Hereinafter, the present invention will be described in detail.
In the phosphites (I) in the present invention, the substituents R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl having 5 to 8 carbon atoms. Group, a C6-C12 alkyl cycloalkyl group, a C7-C12 aralkyl group, or a phenyl group.
R ¹ , R ² , and R ⁴ are preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkyl cycloalkyl group having 6 to 12 carbon atoms, and R ⁵ is a hydrogen atom An atom, an alkyl group having 1 to 8 carbon atoms, and a cycloalkyl group having 5 to 8 carbon atoms are preferable.
Here, typical examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, t-pentyl, i -Octyl, t-octyl, 2-ethylhexyl, etc. are mentioned.
As typical examples of the cycloalkyl group having 5 to 8 carbon atoms, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like are typical examples of the alkylcycloalkyl group having 6 to 12 carbon atoms, for example, 1-methylcyclopentyl. 1-methylcyclohexyl, 1-methyl-4-i-propylcyclohexyl and the like. Typical examples of the aralkyl group having 7 to 12 carbon atoms include benzyl, α-methylbenzyl, α, α-dimethylbenzyl and the like.

Especially, it is preferable that R < ¹ >, R < ⁴ > is t-alkyl groups, such as t-butyl, t-pentyl, t-octyl, cyclohexyl, and 1-methylcyclohexyl group. R ² is preferably an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, t-pentyl, In particular, methyl, t-butyl, and t-pentyl are preferable.
R ⁵ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, t-pentyl and the like. It is preferable.

The substituent R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups as described above. A hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is particularly preferable.

The substituent X represents a methylene group which may be substituted by a simple bond, a sulfur atom, alkyl having 1 to 8 carbon atoms or cycloalkyl having 5 to 8 carbon atoms.
Here, as a C1-C8 alkyl substituted by the methylene group and a C5-C8 cycloalkyl, the same alkyl group and cycloalkyl group as the above are mentioned, respectively.
X is preferably a simple bond, a methylene group or a methylene group substituted with methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl or the like.

Substituent A is an alkylene group having 2 to 8 carbon atoms or * -COR ⁷ -group (R ⁷ is a simple bond or an alkylene group having 1 to 8 carbon atoms, and * is bonded to the oxygen side. ).
Here, typical examples of the alkylene group having 2 to 8 carbon atoms include ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, 2,2-dimethyl-1,3-propylene, and the like. Propylene is preferably used.
Also, * in the * —COR ⁷ — group indicates that carbonyl is bonded to phosphite oxygen. Typical examples of the alkylene group having 1 to 8 carbon atoms in R ⁷ include methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, 2,2-dimethyl-1,3-propylene and the like. It is done. R ⁷ is preferably a simple bond, ethylene or the like.

One of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
Here, examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups as described above. Examples of the alkoxy group having 1 to 8 carbon atoms include an alkyl moiety having the above-described alkyl having 1 to 8 carbon atoms. The alkoxy group which is the same alkyl is mentioned. Moreover, as a C7-C12 aralkyloxy group, the aralkyloxy group whose aralkyl part is the same aralkyl as the said C7-C12 aralkyl is mentioned, for example.

（式中、Ｒ¹、Ｒ²、Ｒ³及びＸは前記と同じ意味を表す。）
で示されるビスフェノール類と、三ハロゲン化リンと下式（ＩＩＩ）

（式中、Ｒ⁴、Ｒ⁵、Ａ、Ｙ及びＺは前記と同じ意味を表す。）
で示されるヒドロキシ化合物とを芳香族炭化水中にて反応させ、得られた粗生成物に脂肪族炭化水素及び／又は脂環式炭化水素を加えて冷却晶析することにより得ることができる。 Phosphites (I) usually have the following formula (II)

(Wherein R ¹ , R ² , R ³ and X represent the same meaning as described above.)
Bisphenols represented by the formula, phosphorus trihalide and the following formula (III)

(Wherein R ⁴ , R ⁵ , A, Y and Z have the same meaning as described above).
Can be obtained by reacting with a hydroxy compound represented by the formula (1) in an aromatic hydrocarbon, adding an aliphatic hydrocarbon and / or an alicyclic hydrocarbon to the resulting crude product, and cooling and crystallization.

  Examples of the phosphorus trihalide used here include phosphorus trichloride and phosphorus tribromide. In particular, phosphorus trichloride is preferably used.

In the reaction, for example, the reaction can be promoted by the coexistence of a dehydrohalogenating agent such as amines, pyridines, pyrrolidines and amides, and alkali metal or alkaline earth metal hydroxides.
Here, the amines may be primary amines, secondary amines, or tertiary amines. For example, t-butylamine, t-pentylamine, t-hexylamine, t-octylamine, di-t-butylamine, di- Examples include t-pentylamine, di-t-hexylamine, di-t-octylamine, trimethylamine, triethylamine, N, N-dimethylaniline, N, N-diethylaniline, and preferably triethylamine.
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, and N, N-dimethylformamide is preferably used.
Examples of the alkali metal or alkaline earth metal hydroxide include sodium hydroxide and calcium hydroxide, with sodium hydroxide being preferred.

The reaction is usually performed 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, oxygen-containing hydrocarbons, and halogenated hydrocarbons.
Examples of aromatic hydrocarbons include benzene, toluene, xylene, and ethylbenzene. Examples of aliphatic hydrocarbons include n-hexane, n-heptane, and n-octane. Examples of alicyclic hydrocarbons include: Cyclopentane, cyclohexane, cycloheptane, etc. are oxygenated hydrocarbons such as diethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, etc., and halogenated hydrocarbons are, for example, chloroform, carbon tetrachloride, monochloro. Examples include benzene, dichloromethane, 1,2-dichloroethane, dichlorobenzene and the like.
Among these, aromatic hydrocarbons are preferable from the viewpoint of dissolving raw materials and products during the reaction, and toluene and xylene are particularly preferably used.

As the reaction method, a two-stage reaction method is generally adopted in which first, a bisphenol (II) and phosphorus trihalide are reacted to form an intermediate, and then a hydroxy compound (III) is reacted.
In this method, the phosphorus trihalide is preferably used in an amount of about 1 to 1.1 mol times, more preferably about 1 to 1.05 mol times relative to the bisphenol (II). Moreover, when using a dehydrohalogenating agent, it is preferable to use about 0.05-2.4 mol times with respect to phosphorus trihalide, More preferably, it is about 2-2.1 mol times.
The reaction between the bisphenol (II) and phosphorus trihalide is usually carried out at about 0 to 200 ° C. This reaction is considered to produce an intermediate halogenophosphite, which may be isolated and then subjected to the next reaction, but is usually subjected to the reaction with the hydroxy compound (III) as the reaction mixture.

