CN112004905B - Particulate ultraviolet absorber and resin composition - Google Patents

Abstract

The particulate ultraviolet absorber of the present invention is a particulate ultraviolet absorber comprising a triazine compound, wherein the cumulative 10% particle diameter of the particulate ultraviolet absorber in the particle diameter distribution by volume as measured by a wet laser diffraction particle size distribution measurement method is denoted by D ₁₀ (μm) the cumulative 90% particle diameter was designated as D ₉₀ (μm), D ₁₀ /D ₉₀ In the range of 0.01 to 0.25.

Description

Particulate ultraviolet absorber and resin composition

Technical Field

The present invention relates to a particulate ultraviolet absorber and a resin composition.

Background

Heretofore, various developments have been made on ultraviolet absorbers. As such a technique, for example, a technique described in patent document 1 is known. Patent document 1 describes the use of a triazine compound obtained by crystallization as an ultraviolet absorber (paragraph 0102 and the like of patent document 1).

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2011-6517

Disclosure of Invention

Problems to be solved by the invention

However, as a result of the studies by the present inventors, it was found that the ultraviolet absorber described in the above patent document 1 has room for improvement in powder characteristics.

Means for solving the problems

The present inventors have further studied and as a result, have found that the powder characteristics of a particulate ultraviolet absorber containing a triazine compound can be appropriately controlled by using a particle size distribution by a wet laser diffraction particle size distribution measurement method as an index. Further studies have been conducted based on these findings, and as a result, it was found that by accumulating 10% of the particle diameter D ₁₀ Cumulative 90% particle diameter D ₉₀ The powder characteristics of the above-mentioned granular ultraviolet absorber can be improved by setting the ultraviolet absorber in the given numerical range, and the present invention has been completed.

According to the present invention, there is provided a particulate ultraviolet absorber comprising a triazine compound, characterized in that,

the cumulative 10% particle diameter of the particulate ultraviolet absorber in the volume-based particle diameter distribution measured by the wet laser diffraction particle size distribution measurement method is denoted as D ₁₀ (μm) the cumulative 90% particle diameter was designated as D ₉₀ When the particle size is (mu m),

D ₁₀ /D ₉₀ in the range of 0.01 to 0.25.

Further, according to the present invention, there is provided a resin composition containing the above-mentioned particulate ultraviolet absorber.

Effects of the invention

According to the present invention, there are provided a particulate ultraviolet absorber having excellent powder characteristics and a resin composition using the particulate ultraviolet absorber.

Drawings

The above objects, other objects, features and advantages will be further illustrated by the following description of the preferred embodiments and the following drawings.

FIG. 1 is an X-ray diffraction pattern of the granular ultraviolet absorber of example 1.

FIG. 2 is an X-ray diffraction pattern of the granular ultraviolet absorber of example 11.

FIG. 3 is an X-ray diffraction pattern of the granular ultraviolet absorber of comparative example 1.

Detailed Description

The particulate ultraviolet absorber of the present embodiment contains a triazine compound.

The triazine compound preferably contains a compound represented by the following general formula (I). These may be used alone or in combination of 2 or more.

The particulate ultraviolet absorber may be composed of only the following triazine compound.

[ chemical formula 1]

In the above-mentioned general formula (I),

R ¹ represents a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a substituent represented by the following general formula (II),

R ² and R is ³ Each independently represents a hydrogen atom, a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 20 carbon atoms, or-O-R, wherein R represents a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,

R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ 、R ¹¹ And R is ¹² Each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted straight or branched alkyl group having 1 to 8 carbon atoms, orStraight-chain or branched alkenyl group having 2 to 8 carbon atoms,

R ¹³ and R is ¹⁴ Each independently represents a hydrogen atom or a hydroxyl group.

Wherein R is ¹ 、R ² 、R ³ And R represents a substituted or unsubstituted straight or branched alkyl group having 1 to 20 carbon atoms, R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ 、R ¹¹ And R is ¹² The methylene group in the alkyl group having 1 to 8 carbon atoms which is substituted or unsubstituted and may be selected from the group consisting of an oxygen atom sulfur atom, carbon-carbon double bond, -CO-O-, -OC-O-, -CO-NH-, -NH-CO-, -CR ⁰¹ =n-and-n=cr ⁰² -at least one or more structural substitutions in the above structure, R in the above structure ⁰¹ And R is ⁰² Each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms.

[ chemical formula 2]

In the above-mentioned general formula (II),

R ²¹ and R is ²² Each independently represents a hydrogen atom, a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 20 carbon atoms, or-O-R, wherein R represents a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,

R ²³ 、R ²⁴ 、R ²⁵ 、R ²⁶ 、R ²⁷ 、R ²⁸ 、R ²⁹ 、R ³⁰ And R is ³¹ Each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkenyl group having 2 to 8 carbon atoms,

R ³² and R is ³³ Each independently represents a hydrogen atom or a hydroxyl group,

X ¹ represents a substituted or unsubstituted straight-chain or branched alkylene group having 8 to 30 carbon atoms,

Y ¹ and Y ² Each independently represents-CO-O-, -O-CO-, -L ¹ -、-O-L ¹ O-、-O-L ¹ -、-L ¹ -O-CO-、-L ¹ -CO-O-、-CO-CH＝CH-、-CH＝CH-CO-、-CH＝CH-CO-O-、-CH＝CH-O-CO-、-CO-O-CH＝CH-，

L ¹ Is a straight-chain or branched alkylene group having 1 to 8 carbon atoms,

m and n each independently represent an integer of 0 to 8,

* Represents R bonded to the compound of formula (I) ¹ The site of the linked oxygen atom.

Wherein R is ²¹ 、R ²² And R represents a substituted or unsubstituted straight or branched alkyl group having 1 to 20 carbon atoms, R ²³ 、R ²⁴ 、R ²⁵ 、R ²⁶ 、R ²⁷ 、R ²⁸ 、R ²⁹ 、R ³⁰ And R is ³¹ Substituted or unsubstituted straight-chain or branched alkyl group having 1 to 8 carbon atoms and X ¹ The methylene group in the straight-chain or branched alkylene group having 8 to 30 carbon atoms may be selected from the group consisting of an oxygen atom sulfur atom, carbon-carbon double bond, -CO-O-, -OC-O-, -CO-NH-, -NH-CO-, -CR ⁰³ =n-and-n=cr ⁰⁴ At least one or more structural substitutions, R ⁰³ And R is ⁰⁴ Each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms.

R as in the above general formula (I) ¹ 、R ² 、R ³ R in the above general formula (II) ²¹ 、R ²² And a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 20 carbon atoms represented by R, for example, a straight-chain or branched alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl, dodecyl, etc. are exemplified.

R as in the above general formula (I) ¹ And cycloalkyl groups having 3 to 20 carbon atoms represented by R include, for example, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.

R as in the above general formula (I) ¹ And an aryl group having 6 to 20 carbon atoms represented by R, for example, phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 2, 3-dimethylphenyl, 2, 4-dimethylphenyl, 2, 5-dimethylphenyl, 2, 6-dimethylphenyl, 3, 4-dimethylphenyl, 3, 5-dimethylphenyl, 2, 4-di-tert-butylphenyl, 2, 5-di-tert-butylphenyl, 2, 6-di-tert-butylphenyl, 2, 4-di-tert-pentylphenyl, 2, 5-di-tert-octylphenyl, biphenyl, 2,4, 5-trimethylphenyl and the like.

As R in the above general formula (I) ¹ And arylalkyl groups having 7 to 20 carbon atoms represented by R include, for example, benzyl, phenethyl, 2-phenylpropane-2-yl, diphenylmethyl and the like.

As R in the above general formula (I) ¹ And alkylaryl groups having 7 to 20 carbon atoms represented by R include those wherein one hydrogen atom of the above alkyl group is substituted with an aryl group, and examples of the aryl group include phenyl group, tolyl group, xylyl group, 2, 6-xylyl group, 2,4, 6-trimethylphenyl group, butylphenyl group, nonylphenyl group, biphenyl group, naphthyl group, anthracenyl group and the like.

As R in the above general formula (I) ⁴ 、R ⁵ 、R ⁶ 、R ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ 、R ¹¹ And R is ¹² And R in the above general formula (II) ²³ 、R ²⁴ 、R ²⁵ 、R ²⁶ 、R ²⁷ 、R ²⁸ 、R ²⁹ 、R ³⁰ And R is ³¹ Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

As R in the above general formula (I) ⁴ 、R ⁵ 、R ⁶ 、R ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ 、R ¹¹ And R is ¹² Andr in the above general formula (II) ²³ 、R ²⁴ 、R ²⁵ 、R ²⁶ 、R ²⁷ 、R ²⁸ 、R ²⁹ 、R ³⁰ And R is ³¹ Examples of the substituted or unsubstituted straight-chain or branched alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, n-octyl, isooctyl, tert-octyl, and 2-ethylhexyl groups. In the particulate ultraviolet absorber of the present embodiment, an alkyl group having 1 to 8 carbon atoms is preferable.

As R in the above general formula (I) ¹ 、R ⁴ 、R ⁵ 、R ⁶ 、R ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ 、R ¹¹ And R is ¹² And R in the above general formula (II) ²³ 、R ²⁴ 、R ²⁵ 、R ²⁶ 、R ²⁷ 、R ²⁸ 、R ²⁹ 、R ³⁰ And R is ³¹ Examples of the straight-chain or branched alkenyl group having 2 to 8 carbon atoms include straight-chain and branched propenyl, butenyl, pentenyl, hexenyl, heptenyl and octenyl groups, and the position of the unsaturated bond is not limited.

As X in the above general formula (II) ¹ The substituted or unsubstituted straight-chain or branched alkylene group having 8 to 30 carbon atoms represented by the formula (I) represents an alkylene group in which 8 to 30 methylene groups are bonded or an alkylene group in which a part of hydrogen atoms of the methylene groups are substituted with an alkyl group. In the particulate ultraviolet absorber of the present embodiment, an alkylene group having 8 to 20 carbon atoms is preferable.

As L in the above general formula (II) ¹ Examples of the straight-chain or branched alkylene group having 1 to 8 carbon atoms include methylene, methyl methylene, dimethyl methylene, ethylene, propylene, isopropylene, butylene, isobutylene and pentylene.

The triazine compound may contain R in the general formula (I) ⁵ 、R ⁶ 、R ⁸ 、R ⁹ 、R ¹¹ And R is ¹² Is a compound having a hydrogen atom.

Examples of the triazine compound represented by the general formula (I) include a compound represented by the following general formula (a) and a compound represented by the following general formula (B).

The particulate ultraviolet absorber of the present embodiment may be a compound represented by the following general formula (a). These may be used alone or in combination of 2 or more.

[ chemical formula 3]

In the above-mentioned general formula (A),

R ^A1 represents a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a linear or branched alkenyl group having 3 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms or an arylalkyl group having 7 to 18 carbon atoms,

R ^A2 and R is ^A3 Are identical or different from each other and represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms or a linear or branched alkoxy group having 1 to 12 carbon atoms,

R ^A4 、R ^A7 、R ^A10 are identical or different from one another and represent a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkenyl group having 3 to 8 carbon atoms,

R ^A13 and R is ^A17 Are identical or different from each other and represent a hydrogen atom or a hydroxyl group,

wherein R is ^A1 、R ^A2 And R is ^A3 Straight-chain or branched alkyl of 1 to 12 carbon atoms, R ^A2 And R is ^A3 The methylene group in the straight-chain or branched alkoxy group having 1 to 12 carbon atoms represented may be selected from the group consisting of an oxygen atom sulfur atom, carbon-carbon double bond, -CO-O-, -OC-O-, -CO-NH-, -NH-CO-, -CR ⁰⁵ =n-and-n=cr ⁰⁶ -at least one or more structural substitutions in said structure, R in said structure ⁰⁵ And R is ⁰⁶ Each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms.