Next, when the hydroxy compound (III) is reacted, it is usually used in an amount of about 1 to 1.1 mol times with respect to the bisphenol (II).
Also in this reaction, a dehydrohalogenating agent can be used, and the amount of the dehydrohalogenating agent in that case is preferably about 0.05 to 1.2 mol times based on the hydroxy compound (III). The amount of this additional dehydrohalogenating agent is usually calculated including the remaining dehydrohalogenating agent when an excessive amount of dehydrohalogenating agent is used in the first reaction.
The reaction is usually carried out at a temperature of about 0 to 200 ° C.

  Here, bisphenols (II), which are raw materials for the phosphites (I), are disclosed in, for example, JP-A-52-122350, US Pat. No. 2,538,355 and JP-B-2-47451. It can be produced by condensing alkylphenols in accordance with the method described in the publication.

  Examples of bisphenols (II) include 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′- Methylene bis (4-n-propyl-6-t-butylphenol), 2,2′-methylene bis (4-i-propyl-6-t-butylphenol), 2,2′-methylene bis (4-n-butyl-6- t-butylphenol), 2,2′-methylenebis (4-i-butyl-6-t-butylphenol), 2,2′-methylenebis (4,6-di-t-butylphenol), 2,2′-methylenebis ( 4-t-pentyl-6-t-butylphenol), 2,2'-methylenebis (4-nonyl-6-t-butylphenol), 2,2'-methylenebis (4-t -Octyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-pentylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2 ' -Methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-nonylphenol), 2,2'-methylenebis (4-methyl-6-t-octylphenol) ), 2,2′-methylenebis (4,6-di-t-pentylphenol), 2,2′-methylenebis [4-nonyl-6- (α-methylbenzyl) phenol], 2,2′-methylenebis [ 4-nonyl-6- (α, α-dimethylbenzyl) phenol], 2,2′-ethylidenebis (4-methyl-6-tert-butylphenol),

2,2′-ethylidenebis (4-ethyl-6-tert-butylphenol), 2,2′-ethylidenebis (4-n-propyl-6-tert-butylphenol), 2,2′-ethylidenebis (4- i-propyl-6-t-butylphenol), 2,2'-ethylidenebis (4-n-butyl-6-t-butylphenol), 2,2'-ethylidenebis (4-i-butyl-6-t-) Butylphenol), 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2,2'-ethylidenebis (4-t-pentyl-6-t-butylphenol), 2,2'-ethylidenebis (4-nonyl-6-t-butylphenol), 2,2′-ethylidenebis (4-t-octyl-6-t-butylphenol), 2,2′-ethylidenebis (4-methyl-6-pen) Tilphenol), 2,2′-ethylidenebis (4-methyl-6-cyclohexylphenol), 2,2′-ethylidenebis [4-methyl-6- (α-methylcyclohexyl) phenol]], 2,2 ′ -Ethylidenebis (4-methyl-6-nonylphenol), 2,2'-ethylidenebis (4-methyl-6-t-octylphenol), 2,2'-ethylidenebis (4,6-di-t-pentylphenol) ), 2,2′-ethylidenebis [4-nonyl-6- (α-methylbenzyl) phenol], 2,2′-ethylidenebis [4-nonyl-6- (α, α-dimethylbenzyl) phenol], 2,2′-propylidenebis (4-methyl-6-tert-butylphenol), 2,2′-propylidenebis (4-ethyl-6-tert-butylphenol),

2,2′-propylidenebis (4-n-propyl-6-tert-butylphenol), 2,2′-propylidenebis (4-i-propyl-6-tert-butylphenol), 2,2′-propylidenebis (4-n -Butyl-6-t-butylphenol), 2,2'-propylidenebis (4-i-butyl-6-t-butylphenol), 2,2'-propylidenebis (4,6-di-t-butylphenol), 2, 2'-propylidenebis (4-t-pentyl-6-t-butylphenol), 2,2'-propylidenebis (4-nonyl-6-t-butylphenol), 2,2'-propylidenebis (4-t-octyl-6) -T-butylphenol), 2,2'-propylidenebis (4-methyl-6-t-pentylphenol), 2,2'-propylidenebis (4-methyl-6-cyclohexylphenol), 2,2′-propylidenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2′-propylidenebis (4-methyl-6-nonylphenol), 2 , 2′-propylidenebis (4-methyl-6-t-octylphenol), 2,2′-propylidenebis (4,6-di-t-pentylphenol), 2,2′-propylidenebis [4-nonyl-6- ( α-methylbenzyl) phenol], 2,2′-propylidenebis [4-nonyl-6- (α, α-dimethylbenzyl) phenol], 2,2′-butylidenebis (4-methyl-6-tert-butylphenol), 2,2′-butylidenebis (4-ethyl-6-tert-butylphenol), 2,2′-butylidenebis (4,6-di-) -Butylphenol), 2,2′-butylidenebis (4-methyl-6-cyclohexylphenol), 2,2′-butylidenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2′-butylidenebis ( 4,6-di-t-pentylphenol), 2,2'-i-butylidenebis (4-methyl-6-t-butylphenol), 2,2'-i-butylidenebis (4-ethyl-6-t-butylphenol) ), 2,2′-i-butylidenebis (4,6-di-t-butylphenol), 2,2′-i-butylidenebis (4-methyl-6-cyclohexylphenol), 2,2′-i-butylidenebis [ 4-methyl-6- (α-methylcyclohexyl) phenol]], 2,2′-i-butylidenebis (4,6-di-t-pentylph Nol), 2,2′-pentylidenebis (4-methyl-6-tert-butylphenol), 2,2′-pentylidenebis (4-ethyl-6-tert-butylphenol), 2,2′-pentylidene Bis (4,6-di-t-butylphenol), 2,2′-pentylidenebis (4-methyl-6-cyclohexylphenol), 2,2′-pentylidenebis [4-methyl-6- (α- Methylcyclohexyl) phenol]], 2,2′-pentylidenebis (4,6-di-t-pentylphenol), biphenyl-2,2′-diol, 3,3 ′, 5,5′-tetra-t -Butylbiphenyl-2,2'-diol, 1,1'-binaphthyl-2,2'-diol and the like.

The other starting material, hydroxy compound (III), is a compound of the corresponding phenylcarboxylic acids or esters thereof, benzaldehydes, etc. according to known methods when A is alkylene having 2 to 8 carbon atoms. Can be produced by reducing
Here, examples of the reducing agent include aluminum lithium hydride, aluminum sodium hydride, lithium borohydride, sodium borohydride, calcium borohydride, aluminum sodium triethoxyhydride, sodium triacetoxyborohydride, tributyltin hydride, 9-BBN-pyridine, Examples thereof include boron trihydride, sodium, sodium / ammonia in the presence of alcohol, lithium / ammonia in the presence of alcohol, and di-iso-butylaluminum hydride.

  Typical examples of the hydroxy compound (III) when A is alkylene having 2 to 8 carbon atoms include 2- (3-t-butyl-4-hydroxyphenyl) ethanol and 2- (3-t-pentyl). -4-hydroxyphenyl) ethanol, 2- (3-t-octyl-4-hydroxyphenyl) ethanol, 2- (3-cyclohexyl-4-hydroxyphenyl) ethanol, 2- [3- (1-methylcyclohexyl)- 4-hydroxyphenyl] ethanol, 2- (3-tert-butyl-4-hydroxy-5-methylphenyl) ethanol, 2- (3-tert-pentyl-4-hydroxy-5-methylphenyl) ethanol, 2- ( 3-t-octyl-4-hydroxy-5-methylphenyl) ethanol, 2- (3-cyclohexyl-4-hydroxy) -5-methylphenyl) ethanol, 2- [3- (1-methylcyclohexyl) -4-hydroxy-5-methylphenyl] ethanol, 2- (3-t-butyl-4-hydroxy-5-ethylphenyl) ethanol 2- (3-t-pentyl-4-hydroxy-5-ethylphenyl) ethanol, 2- (3-t-octyl-4-hydroxy-5-ethylphenyl) ethanol, 2- (3-cyclohexyl-4- Hydroxy-5-ethylphenyl) ethanol, 2- [3- (1-methylcyclohexyl) -4-hydroxy-5-ethylphenyl] ethanol,

2- (3,5-di-tert-butyl-4-hydroxyphenyl) ethanol, 2- (3-tert-pentyl-4-hydroxy-5-tert-butylphenyl) ethanol, 2- (3-tert-octyl) -4-hydroxy-5-t-butylphenyl) ethanol, 2- (3-cyclohexyl-4-hydroxy-5-t-butylphenyl) ethanol, 2- [3- (1-methylcyclohexyl) -4-hydroxy- 5-t-butylphenyl] ethanol, 2- (3-t-butyl-4-methoxyphenyl) ethanol, 2- (3-t-pentyl-4-methoxyphenyl) ethanol, 2- (3-t-octyl- 4-methoxyphenyl) ethanol, 2- (3-cyclohexyl-4-methoxyphenyl) ethanol, 2- [3- (1-methylcyclohexyl) -4-me Xylphenyl] ethanol, 2- (3-t-butyl-4-methoxy-5-methylphenyl) ethanol, 2- (3-t-pentyl-4-methoxy-5-methylphenyl) ethanol, 2- (3-t -Octyl-4-methoxy-5-methylphenyl) ethanol, 2- (3-cyclohexyl-4-methoxy-5-methylphenyl) ethanol, 2- [3- (1-methylcyclohexyl) -4-methoxy-5 Methylphenyl] ethanol, 2- (3-t-butyl-4-methoxy-5-ethylphenyl) ethanol, 2- (3-t-pentyl-4-methoxy-5-ethylphenyl) ethanol, 2- (3- t-octyl-4-methoxy-5-ethylphenyl) ethanol, 2- (3-cyclohexyl-4-methoxy-5-ethylphenyl) ethane Lumpur,

2- [3- (1-methylcyclohexyl) -4-methoxy-5-ethylphenyl] ethanol, 2- (3,5-di-t-butyl-4-methoxyphenyl) ethanol, 2- (3-t- Pentyl-4-methoxy-5-t-butylphenyl) ethanol, 2- (3-t-octyl-4-methoxy-5-t-butylphenyl) ethanol, 2- (3-cyclohexyl-4-methoxy-5- t-butylphenyl) ethanol, 2- [3- (1-methylcyclohexyl) -4-methoxy-5-t-butylphenyl] ethanol, 3- (3-t-butyl-2-hydroxyphenyl) propanol, 3- (3-t-butyl-4-hydroxyphenyl) propanol, 3- (5-t-butyl-2-hydroxyphenyl) propanol, 3- (3-t-pentyl) 4-hydroxyphenyl) propanol, 3- (3-t-octyl-4-hydroxyphenyl) propanol, 3- (3-cyclohexyl-4-hydroxyphenyl) propanol, 3- [3- (1-methylcyclohexyl) -4 -Hydroxyphenyl] propanol, 3- (3-tert-butyl-2-hydroxy-5-methylphenyl) propanol, 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanol, 3- (5 -T-butyl-2-hydroxy-3-methylphenyl) propanol, 3- (3-t-pentyl-4-hydroxy-5-methylphenyl) propanol, 3- (3-t-octyl-4-hydroxy-5) -Methylphenyl) propanol, 3- (3-cyclohexyl-4-hydroxy-5-methylpheny ) Propanol, 3- [3- (1-methylcyclohexyl) -4-hydroxy-5-methylphenyl] propanol, 3- (3-t-butyl-4-hydroxy-5-ethylphenyl) propanol,

3- (3-t-pentyl-4-hydroxy-5-ethylphenyl) propanol, 3- (3-t-octyl-4-hydroxy-5-ethylphenyl) propanol, 3- (3-cyclohexyl-4-hydroxy -5-ethylphenyl) propanol, 3- [3- (1-methylcyclohexyl) -4-hydroxy-5-ethylphenyl] propanol, 3- (3,5-di-t-butyl-2-hydroxyphenyl) propanol 3- (3,5-di-t-butyl-4-hydroxyphenyl) propanol, 3- (3-t-pentyl-4-hydroxy-5-t-butylphenyl) propanol, 3- (3-t- Octyl-4-hydroxy-5-tert-butylphenyl) propanol, 3- (3-cyclohexyl-4-hydroxy-5-tert-butylphen ) Propanol, 3- [3- (1-methylcyclohexyl) -4-hydroxy-5-tert-butylphenyl] propanol, 3- (3-tert-butyl-2-methoxyphenyl) propanol, 3- (3- t-butyl-4-methoxyphenyl) propanol, 3- (3-t-butyl-5-methoxyphenyl) propanol, 3- (3-t-pentyl-4-methoxyphenyl) propanol, 3- (3-t- Octyl-4-methoxyphenyl) propanol, 3- (3-cyclohexyl-4-methoxyphenyl) propanol, 3- [3- (1-methylcyclohexyl) -4-methoxyphenyl] propanol,

3- (3-t-butyl-2-methoxy-5-methylphenyl) propanol, 3- (3-t-butyl-4-methoxy-5-methylphenyl) propanol, 3- (5-t-butyl-2 -Methoxy-3-methylphenyl) propanol, 3- (3-t-pentyl-4-methoxy-5-methylphenyl) propanol, 3- (3-t-octyl-4-methoxy-5-methylphenyl) propanol, 3- (3-cyclohexyl-4-methoxy-5-methylphenyl) propanol, 3- [3- (1-methylcyclohexyl) -4-methoxy-5-methylphenyl] propanol, 3- (3-t-butyl- 4-methoxy-5-ethylphenyl) propanol, 3- (3-t-pentyl-4-methoxy-5-ethylphenyl) propanol, 3- (3 t-octyl-4-methoxy-5-ethylphenyl) propanol, 3- (3-cyclohexyl-4-methoxy-5-ethylphenyl) propanol, 3- [3- (1-methylcyclohexyl) -4-methoxy-5 -Ethylphenyl] propanol, 3- (3,5-di-t-butyl-2-methoxyphenyl) propanol, 3- (3,5-di-t-butyl-4-methoxyphenyl) propanol, 3- (3 -T-pentyl-4-methoxy-5-t-butylphenyl) propanol, 3- (3-t-octyl-4-methoxy-5-t-butylphenyl) propanol, 3- (3-cyclohexyl-4-methoxy) -5-t-butylphenyl) propanol,