R in the above general formula (A) ^A1 、R ^A2 R is R ^A3 Examples of the straight-chain or branched alkyl group having 1 to 20 carbon atoms include straight-chain or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl, and dodecyl.

R in the above general formula (A) ^A2 And R is ^A3 Examples of the straight-chain or branched alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, isobutoxy, pentoxy, isopentoxy, tert-pentoxy, hexoxy, 2-hexoxy, 3-hexoxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptoxy, 2-heptoxy, 3-heptoxy, isoheptoxy, tert-heptoxy, 1-octoxy, isooctoxy, tert-octoxy and the like.

As R in the above general formula (A) ^A1 Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclopentyl, cyclohexyl, and cycloheptyl.

As R in the above general formula (A) ^A1 Examples of the aryl group having 6 to 18 carbon atoms or alkylaryl group having 7 to 18 carbon atoms represented by the formula (I) include phenyl group, naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-vinylphenyl group, 3-isopropylphenyl group, 4-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-octylphenyl group, 4- (2-ethylhexyl) phenyl group, 2, 3-dimethylphenyl group, 2, 4-dimethylphenyl group, 2, 5-dimethylphenyl group, 2, 6-dimethylphenyl group, 3, 4-dimethylphenyl group, 3, 5-dimethylphenyl group, 2, 4-di-tert-butylphenyl group, 2, 5-di-tert-butylphenyl group, 2, 6-di-tert-butylphenyl group, 2, 4-di-tert-pentylphenyl group, 2, 5-di-tert-octylphenyl group, biphenyl group, 2,4, 5-trimethylphenyl group and examples of the alkylaryl group having 7 to 18 carbon atoms include benzyl group, phenethyl group, 2-phenylpropane and the like.

As the aboveR in the general formula (A) ^A1 、R ^A4 、R ^A7 And R is ^A10 Examples of the straight-chain or branched alkenyl group having 3 to 8 carbon atoms include straight-chain and branched propenyl, butenyl, pentenyl, hexenyl, heptenyl and octenyl groups, and the position of the unsaturated bond is not limited.

As R in the above general formula (A) ^A4 、R ^A7 And R is ^A10 Examples of the straight-chain or branched alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, octyl, tert-octyl and the like. Among them, methyl groups are preferable because of their excellent ultraviolet absorption ability.

The triazine compound represented by the general formula (a) preferably contains one or more triazine compounds represented by any one of the following compounds No.1a to No.5 a.

[ chemical formula 4]

The triazine compound represented by the general formula (a) preferably contains one or more triazine compounds represented by any one of the following compounds nos. 6a to 8 a.

[ chemical formula 5]

The particulate ultraviolet absorber of the present embodiment may be a compound represented by the following general formula (B). These compounds may be used alone or in combination of 2 or more.

[ chemical formula 6]

In the above-mentioned general formula (B),

R ^B4 、R ^B5 、R ^B7 ～R ^B9 、R ^B10 ～R ^B12 、R ^B23 、R ^B24 、R ^B26 ～R ^B28 、R ^B29 ～R ^B31 each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkenyl group having 2 to 8 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and n represents an integer of 8 to 14. Among the 3 benzene rings bonded to the triazine ring, the para position of 2 benzene rings represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkoxy group having 1 to 20 carbon atoms, and one of the ortho positions represents a hydrogen atom or a hydroxyl group.

In the general formula (B), R ^B4 、R ^B5 、R ^B7 ～R ^B9 、R ^B10 ～R ^B12 、R ^B23 、R ^B24 、R ^B26 ～R ^B28 、R ^B29 ～R ^B31 Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

In the general formula (B), R ^B4 、R ^B5 、R ^B7 ～R ^B9 、R ^B10 ～R ^B12 、R ^B23 、R ^B24 、R ^B26 ～R ^B28 、R ^B29 ～R ^B31 Examples of the straight-chain or branched alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, 2-propyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, decyl, dodecyl, and octadecyl groups.

In the general formula (B), R ^B4 、R ^B5 、R ^B7 ～R ^B9 、R ^B10 ～R ^B12 、R ^B23 、R ^B24 、R ^B26 ～R ^B28 、R ^B29 ～R ^B31 Examples of the straight-chain or branched alkenyl group having 2 to 8 carbon atoms include vinyl, 1-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-ethyl-1-butanAlkenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, and the like.

In the general formula (B), R ^B4 、R ^B5 、R ^B7 ～R ^B9 、R ^B10 ～R ^B12 、R ^B23 、R ^B24 、R ^B26 ～R ^B28 、R ^B29 ～R ^B31 Examples of the straight-chain or branched alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, tert-pentyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, isoheptyloxy, tert-heptyloxy, 1-octyloxy, isooctyloxy, tert-octyloxy and the like.