3- [3- (1-Methylcyclohexyl) -4-methoxy-5-tert-butylphenyl] propanol, 3- (3-tert-butyl-2-ethoxyphenyl) propanol, 3- (3-tert-butyl- 4-ethoxyphenyl) propanol, 3- (3-tert-butyl-4-ethoxy-5-methylphenyl) propanol, 3- (3-tert-butyl-2-ethoxy-5-methylphenyl) propanol, 3- ( 5-t-butyl-2-ethoxy-3-methylphenyl) propanol, 3- (3,5-di-t-butyl-4-ethoxyphenyl) propanol, 3- (3,5-di-t-butyl- 2-ethoxyphenyl) propanol, 4- (3-tert-butyl-2-hydroxyphenyl) butanol, 4- (3-tert-butyl-4-hydroxyphenyl) butanol, -(3-t-butyl-4-hydroxy-5-methylphenyl) butanol, 4- (3-t-butyl-2-hydroxy-5-methylphenyl) butanol, 4- (5-t-butyl-2-) Hydroxy-3-methylphenyl) butanol, 4- (3,5-di-tert-butyl-4-hydroxyphenyl) butanol, 4- (3,5-di-tert-butyl-2-hydroxyphenyl) butanol, 4 -(3-t-butyl-2-methoxyphenyl) butanol, 4- (3-t-butyl-4-methoxyphenyl) butanol, 4- (3-t-butyl-4-methoxy-5-methylphenyl) butanol 4- (3-t-butyl-2-methoxy-5-methylphenyl) butanol, 4- (5-t-butyl-2-methoxy-3-methylphenyl) butanol, 4- (3 5-di -t- butyl-4-methoxyphenyl) butanol, 4- (3,5-di -t- butyl-2-methoxyphenyl) butanol,

5- (3-t-butyl-2-hydroxyphenyl) pentanol, 5- (3-t-butyl-4-hydroxyphenyl) pentanol, 5- (3-t-butyl-4-hydroxy-5-methyl) Phenyl) pentanol, 5- (3-t-butyl-2-hydroxy-5-methylphenyl) pentanol, 5- (5-t-butyl-2-hydroxy-3-methylphenyl) pentanol, 5- ( 3,5-di-t-butyl-4-hydroxyphenyl) pentanol, 6- (3,5-di-t-butyl-2-hydroxyphenyl) hexanol, 6- (3-t-butyl-2-hydroxy Phenyl) hexanol, 6- (3-tert-butyl-4-hydroxyphenyl) hexanol, 6- (3-tert-butyl-4-hydroxy-5-methylphenyl) hexanol, 6 (3-t-butyl-2-hydroxy-5-methylphenyl) hexanol, 6- (5-t-butyl-2-hydroxy-3-methylphenyl) hexanol, 6- (3,5-di-t-butyl) -4-hydroxyphenyl) hexanol, 6- (3,5-di-t-butyl-2-hydroxyphenyl) hexanol and the like.

Further, when A is a * -COR ⁷ -group, the hydroxy compound (III) can be produced according to the following method or the like.
When R ⁷ is a simple bond, it can be produced, for example, by subjecting the corresponding hydroxybenzoic acid, alkoxybenzoic acid, aralkyloxybenzoic acid or the like to a Friedel-Craft reaction using a catalyst such as aluminum chloride or zinc chloride. it can. In addition, when Z is a hydroxy group, an alkoxy group or an aralkyloxy group, a Kolbe-Schmidt reaction is performed using a corresponding phenol, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, and carbon dioxide. (See Japanese Patent Laid-Open Nos. 62-61949 and 63-165341).
When R ⁷ is an alkylene having 1 to 8 carbon atoms, the corresponding phenol is acylated using a Friedel-Crafts catalyst such as aluminum chloride or zinc chloride, a carboalkoxyalkanoyl halogenoid, and then palladium on carbon. It can be produced by reducing the carbonyl group at the benzyl position to an alkylene with a hydrogenation catalyst such as platinum charcoal, and then hydrolyzing the ester with an acid or alkali (Rubber Chemistry and Technology 46, 96 (1973) See).
Examples of the hydroxy compound (III) when A is a * —COR ⁷ — group include 3-t-butyl-2-hydroxybenzoic acid, 3-t-butyl-4-hydroxybenzoic acid, and 5-t-butyl. 2-hydroxybenzoic acid, 3-t-pentyl-4-hydroxybenzoic acid, 3-t-octyl-4-hydroxybenzoic acid, 3-cyclohexyl-4-hydroxybenzoic acid, 3- (1-methylcyclohexyl)- 4-hydroxybenzoic acid, 3-t-butyl-2-hydroxy-5-methylbenzoic acid, 3-t-butyl-4-hydroxy-5-methylbenzoic acid, 5-t-butyl-2-hydroxy-3- Methylbenzoic acid, 3-t-pentyl-4-hydroxy-5-methylbenzoic acid, 3-t-octyl-4-hydroxy-5-methylbenzoic acid, 3-cyclohexyl-4 Hydroxy-5-methylbenzoic acid, 3- (1-methylcyclohexyl) -4-hydroxy-5-methylbenzoic acid, 3-t-butyl-4-hydroxy-5-ethylbenzoic acid, 3-t-pentyl-4 -Hydroxy-5-ethylbenzoic acid, 3-t-octyl-4-hydroxy-5-ethylbenzoic acid, 3-cyclohexyl-4-hydroxy-5-ethylbenzoic acid,

3- (1-methylcyclohexyl) -4-hydroxy-5-ethylbenzoic acid, 3,5-di-tert-butyl-2-hydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid 3-t-pentyl-4-hydroxy-5-t-butylbenzoic acid, 3-t-octyl-4-hydroxy-5-t-butylbenzoic acid, 3-cyclohexyl-4-hydroxy-5-t-butyl Benzoic acid, 3- (1-methylcyclohexyl) -4-hydroxy-5-t-butylbenzoic acid, 3-t-butyl-2-methoxybenzoic acid, 3-t-butyl-4-methoxybenzoic acid, 3- t-butyl-5-methoxybenzoic acid, 3-t-pentyl-4-methoxybenzoic acid, 3-t-octyl-4-methoxybenzoic acid, 3-cyclohexyl-4-methoxybenzoic acid, 3- (1-methyl) (Cyclohexyl) -4-methoxybenzoic acid, 3-t-butyl-2-methoxy-5-methylbenzoic acid, 3-t-butyl-4-methoxy-5-methylbenzoic acid, 5-t-butyl-2-methoxy -3-Methylbenzoic acid, 3-tert-pentyl-4-methoxy-5-methylbenzoic acid, 3-tert-octyl-4-methoxy-5-methylbenzoic acid, 3-cyclohexyl-4-methoxy-5-methyl Benzoic acid, 3- (1-methylcyclohexyl) -4-methoxy-5-methylbenzoic acid, 3-tert-butyl-4-methoxy-5-ethylbenzoic acid, 3-tert-pentyl-4-methoxy-5 Ethyl benzoic acid, 3-t-octyl-4-methoxy-5-ethylbenzoic acid, 3-cyclohexyl-4-methoxy-5-ethylbenzoic acid,