In the general formula (B), R ^B4 、R ^B5 、R ^B7 ～R ^B9 、R ^B10 ～R ^B12 、R ^B23 、R ^B24 、R ^B26 ～R ^B28 、R ^B29 ～R ^B31 Examples of the aryl group having 6 to 20 carbon atoms represented by the above formula include phenyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, indenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-vinylphenyl group, 3-isopropylphenyl group, 4-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-octylphenyl group, 4- (2-ethylhexyl) phenyl group, 4-stearylphenyl group, 2, 3-dimethylphenyl group, 2, 4-dimethylphenyl group, 2, 5-dimethylphenyl group, 2, 6-dimethylphenyl group, 3, 4-dimethylphenyl group, 3, 5-dimethylphenyl group, 2, 4-di-tert-butylphenyl group, 2, 5-di-tert-butylphenyl group, 2, 6-di-tert-butylphenyl group, 2, 4-di-tert-pentylphenyl group, 2, 5-di-tert-octylphenyl group, 2, 4-dicumylphenyl group, 4-cyclohexylphenyl group, (1, 1' -biphenyl) -4, 5-trimethylphenyl group, and the like.

The triazine compound represented by the general formula (B) preferably contains one or more triazine compounds represented by any one of the following compounds nos. 1B to 4B.

[ chemical formula 7]

In the above-mentioned compounds No.1B to No.4B, R ^A1 、R ^A2 、R ^B1 、R ^B2 、R ^C1 、R ^C2 、R ^D1 And R is ^D2 Which may be the same or different from each other, represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 4 carbon atoms.

The synthesis method of the above triazine compound is not particularly limited, and may be any synthesis method generally used for synthesizing compounds having a triazine structure. Examples of the method include a method of adding a phenol derivative or a resorcinol derivative to cyanuric chloride using aluminum trichloride. The substituent on the benzene ring bonded to the triazine ring through a single bond may be introduced after the formation of the triazine structure, or may be introduced into the phenol compound or resorcinol derivative before the formation of the triazine structure.

Examples of the method for synthesizing the triazine compound include an esterification reaction or a transesterification reaction between 2- [ 2-hydroxy-4- (2-hydroxyethyloxy) phenyl ] -4, 6-diphenyl-1, 3, 5-triazine as an alcohol component and a corresponding ester derivative compound (carboxylic acid, carboxylic acid halide, carboxylic acid ester), and these reactions may be either sequential reactions or disposable reactions.

Examples of the alcohol component include ester derivative compounds of monocarboxylic acids (monocarboxylic acids, acid halides or monocarboxylic acid esters of monocarboxylic acids), and ester derivative compounds of dicarboxylic acids (dicarboxylic acids, acid halides or dicarboxylic acid esters of dicarboxylic acids).

The triazine compounds may be purified after synthesis. As the purification method, distillation, recrystallization, reprecipitation, a method using a filter/adsorbent, and the like can be suitably used. These methods may be used alone or in combination of 2 or more.

If necessary, the triazine compound may be subjected to processing such as pulverization, granulation, classification, and melt solidification after purification. These treatments may be used alone or in combination of 2 or more. Thus, the desired powder characteristics of the particulate triazine compound can be obtained.

The particles of the particulate ultraviolet absorber of the present embodiment are powder or particulate. The particulate ultraviolet absorber may be used as it is in the form of powder or granules, or may be processed into a predetermined shape such as granules, pellets, tablets, or the like.

The particulate ultraviolet absorber of the present embodiment has characteristics defined by the following particle size distribution.

When the particle size distribution of the particulate ultraviolet absorber of the present embodiment is measured by a wet laser diffraction particle size distribution measurement method, the cumulative 10% particle size in the volume-based particle size distribution is denoted as D ₁₀ (μm), the cumulative 90% particle diameter was designated as D ₉₀ (μm), the cumulative 98% particle diameter in the volume-based particle diameter distribution was designated as D ₉₈ Volume average particle diameter in the particle diameter distribution based on volume is denoted as MV (μm) and number average particle diameter is denoted as MN (μm).

According to the findings of the present inventors, it was found that by using wet conditions, even a powder having a relatively broad particle size distribution and containing fine particles, the particle size distribution can be measured more stably than in dry conditions.

In the present embodiment, D ₁₀ /D ₉₀ For example, the range is from 0.01 to 0.25, preferably from 0.02 to 0.20, and more preferably from 0.03 to 0.15. By making D ₁₀ /D ₉₀ The above upper limit or less can be used to widen the particle size distribution in a relatively wide range, and thus the compression granulation property and the melt kneading property can be improved. Thus, a granular ultraviolet absorber having excellent powder characteristics can be realized. In addition, by making D ₁₀ /D ₉₀ Above the lower limit, a particulate ultraviolet absorber excellent in melt-kneading property and production stability can be obtained。

Although the detailed mechanism is not yet clear, it is considered that by appropriately widening (widening) the particle size distribution, fine particles can enter the gaps between particles to reduce the void ratio, and thus lamination can be suppressed, heat conduction can be enhanced to improve compatibility with the resin.

In the present embodiment, D ₉₈ /D ₉₀ For example, the range is 1.70 to 5.00, preferably 1.80 to 4.50, more preferably 1.90 to 4.00. By setting this value within such a numerical range, a granular ultraviolet absorber excellent in powder characteristics and ultraviolet absorption characteristics can be realized.

In the present embodiment, D ₁₀ For example, the particle size is in the range of 8.0 μm or more and 22.0 μm or less, preferably 9.0 μm or more and 20.0 μm or less, more preferably 10.0 μm or more and 18.0 μm or less. By setting it within such a numerical range, the powder characteristics can be improved.

In the present embodiment, D ₉₀ For example, the particle size is in the range of 120.0 μm to 500.0 μm, preferably 125.0 μm to 450.0 μm, more preferably 130.0 μm to 400.0 μm. By setting it within such a numerical range, the powder characteristics can be improved.

In the present embodiment, MV/MN is, for example, in the range of 5.0 to 30.0, preferably in the range of 8.0 to 28.0, more preferably in the range of 10.0 to 25.0. By setting this value within such a numerical range, a granular ultraviolet absorber excellent in powder characteristics and ultraviolet absorption characteristics can be realized.