3- (1-methylcyclohexyl) -4-methoxy-5-ethylbenzoic acid, 3,5-di-tert-butyl-2-methoxybenzoic acid, 3,5-di-tert-butyl-4-methoxybenzoic acid 3-t-pentyl-4-methoxy-5-t-butylbenzoic acid, 3-t-octyl-4-methoxy-5-t-butylbenzoic acid, 3-cyclohexyl-4-methoxy-5-t-butyl Benzoic acid, 3- (3- (1-methylcyclohexyl) -4-methoxy-5-t-butylbenzoic acid, 3-t-butyl-2-ethoxybenzoic acid, 3-t-butyl-4-ethoxybenzoic acid 3-t-butyl-4-ethoxy-5-methylbenzoic acid, 3-t-butyl-2-ethoxy-5-methylbenzoic acid, 5-t-butyl-2-ethoxy-3-methylbenzoic acid, 3 , 5-Di-tert-butyl-4-eth Cibenzoic acid, 3,5-di-t-butyl-2-ethoxybenzoic acid, (3-t-butyl-2-hydroxyphenyl) acetic acid, (3-t-butyl-4-hydroxyphenyl) acetic acid, (5 -T-butyl-2-hydroxyphenyl) acetic acid, (3-t-pentyl-4-hydroxyphenyl) acetic acid, (3-t-octyl-4-hydroxyphenyl) acetic acid, (3-cyclohexyl-4-hydroxyphenyl) Acetic acid, [3- (1-methylcyclohexyl) -4-hydroxyphenyl] acetic acid, (3-t-butyl-2-hydroxy-5-methylphenyl) acetic acid, (3-t-butyl-4-hydroxy-5- Methylphenyl) acetic acid,

(5-t-butyl-2-hydroxy-3-methylphenyl) acetic acid, (3-t-pentyl-4-hydroxy-5-methylphenyl) acetic acid, (3-t-octyl-4-hydroxy-5-methyl) Phenyl) acetic acid, (3-cyclohexyl-4-hydroxy-5-methylphenyl) acetic acid, [3- (1-methylcyclohexyl) -4-hydroxy-5-methylphenyl] acetic acid, (3-t-butyl-4- Hydroxy-5-ethylphenyl) acetic acid, (3-t-pentyl-4-hydroxy-5-ethylphenyl) acetic acid, (3-t-octyl-4-hydroxy-5-ethylphenyl) acetic acid, (3-cyclohexyl- 4-hydroxy-5-ethylphenyl) acetic acid, [3- (1-methylcyclohexyl) -4-hydroxy-5-ethylphenyl] acetic acid, (3,5-di- -Butyl-2-hydroxyphenyl) acetic acid, (3,5-di-t-butyl-4-hydroxyphenyl) acetic acid, (3-t-pentyl-4-hydroxy-5-t-butylphenyl) acetic acid, (3 -T-octyl-4-hydroxy-5-t-butylphenyl) acetic acid, (3-cyclohexyl-4-hydroxy-5-t-butylphenyl) acetic acid,

[3- (1-Methylcyclohexyl) -4-hydroxy-5-t-butylphenyl] acetic acid, (3-t-butyl-2-methoxyphenyl) acetic acid, (3-t-butyl-4-methoxyphenyl) acetic acid , (3-t-butyl-5-methoxyphenyl) acetic acid, (3-t-pentyl-4-methoxyphenyl) acetic acid, (3-t-octyl-4-methoxyphenyl) acetic acid, (3-cyclohexyl-4- Methoxyphenyl) acetic acid, [3- (1-methylcyclohexyl) -4-methoxyphenyl] acetic acid, (3-tert-butyl-2-methoxy-5-methylphenyl) acetic acid, (3-tert-butyl-4-methoxy) -5-methylphenyl) acetic acid, (5-t-butyl-2-methoxy-3-methylphenyl) acetic acid, (3-t-pentyl-4-methoxy-5-methylphenyl) acetic acid, ( -T-octyl-4-methoxy-5-methylphenyl) acetic acid, (3-cyclohexyl-4-methoxy-5-methylphenyl) acetic acid, [3- (1-methylcyclohexyl) -4-methoxy-5-methylphenyl ] Acetic acid, (3-t-butyl-4-methoxy-5-ethylphenyl) acetic acid, (3-t-pentyl-4-methoxy-5-ethylphenyl) acetic acid, (3-t-octyl-4-methoxy-) 5-ethylphenyl) acetic acid, (3-cyclohexyl-4-methoxy-5-ethylphenyl) acetic acid, [3- (1-methylcyclohexyl) -4-methoxy-5-ethylphenyl] acetic acid, (3,5-di- -T-butyl-2-methoxyphenyl) acetic acid,

(3,5-di-tert-butyl-4-methoxyphenyl) acetic acid, (3-tert-pentyl-4-methoxy-5-tert-butylphenyl) acetic acid, (3-tert-octyl-4-methoxy-5) -T-butylphenyl) acetic acid, (3-cyclohexyl-4-methoxy-5-t-butylphenyl) acetic acid, [3- (1-methylcyclohexyl) -4-methoxy-5-t-butylphenyl] acetic acid, ( 3-t-butyl-2-ethoxyphenyl) acetic acid, (3-t-butyl-4-ethoxyphenyl) acetic acid, (3-t-butyl-4-ethoxy-5-methylphenyl) acetic acid, (3-t- (Butyl-2-ethoxy-5-methylphenyl) acetic acid, (5-t-butyl-2-ethoxy-3-methylphenyl) acetic acid, (3,5-di-t-butyl-4-ethoxyphenyl) acetic acid, ( 3,5-di-t- Til-2-ethoxyphenyl) acetic acid, 3- (3-t-butyl-2-hydroxyphenyl) propionic acid, 3- (3-t-butyl-4-hydroxyphenyl) propionic acid, 3- (5-t- Butyl-2-hydroxyphenyl) propionic acid, 3- (3-t-pentyl-4-hydroxyphenyl) propionic acid, 3- (3-t-octyl-4-hydroxyphenyl) propionic acid, 3- (3-cyclohexyl) -4-hydroxyphenyl) propionic acid, 3- [3- (1-methylcyclohexyl) -4-hydroxyphenyl] propionic acid, 3- (3-tert-butyl-2-hydroxy-5-methylphenyl) propionic acid, 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid, 3- (5-tert-butyl-2-hydroxy-3) Methylphenyl) propionic acid,