In the present embodiment, the above-mentioned D can be controlled by appropriately selecting, for example, the kind or shape of the triazine compound, the production method of the triazine compound, and the like ₁₀ /D ₉₀ 、D ₉₈ /D ₉₀ And MV/MN. Wherein, as D ₁₀ /D ₉₀ 、D ₉₈ /D ₉₀ Examples of the elements for controlling MV/MN within a desired range include processing with a triazine compound, such as melt-curing, pulverizing and classifying, as appropriateConditions, etc.

Further, as a result of further studies, the present inventors have found that the powder properties of a triazine compound and a particulate ultraviolet absorber using the same can be appropriately controlled by using an X-ray diffraction analysis chart as an index. Further studies based on such findings have found that the powder properties in the triazine compound and the particulate ultraviolet absorber using the same can be improved by setting the diffraction angle 2θ at which the strongest peak in the powder X-ray diffraction analysis chart exists to a given numerical range.

The triazine compound (particulate ultraviolet absorber) according to the present embodiment may have characteristics defined by the following powder X-ray diffraction analysis chart.

The triazine compound according to the present embodiment may have a strongest peak in the powder X-ray diffraction analysis chart within a range of 5.00 ° to 6.50 °, preferably 5.20 ° to 6.00 °, and more preferably 5.40 ° to 5.80 °. Thus, the feeding property and the compression granulation property can be improved, and therefore, the triazine compound and the particulate ultraviolet absorber having excellent powder characteristics can be realized.

Here, the strongest peak means a peak having the strongest peak intensity in an X-ray diffraction pattern obtained in a scanning range (for example, diffraction angle 2θ=3 ° to 60 ° or 3 ° to 90 °) in powder X-ray diffraction measurement.

In the powder X-ray diffraction analysis chart of the triazine compound, the half-width of the strongest peak is, for example, 0.05 ° or more and 0.20 ° or less, preferably 0.10 ° or more and 0.19 ° or less, and more preferably 0.15 ° or more and 0.18 ° or less. By appropriately setting the peak width of the strongest peak (maximum peak) within such a numerical range, a particulate ultraviolet absorber excellent in powder characteristics and ultraviolet absorption characteristics can be realized.

In the powder X-ray diffraction analysis chart of the triazine compound, when the relative intensity of the strongest peak is 100, diffraction peaks having a relative intensity of, for example, 30 to 60, preferably 25 to 60, more preferably 22 to 60, and more preferably 60, are not present in the range of 3.0 ° to 45.0 ° in terms of diffraction angle 2θ. That is, by relatively increasing the peak intensity of the strongest peak, it is possible to realize a granular ultraviolet absorber excellent in powder characteristics and ultraviolet absorption characteristics.

In the powder X-ray diffraction analysis chart of the triazine compound, when the relative intensity of the strongest peak is set to 100, the diffraction peak having a relative intensity of 1 to 5 does not exist in a range where the diffraction angle 2θ is, for example, greater than 45.0 ° and 60.0 ° or less, preferably greater than 45.0 ° and 90.0 ° or less. That is, by setting the region where the peak of the minute intensity does not exist within an appropriate numerical range, it is possible to realize a granular ultraviolet absorber excellent in powder characteristics and ultraviolet absorption characteristics.

In this embodiment, for example, by appropriately selecting the type or shape of the triazine compound, the method for producing the triazine compound, and the like, it is possible to control the diffraction angle 2θ of the strongest peak, the half-width of the strongest peak, and the like of the powder X-ray diffraction analysis chart. Among them, for example, as the diffraction angle 2θ of the strongest peak, the half width of the strongest peak, and other powder X-ray diffraction analysis pattern is set in a desired numerical range, can be cited as suitable use of triazine compounds processing conditions, such as melt solidification, grinding, classification.

The resin composition of the present embodiment will be described below.

The resin composition contains the granular ultraviolet absorber. The resin composition may also contain a synthetic resin. Thus, desired resin characteristics corresponding to various applications can be obtained.

Examples of the synthetic resin include thermoplastic resins, thermosetting resins, and elastomers. These may be used alone or in combination of 2 or more.

Specific examples of the synthetic resin include the following resins.

Examples of the thermoplastic resin include, for example, polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, crosslinked polyethylene, ultra-high molecular weight polyethylene, polyethylene-1, polyolefin such as poly-3-methylpentene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-propylene copolymer, and copolymers thereof, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-cyclohexylmaleimide copolymer, and other halogen-containing resins; petroleum resin, coumarone resin, polystyrene, polyvinyl acetate, acrylic resin, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, and polyvinyl butyral; polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate and polycyclohexane dimethanol terephthalate, aromatic polyesters such as polyethylene naphthalate and polyalkylene naphthalate such as polybutylene naphthalate, and linear polyesters such as polybutylene terephthalate; degradable aliphatic polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid resin, polymalic acid, polyglycolic acid, polydioxanes, and poly (2-oxetanone); polyamides such as polyphenylene ether, polycaprolactam and polyhexamethylene adipamide, polycarbonates, branched polycarbonates, polyacetals, polyphenylene sulfides, polyurethanes, fiber resins, and the like.

Examples of the thermosetting resin include phenol resins, urea resins, melamine resins, epoxy resins, and unsaturated polyester resins.

Examples of the elastomer include a fluororesin, a silicone resin, a silicone rubber polyether sulfone, polysulfone, polyphenylene oxide, polyether ketone, polyether ether ketone, and a liquid crystal polymer. Further, isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, silicone rubber, and the like can be cited.