3- (3-t-pentyl-4-hydroxy-5-methylphenyl) propionic acid, 3- (3-t-octyl-4-hydroxy-5-methylphenyl) propionic acid, 3- (3-cyclohexyl-4 -Hydroxy-5-methylphenyl) propionic acid, 3- [3- (1-methylcyclohexyl) -4-hydroxy-5-methylphenyl] propionic acid, 3- (3-t-butyl-4-hydroxy-5- Ethylphenyl) propionic acid, 3- (3-t-pentyl-4-hydroxy-5-ethylphenyl) propionic acid, 3- (3-t-octyl-4-hydroxy-5-ethylphenyl) propionic acid, 3- (3-cyclohexyl-4-hydroxy-5-ethylphenyl) propionic acid, 3- [3- (1-methylcyclohexyl) -4-hydroxy- -Ethylphenyl] propionic acid, 3- (3,5-di-t-butyl-2-hydroxyphenyl) propionic acid, 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid, 3 -(3-t-pentyl-4-hydroxy-5-t-butylphenyl) propionic acid, 3- (3-t-octyl-4-hydroxy-5-t-butylphenyl) propionic acid, 3- (3- Cyclohexyl-4-hydroxy-5-t-butylphenyl) propionic acid, 3- [3- (1-methylcyclohexyl) -4-hydroxy-5-t-butylphenyl] propionic acid, 3- (3-t-butyl -2-methoxyphenyl) propionic acid,

3- (3-t-butyl-4-methoxyphenyl) propionic acid, 3- (3-t-butyl-5-methoxyphenyl) propionic acid, 3- (3-t-pentyl-4-methoxyphenyl) propionic acid , 3- (3-t-octyl-4-methoxyphenyl) propionic acid, 3- (3-cyclohexyl-4-methoxyphenyl) propionic acid, 3- [3- (1-methylcyclohexyl) -4-methoxyphenyl] Propionic acid, 3- (3-tert-butyl-2-methoxy-5-methylphenyl) propionic acid, 3- (3-tert-butyl-4-methoxy-5-methylphenyl) propionic acid, 3- (5- t-butyl-2-methoxy-3-methylphenyl) propionic acid, 3- (3-t-pentyl-4-methoxy-5-methylphenyl) propionic acid, 3- (3- -Octyl-4-methoxy-5-methylphenyl) propionic acid, 3- (3-cyclohexyl-4-methoxy-5-methylphenyl) propionic acid, 3- [3- (1-methylcyclohexyl) -4-methoxy- 5-methylphenyl] propionic acid, 3- (3-tert-butyl-4-methoxy-5-ethylphenyl) propionic acid, 3- (3-tert-pentyl-4-methoxy-5-ethylphenyl) propionic acid, 3- (3-t-octyl-4-methoxy-5-ethylphenyl) propionic acid, 3- (3-cyclohexyl-4-methoxy-5-ethylphenyl) propionic acid, 3- [3- (1-methylcyclohexyl) ) -4-methoxy-5-ethylphenyl] propionic acid,

3- (3,5-di-tert-butyl-2-methoxyphenyl) propionic acid, 3- (3,5-di-tert-butyl-4-methoxyphenyl) propionic acid, 3- (3-tert-pentyl) -4-methoxy-5-t-butylphenyl) propionic acid, 3- (3-t-octyl-4-methoxy-5-t-butylphenyl) propionic acid, 3- (3-cyclohexyl-4-methoxy-5 -T-butylphenyl) propionic acid, 3- [3- (1-methylcyclohexyl) -4-methoxy-5-t-butylphenyl] propionic acid, 3- (3-t-butyl-2-ethoxyphenyl) propion Acid, 3- (3-t-butyl-4-ethoxyphenyl) propionic acid, 3- (3-t-butyl-4-ethoxy-5-methylphenyl) propionic acid, 3- (3-t-butyl-2 − Toxi-5-methylphenyl) propionic acid, 3- (5-tert-butyl-2-ethoxy-3-methylphenyl) propionic acid, 3- (3,5-di-tert-butyl-4-ethoxyphenyl) propion Acid, 3- (3,5-di-tert-butyl-2-ethoxyphenyl) propionic acid, 3- (3-tert-butyl-2-hydroxyphenyl) butanoic acid, 3- (3-tert-butyl) -4-hydroxyphenyl) butanoic acid, 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) butanoic acid, 3- (3-tert-butyl-2-hydroxy-5-methyl) Phenyl) butanoic acid,

3- (5-t-butyl-2-hydroxy-3-methylphenyl) butanoic acid, 3- (3,5-di-t-butyl-4-hydroxyphenyl) butanoic acid, 3- (3 , 5-Di-tert-butyl-2-hydroxyphenyl) butanoic acid, 3- (3-tert-butyl-2-methoxyphenyl) butanoic acid, 3- (3-tert-butyl-4-methoxy) Phenyl) butanoic acid, 3- (3-tert-butyl-4-methoxy-5-methylphenyl) butanoic acid, 3- (3-tert-butyl-2-methoxy-5-methylphenyl) butano Ic acid, 3- (5-t-butyl-2-methoxy-3-methylphenyl) butanoic acid, 3- (3,5-di-t-butyl-4-methoxyphenyl) butanoic acid De, 3- (3,5-di -t- butyl-2-methoxyphenyl) butanoate dichroic acid, and the like. ,

  After completion of the reaction, when a dehydrohalogenating agent is used, the hydrohalide salt of the dehydrohalogenating agent produced by the reaction is removed by washing with water, and the solvent is distilled off, and then a crystallization solvent is added. By cooling and crystallization, the phosphites (I) of the present invention can be obtained.

The cooling crystallization includes, for example, a first step of cooling a solution containing the crude phosphite ester (I) and the crystallization solvent such as the reaction solution to precipitate a part of the phosphite ester (I). The second step of heating to a temperature lower than the temperature at which the phosphites (I) precipitated in the first step are dissolved, and the phosphites (I) by cooling the liquid obtained in the second step And a third step of precipitating is recommended. In the cooling crystallization described above, the following relationship between T ₁ , T ₂ and T ₃ satisfies the following formula (1).
T ₃ <T ₁ <T ₂ (1)
Here, T ₁ represents the lowest liquid temperature (° C.) in the first step, T ₂ represents the highest liquid temperature (° C.) in the second step, and T ₃ represents the liquid temperature in the third step. Represents the lowest value (° C).