More specific examples of the elastomer include olefinic thermoplastic elastomer, styrenic thermoplastic elastomer, polyester thermoplastic elastomer, nitrile thermoplastic elastomer, nylon thermoplastic elastomer, vinyl chloride thermoplastic elastomer, polyamide thermoplastic elastomer, and polyurethane thermoplastic elastomer.

Examples of the synthetic resin having excellent transparency include polyethylene, polypropylene, polystyrene, copolymers of polyethylene and cycloolefin such as norbornene, polyacrylic acid, polyacrylate, polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, addition polymers of a vinyl compound and a vinyl compound such as polyvinyl fluoride, polymethacrylic acid, polymethacrylate, polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene cyanide, vinylidene fluoride/trifluoroethylene copolymer, polyvinylidene fluoride/tetrafluoroethylene copolymer, copolymers of a vinyl compound or fluorine compound such as vinylidene cyanide/vinyl acetate copolymer, fluorine-containing compounds such as polytrifluoroethylene, polytetrafluoroethylene, and polyhexafluoropropylene, polyamides such as nylon 6, nylon 66, polyimides, polyurethanes, polypeptides, polyesters such as polybutylene terephthalate, polyesters such as polyethylene terephthalate, polycarbonates, polyoxymethylene, polyethers such as polyethylene oxide and polypropylene oxide, epoxy resins, polyvinyl alcohol, polyvinyl butyral, and the like.

In addition, from the viewpoints of compatibility and transparency, examples of the synthetic resin include polycarbonate resin, polyester resin, acrylic resin, ABS resin, and the like.

The synthetic resin may be used alone or in combination of 2 or more kinds, and may be alloyed.

The amount of the particulate ultraviolet absorber blended in the resin composition is, for example, preferably 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and still more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the synthetic resin. When the lower limit value is not less than the above, the effect of the granular ultraviolet absorber can be sufficiently obtained. In addition, by the above upper limit value or less, desired resin properties can be achieved while improving the effect of adding the particulate ultraviolet absorber.

In the present specification, unless otherwise specified, "to" means that the upper limit value and the lower limit value are included.

The resin composition of the present embodiment may contain other additive components in addition to the above components as necessary. Examples of the other additive components include antioxidants, ultraviolet absorbers other than the triazine compounds of the present embodiment, hindered amine light stabilizers, near infrared absorbers, nucleating agents (transparencies), antistatic agents, lubricants, plasticizers, light-absorbing pigments, fillers (fillers), pigments, dyes, metal soaps, processing aids, flame retardants, flame retardant aids, zeolite compounds, foaming agents, (heavy) metal deactivators, crosslinking agents, epoxy stabilizers, matting agents, antifogging agents, precipitation preventing agents, surface treating agents, fluorescent brighteners, antifungal agents, antibacterial agents, and mold release agents.

Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants.

As the above-mentioned phenolic antioxidant, there is provided, examples thereof include 2, 6-di-t-butyl-p-cresol, 2, 6-diphenyl-4-octadecyloxyphenol, distearyl (3, 5-di-t-butyl-4-hydroxybenzyl) phosphonate, 1, 6-hexamethylenebis [ (3, 5-di-t-butyl-4-hydroxyphenyl) propionamide ], 4 '-thiobis (6-t-butyl-m-cresol), 2' -methylenebis (4-methyl-6-t-butylphenol), 2 '-methylenebis (4-ethyl-6-t-butylphenol), 4' -butylidenebis (6-t-butyl-m-cresol) 2,2 '-ethylenebis (4, 6-di-tert-butylphenol), 2' -ethylenebis (4-sec-butyl-6-tert-butylphenol), 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3, 5-tris (2, 6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -2,4, 6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, methyl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] methane, thiodiglycol bis [ (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 1, 6-hexamethylenebis [ (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], ethylene glycol bis [3, 3-bis (4-hydroxy-3-tert-butylphenyl) butyrate ], bis [ 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl ] terephthalate, 1,3, 5-tris [ (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl ] isocyanurate, 3, 9-bis [ (1, 1-dimethyl-2- { (3-tert-butyl-4-hydroxyphenyl) propionyloxyethyl ] isocyanurate, 3, 9-bis [ (3, 3-tert-butyl-4-hydroxyphenyl) propionyloxyethyl ] 4, 5-hydroxy-5-methyl-5-tert-butyl-4-hydroxy-phenyl ] propionate, and the like.

Examples of the phosphorus antioxidant include trisnonylphenyl phosphite and tris [ 2-t-butyl-4- (3-t-butyl-4-hydroxy-5-methylphenylsulfanyl) -5-methylphenyl ]]Phosphites, tridecyl phosphites, triisodecyl phosphites, trilauryl phosphites, octyldiphenyl phosphites, di (decyl) monophenyl phosphite, ditridecyl pentaerythritol bisphosphite, di (nonylphenyl) pentaerythritol bisphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol bisphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol bisphosphite, bis (2, 4, 6-tri-tert-butylphenyl) pentaerythritol bisphosphite, bis (2, 4-dicumylphenyl) pentaerythritol bisphosphite, tetra (tridecyl) isopropylidenediphenyl phosphite, tetra (tridecyl) -4,4' -n-butylidenebis (2-tert-butyl-5-methylphenol) bisphosphite, hexa (tridecyl) -1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetra (2, 4-di-tert-butylphenyl) diphenyl bisphosphite, 9, 10-dihydro-9-oxa-10-phospha-10-p-hosphite, 2, 4' -di-tert-butylphenyl) bis (2, 4' -n-butylphenyl) bisphosphite, 2, 4' -n-butylidene-bis (2-tert-butylphenyl) 2,6 ' -di-butylphenyl) 2' -2-tert-butylphenyl) bisphosphite, 4' -bis (2-tert-butylphenyl) 2-4-di-butylphenyl) bisphosphite, tris (2- [ (2, 4,8, 10-tetra-tert-butyldibenzo [ d, f) ][1,3,2]Dioxaphospha-s-6-yl) oxy]Ethyl) amine, 2-ethyl-2-butyl propanediol, and 2,4, 6-tri-tert-butylphenol.

Examples of the sulfur-based antioxidant include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate and distearyl thiodipropionate, and pentaerythritol tetra (. Beta. -alkylthio propionic acid) esters.

Examples of the ultraviolet absorbers other than the triazine compound according to the present embodiment include 2-hydroxybenzophenones such as 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5' -methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2 '-hydroxyphenyl) benzotriazoles such as 2- (2' -hydroxy-5 '-methylphenyl) benzotriazole, 2- (2' -hydroxy-3 ',5' -di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3' -t-butyl-5 '-methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-5 '-t-octylphenyl) benzotriazole, 2- (2' -hydroxy-3 ',5' -dicumylphenyl) benzotriazole, 2 '-methylenebis (4-t-octyl-6- (benzotriazolyl) phenol), and 2- (2' -hydroxy-3 '-t-butyl-5' -carboxyphenyl) benzotriazole; benzoates such as phenyl salicylate, resorcinol monobenzoate, 2, 4-di-tert-butylphenyl-3, 5-di-tert-butyl-4-hydroxybenzoate, 2, 4-di-tert-pentylphenyl-3, 5-di-tert-butyl-4-hydroxybenzoate, and hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate; substituted oxamides such as 2-ethyl-2 '-ethoxyoxanilide and 2-ethoxy-4' -dodecyloxanilide; cyanoacrylates such as ethyl- α -cyano- β, β -diphenylacrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, and the like.

As the above-mentioned hindered amine-based light stabilizer, examples thereof include 2, 6-tetramethyl-4-piperidinyl stearate, 1,2, 6-pentamethyl-4-piperidinyl stearate, 2, 6-tetramethyl-4-piperidinyl benzoate, bis (2, 6-tetramethyl-4-piperidinyl) sebacate, and bis (1, 2, 6-tetramethyl-4-piperidinyl) sebacate, bis (1-octyloxy-2, 6-tetramethyl-4-piperidinyl) sebacate, tetrakis (2, 6-tetramethyl-4-piperidinyl) -1,2,3, 4-butanetetracarboxylate bis (1, 2, 6-tetramethyl-4-piperidinyl) sebacate, bis (1-octyloxy-2, 6-tetramethyl-4-piperidinyl) sebacate tetra (2, 6-tetramethyl-4-piperidinyl) -1,2,3, 4-butanetetracarboxylate, 1, 6-bis (2, 6) -tetramethyl-4-piperidylamino) hexane/2, 4-dichloro-6-morpholino-s-triazine polycondensate, 1, 6-bis (2, 6-tetramethyl-4-piperidylamino) hexane/2, 4-dichloro-6-tert-octylamino-s-triazine polycondensate 1,5,8, 12-tetrakis [2, 4-bis (N-butyl-N- (2, 6-tetramethyl-4-piperidinyl) amino) -s-triazin-6-yl ] -1,5,8, 12-tetraazadodecane 1,5,8, 12-tetrakis [2, 4-bis (N-butyl-N- (1, 2, 6-pentamethyl-4-piperidinyl) amino) -s-triazin-6-yl ] -1,5, 8-12-tetraazadodecane, 1,6, 11-tris [2, 4-bis (N-butyl-N- (2, 6-tetramethyl-4-piperidinyl) amino) -s-triazin-6-yl ] aminoundecane hindered amine compounds such as 1,6, 11-tris [2, 4-bis (N-butyl-N- (1, 2, 6-pentamethyl-4-piperidinyl) amino) -s-triazin-6-yl ] aminoundecane.

Examples of the near infrared absorbing agent include polymethine dyes (cyanine dyes), indole cyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, naphthol metal complex dyes, squaraine dyes, trisazo dyes, dithiol metal complex salt dyes, pyrylium dyes, thiopyranium dyes, indoloaniline dyes, azo anthraquinone dyes, naphthoquinone dyes, anthraquinone dyes, bis (dithioene) dyes, triphenylmethane dyes, aluminum (aluminum) dyes, and diimmonium dyes. Further, inorganic near infrared ray absorbers may be used, and examples thereof include carbon black, tin oxide doped with antimony oxide or indium oxide, and oxides, carbides or borides of metals belonging to groups 4A, 5A or 6A of the periodic table.

Examples of the nucleating agent include metal salts of benzoic acids such as aluminum p-tert-butylbenzoate and sodium benzoate, sodium bis (2, 4-di-tert-butylphenyl) phosphate, sodium methylenebis (2, 4-di-tert-butylphenyl) phosphate, metal salts of aromatic phosphates and metal salts of aromatic phosphates such as aluminum bis [ methylenebis (2, 4-di-tert-butylphenyl) phosphate ] hydroxy group, alkali metal compounds, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, dibenzylidene sorbitol such as bis (p-ethylbenzylidene) sorbitol, bis (dimethylbenzylidene sorbitol), metal salts of amino acids, metal salts of abietic acid, N, amide compounds such as N ', N' -tris [ 2-methylcyclohexyl ] -1,2, 3-propanetricarboxylic acid amide, N '-tricyclohexyl-1, 3, 5-benzenetricarboxylic acid amide, N' -dicyclohexylnaphthalene dicarboxamide, and 1,3, 5-tris (dimethylisopropylamido) benzene.