As the crystallization solvent, aliphatic hydrocarbons and / or alicyclic hydrocarbons having a boiling point of 150 ° C. or lower are used, preferably having a boiling point of 30 to 120 ° C., particularly preferably 30 to 100 ° C. (Hereinafter, aliphatic hydrocarbons having a boiling point of 150 ° C. or lower and alicyclic hydrocarbons having a boiling point of 150 ° C. or lower may be collectively referred to as containing hydrocarbons). At this time, the crystallization solvent may be added in a state in which the reaction solvent remains slightly, but usually the reaction solvent is 10 parts by weight or less with respect to 100 parts by weight of the phosphites. Preferably, it is 5 parts by weight or less. It is preferable that the reaction solvent in the previous period is 10 parts by weight or less because the crystallization yield tends to be improved.
Examples of the aliphatic hydrocarbon having a boiling point of 150 ° C. or lower include n-pentane (boiling point 36 ° C.), n-hexane (boiling point 69 ° C.), n-heptane (boiling point 98 ° C.), n-octane (boiling point 126 ° C.). Examples of the alicyclic hydrocarbon having a boiling point of 150 ° C. or lower include cyclopentane (boiling point 49 ° C.), cyclohexane (boiling point 81 ° C.), cycloheptane (boiling point 117 ° C.), and the like.
The contained hydrocarbons may be different kinds of contained hydrocarbons.
By using the containing hydrocarbons as a crystallization solvent, crystals of the phosphite esters (I) with high purity and high yield can be obtained.
When the contained hydrocarbons have a boiling point of 150 ° C. or lower, blocking during drying and / or storage is suppressed, and even if the crystal of the present invention is added to the thermoplastic resin, the change in hue of the thermoplastic resin is reduced. It tends to be.
Among these, n-hexane or n-heptane is preferable.

  As the amount of the crystallization solvent used, the solution concentration of the phosphites (I) is adjusted to 10 to 60% by weight, preferably 20 to 55% by weight, when batch crystallization is performed. Amount.

In the first step of the formula (1), the ester is cooled to a temperature (saturation temperature) or lower at which the esters (I) are precipitated as crystals from a solution containing the phosphites (I) and the crystallization solvent, and the ester A part of the crystal of class (I) is precipitated. Minimum temperature (minimum value of the liquid temperature (° C.)) in the first step is T _1. The precipitation rate of the phosphites (I) at the temperature T ₁ is preferably in the range of 5 to 60 parts by weight when the total amount of the esters (I) in the solution is 100 parts by weight. More preferably, it is in the range of 40 parts by weight. The temperatures T ₁ varies with a solution concentration of the phosphorous acid esters (I), usually not more than the saturation temperature, preferably in the range of 20 to 50 ° C..
In the cooling operation in the first step, seed crystals of phosphites (I) may be added as necessary. In the first step, at temperatures T ₁ or less, it is preferable to 3 hours cold 30 minutes.

In the second step of formula (2), the slurry is heated from the slurry containing the phosphite (I) crystals precipitated in the first step until some of the crystals are dissolved. In the second step, the slurry is heated to a temperature below which a saturated solution of the phosphites (I) is formed. The maximum temperature of the slurry in the second step (the maximum value of the liquid temperature (° C.)) is T _2. In the temperature T _2, is 100 parts by weight of the total amount of the phosphites of the solution in the first step (I), preferably crystals remaining in the slurry is in the range of 5 to 40 parts by weight, More preferably, it is in the range of 10 to 35 parts by weight. In the second step, it is preferable to kept below a temperature T ₂ 30 minutes to 3 hours.

In the third step of the formula (3), the slurry containing the crystals of the phosphites (I) remaining in the second step and the crystallization solvent is cooled and crystallized.
The minimum temperature in the third step (minimum liquid temperature (° C.)) is T ₃ . T ₃ is usually not lower than the melting point of the crystallization solvent and lower than T ₁ , and specifically −20 to 10 ° C. The cooling rate from T ₂ to T ₃ is preferably a rate of 20 ° C. or less per hour, more preferably a rate of 15 ° C. or less per hour, and particularly preferably a rate of 10 ° C. or less per hour. If the cooling rate during crystallization is 20 ° C. or less per hour, the crystals of the phosphite esters (I) become large and the fluidity tends to improve. In a 3rd process, it is preferable to hold | maintain at temperature T3 for ₃ to 20 hours.

The slurry containing the phosphites (I) and the crystallization solvent produced by cooling crystallization is filtered to obtain coarse wet crystals (wet cake). Preferably, the first carried out to third step, after holding the slurry obtained in the third step at a temperature T _3, and filtered at the same temperature, the crude wet crystals of the phosphite esters (wet cake) Get. As a filtration method, it isolate | separates by normal separation means, such as pressure filtration, vacuum filtration, and centrifugal filtration, for example.

  In this way, the wet wet crystals containing 3 to 20 parts by weight of the hydrocarbons contained in 100 parts by weight of the phosphite (I) crystals can be obtained. Further, the wet crystals can be washed with the containing hydrocarbons. At this time, for example, a solvent other than the hydrocarbon containing water, aromatic hydrocarbon, alcohol and the like may be contained in the wet crystal, but usually 1 part by weight or less, preferably 100 parts by weight of the wet crystal. Is preferably 0.1 parts by weight or less, particularly preferably not substantially contained. When the content of the solvent other than the contained hydrocarbons is 1 part by weight or less, there is a tendency not to solidify during drying, a tendency to prevent blocking when storing the obtained crystals, and thermoplasticity of the obtained crystals. Even if it mix | blends with resin, since coloring of a thermoplastic resin tends to be reduced, it is preferable.

The wet crystals can be dried using a dryer under the following conditions to obtain the crystals of the present invention (dried product).
When the drying pressure is carried out under a vacuum of 5 to 20 kPa, the crystals are not heated to a high temperature or dried over time. Even if the obtained dried crystals are blended with the thermoplastic resin, the thermoplastic resin is colored. Is preferred because it tends to be reduced.
Furthermore, it is preferable that the drying temperature is 40 to 60 ° C., since the coloring of the thermoplastic resin tends to be reduced even when the obtained dry crystal is blended with the thermoplastic resin.
Of course, when the drying pressure is 5 kPa or more, a special vacuum facility is unnecessary, which is preferable from the viewpoint of industrial productivity and economy. If the drying pressure is 20 kPa or less, the drying is sufficient and the occurrence of blocking tends to be suppressed during drying or storage. On the other hand, when the drying temperature is 40 ° C. or higher, the drying becomes sufficient, and the occurrence of blocking during drying or storage tends to be suppressed. Furthermore, when the drying temperature is 60 ° C. or less, there is a tendency that the hue of the thermoplastic resin is prevented from changing when blended with the thermoplastic resin.
The drying conditions of the present invention can be carried out at a drying pressure of 5 to 20 kPa and a drying temperature of 40 to 60 ° C. At this time, the drying pressure is first reduced to 5 to 20 kPa under vacuum at room temperature. After the setting, a method of heating to 40 to 60 ° C. and heating is preferable. By this method, when the crystal is applied to a blocking or thermoplastic resin during drying, the hue of the thermoplastic resin tends to be reduced. Furthermore, the present invention may be dried in a stationary state or may be dried while rotating the dryer, but drying while rotating is preferable from the viewpoint of suppressing caking during drying. Specific examples of the rotary dryer include a conical dryer and a nauter dryer. Specific examples of the stationary dryer include an oven and a vibration fluidized dryer.

In 100 parts by weight of the crystals of the present invention thus obtained, the content of the hydrocarbons contained is 0.005 to 0.3 parts by weight, preferably 0.01 to 0.2 parts by weight, more preferably 0.04 to 0.12 parts by weight.
If it is 0.005 part by weight or more, there is a tendency to reduce coloring of the thermoplastic resin even if blended with the thermoplastic resin, and if it is 0.3 part by weight or less, blocking occurs during drying or storage. It is preferable because of its tendency to suppress.

  EXAMPLES Next, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited by these examples.

(Reaction between bisphenol and hydroxy compound)
620 parts by weight of phosphorus trichloride is added to 6130 parts by weight of a xylene solution of 3,3 ′, 5,5′-tetra-t-butylbiphenyl-2,2′-diol, and the temperature is maintained at 50 to 65 ° C. with stirring. However, 1880 parts by weight of diisopropylethylamine was added in 3 hours. Then, it kept at the same temperature for 1 hour.
Then, while maintaining the temperature of 50~65 ℃, 3- (3-t- butyl-4-hydroxy-5-methylphenyl) propanol 1040 parts by weight was added, then incubated 1 hour at 60-80 ° C. 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3,2 A reaction solution containing dioxaphosphine (hereinafter simply referred to as dioxaphosphine) was obtained. The obtained reaction solution was washed with water, and further washed with a 3 wt% aqueous sodium hydroxide solution.
The organic layer after washing was distilled under reduced pressure with heating to distill off water and xylene. (The xylene content in the reaction solution was 5% by weight or less.)

Example 1
2100 parts by weight of n-heptane was added to the remaining liquid after the distillation, and then a small amount of the above dioxaphosphepine seed crystals was added. Then, it cooled and the crystal | crystallization was deposited. The precipitated crystals were filtered off with a pressure filter to obtain wet crystals on the filter.
The n-heptane content in the wet crystals was measured by gas chromatography (in the following Examples and Comparative Examples, the residual solvents were all quantified by gas chromatography) and found to be 13% by weight.
The wet crystals were washed with n-heptane to obtain wet crystals. Subsequently, it was dried for 15 hours at a jacket inlet temperature of 50 ° C. under a vacuum of 6.6 kPa using a stainless steel vacuum vacuum dryer with a capacity of 2 m ³ . The content of n-heptane (boiling point 98 ° C.) in the dioxaphosphin crystals after drying was 0.12% by weight.
Even when the obtained dioxaphosphepine crystals were stored for 3 months under the condition of 23 ° C. × 50% RH, no solidification (blocking) occurred.

(Comparative Example 1)
The same operation as in Example 1 was conducted except that n-decane (boiling point 174 ° C.) was used as a solvent for crystallization and washing instead of n-heptane. The results are shown in Table 1 together with Example 1.

(Comparative Example 2)
Similar to Example 1 except that n-decane was used in place of n-heptane as a solvent for crystallization and washing, and drying was performed at a jacket inlet temperature of 80 ° C. for 3 hours under a vacuum of 1.3 kPa. Operated. The results are summarized in Table 1.

＊１：２３℃×５０％ＲＨの条件下で３ヶ月保管の結果

* 1: Results of storage for 3 months under conditions of 23 ° C x 50% RH

(Example 2)
The wet crystal was operated in the same manner as in Example 1 except that the bath temperature was set to 50 ° C. under a vacuum of 19 kPa and dried for 45 minutes on a rotary evaporator. The results are summarized in Table 1.
Even when the obtained dioxaphosphepine crystals were stored at 50 ° C. × 80% RH for 4 days, no solidification (blocking) occurred.

(Example 3)
In the same manner as in Example 1, coarse wet crystals were obtained. Next, wet crystals are obtained in the same manner as in Example 1 except that n-hexane is used instead of n-heptane, and then the bath temperature is set to 40 ° C. under a vacuum of 19 kPa on a rotary evaporator. Setting and drying for 30 minutes gave dioxaphosphepine crystals. The results are summarized in Table 2 together with Example 2.

(Comparative Example 3)
The operation was performed in the same manner as in Example 2 except that the bath temperature was set to 98 ° C. under a vacuum of 91 kPa, and drying was performed for 45 minutes. The results are summarized in Table 2.

(Comparative Example 4)
The wet crystals obtained in the same manner as in Example 1 were dried at a bath temperature of 105 ° C. under atmospheric pressure. The results are summarized in Table 2.

＊２：５０℃×８０％ＲＨの条件下で４日間保管の結果

* 2: Results of storage for 4 days under conditions of 50 ° C x 80% RH

(Stabilization test for thermoplastic resin)
50 mg of dioxaphosphepine obtained in Example 1, Comparative Example 3 and Comparative Example 4 and 50 g of low density polyethylene were put into a lab plast mill and kneaded for 30 minutes at 200 ° C. under conditions of 50 revolutions / minute. . After kneading for 30 minutes, pressing was performed, and the yellowness index (YI) of the hue of the press sheet was measured with a color computer to evaluate the color resistance during resin processing. Furthermore, the torque at the time of kneading was tracked, and the torque rise start time was measured. It means that the longer the torque rise start time is, the better the processing stabilization effect is. The results are summarized in Table 3.

Claims (2)

A method for producing crystals by drying wet crystals phosphite esters composed mainly of phosphite represented by the following Symbol formula (I), the aliphatic boiling point of 0.99 ° C. or less in the wet crystals Under vacuum in which at least one hydrocarbon selected from the group consisting of hydrocarbons and alicyclic hydrocarbons having a boiling point of 150 ° C. or lower is contained in a range of 3 to 10% by weight, and a pressure is in a range of 5 to 20 kPa. The heating medium is adjusted to 40 to 60 ° C. to dry the wet crystals, and the content of the hydrocarbon in 100 parts by weight of the obtained phosphite crystals is 0.005 to 0.3 parts by weight. A method for producing crystals of phosphites characterized by adjusting.

[Wherein R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkyl having 6 to 12 carbon atoms. A cycloalkyl group, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X represents a single bond, a sulfur atom or a —CHR ⁶ — group. . Here, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, A represents an alkylene group having 2 to 8 carbon atoms or a * —COR ⁷ — group, and R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond to the oxygen atom side. One of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ] The following formula (I) containing 3 to 20% by weight of at least one hydrocarbon selected from the group consisting of an aliphatic hydrocarbon having a boiling point of 150 ° C. or lower and an alicyclic hydrocarbon having a boiling point of 150 ° C. or lower

[Wherein R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkyl having 6 to 12 carbon atoms. A cycloalkyl group, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X represents a single bond, a sulfur atom or a —CHR ⁶ — group. . Here, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, A represents an alkylene group having 2 to 8 carbon atoms or a * —COR ⁷ — group, and R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond to the oxygen atom side. One of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]
Is dried at a pressure of 5 to 20 kPa and a temperature of 40 to 60 ° C., and the hydrocarbon content relative to 100 parts by weight of the crystals is 0.005 to 0.3 parts by weight. A method for producing crystals of phosphate esters.