Examples of the antistatic agent include cationic antistatic agents such as fatty acid quaternary ammonium salts and polyammonium quaternary salts; anionic antistatic agents such as higher alcohol phosphate, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anionic alkyl sulfonates, higher alcohol sulfate, higher alcohol ethylene oxide adduct sulfate, and higher alcohol ethylene oxide adduct phosphate; nonionic antistatic agents such as polyol fatty acid esters, polyethylene glycol phosphate esters, and polyoxyethylene alkyl allyl ethers; amphoteric antistatic agents such as amphoteric alkyl betaines such as alkyl dimethyl glycine betaine and imidazoline type amphoteric activators, and polymeric antistatic agents containing block polymers having ionomers or polyethylene glycol as hydrophilic units.

Examples of the lubricant include hydrocarbon lubricants such as liquid paraffin, paraffin wax, and polyethylene wax; aliphatic lubricants such as stearyl alcohol, stearic acid, and 12-hydroxystearic acid; amide lubricants such as stearic acid amide, oleic acid amide, erucic acid amide, methylene distearate amide and ethylene stearic acid amide; metallic soap lubricants such as calcium stearate, zinc stearate, magnesium stearate, lead stearate, aluminum stearate, barium stearate/zinc stearate composite, zinc stearate/calcium stearate composite, and the like; ester lubricants such as hardened oils and fats, glycerin monostearate, butyl stearate, pentaerythritol stearate, and stearyl stearate.

Examples of the plasticizer include phthalic acid esters, dibasic acid esters, chlorinated paraffin, polyesters, epoxidized esters, phosphoric acid esters, and trimellitic acid esters.

Examples of the light-absorbing dye include cyanines, quinolines, coumarins, thiazoles, chlorocyanines, chamomile blue, squarylium, azomethines, azo compounds, benzylidene compounds, xanthenes, phthalocyanines, dithiol metal complex compounds, and the like.

Examples of the filler include metal silicate such as calcium carbonate, calcium oxide, calcium hydroxide, zinc carbonate, zinc sulfide, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, sodium aluminum silicate, hydrocalumite, aluminum silicate, magnesium silicate, calcium silicate, zeolite, activated clay, talc, clay, red iron oxide, asbestos, antimony trioxide, silica, glass beads, mica, sericite, glass flakes, asbestos, wollastonite, potassium titanate, PMF (mineral fiber), gypsum fiber, diatomaceous earth, MOS (magnesium hydroxide sulfate hydrate, fibrous magnesium compound), phosphate fiber, glass fiber, carbon fiber, aramid fiber, cellulose nanofiber, and the like.

Examples of the pigment that can be used include pigment red 1, pigment red 2, pigment red 3, pigment red 9, pigment red 10, pigment red 17, pigment red 22, pigment red 23, pigment red 31, pigment red 38, pigment red 41, pigment red 48, pigment red 49, pigment red 88, pigment red 90, pigment red 97, pigment red 112, pigment red 119, pigment red 122, pigment red 123, pigment red 144, pigment red 149, pigment red 166, pigment red 168, pigment red 169, pigment red 170, pigment red 171, pigment red 177, pigment red 179, pigment red 180, pigment red 184, pigment red 185, pigment red 192, pigment red 200, pigment red 202, pigment red 209, pigment red 215, pigment red 216, pigment red 217, pigment red 220, pigment red 223, pigment red 224, pigment red 226, pigment red 227, pigment red 228, pigment red 240, and pigment red 254; pigment orange 13, pigment orange 31, pigment orange 34, pigment orange 36, pigment orange 38, pigment orange 43, pigment orange 46, pigment orange 48, pigment orange 49, pigment orange 51, pigment orange 52, pigment orange 55, pigment orange 59, pigment orange 60, pigment orange 61, pigment orange 62, pigment orange 64, pigment orange 65, pigment orange 71; pigment yellow 1, pigment yellow 3, pigment yellow 12, pigment yellow 13, pigment yellow 14, pigment yellow 16, pigment yellow 17, pigment yellow 20, pigment yellow 24, pigment yellow 55, pigment yellow 60, pigment yellow 73, pigment yellow 81, pigment yellow 83, pigment yellow 86, pigment yellow 93, pigment yellow 95, pigment yellow 97, pigment yellow 98, pigment yellow 100, pigment yellow 109, pigment yellow 110, pigment yellow 113, pigment yellow 114, pigment yellow 117, pigment yellow 120, pigment yellow 125, pigment yellow 126, pigment yellow 127, pigment yellow 129, pigment yellow 137, pigment yellow 138, pigment yellow 139, pigment yellow 147, pigment yellow 148, pigment yellow 150, pigment yellow 151, pigment yellow 152, pigment yellow 153, pigment yellow 154, pigment yellow 166, pigment yellow 168, pigment yellow 175, pigment yellow 180, pigment yellow 185; pigment green 7, pigment green 10, pigment green 36; pigment blue 15, pigment blue 15:1, pigment blue 15:2, pigment blue 15:3, pigment blue 15:4, pigment blue 15:5, pigment blue 15:6, pigment blue 22, pigment blue 24, pigment blue 56, pigment blue 60, pigment blue 61, pigment blue 62, pigment blue 64; pigment violet 1, pigment violet 19, pigment violet 23, pigment violet 27, pigment violet 29, pigment violet 30, pigment violet 32, pigment violet 37, pigment violet 40, pigment violet 50, and the like.

Examples of the dye include azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indane dyes, oxazine dyes, phthalocyanine dyes, and cyanine dyes.

As the metal soap, for example, salts of metals such as lithium, sodium, potassium, magnesium, calcium, aluminum hydroxyls, barium, and zinc with saturated or unsaturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid can be used.

The processing aid may be appropriately selected from known processing aids, and an acrylic processing aid is preferable. Examples of the processing aid include homopolymers and copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; copolymers of the above alkyl methacrylates with alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate; copolymers of the above alkyl methacrylates with aromatic vinyl compounds such as styrene, α -methylstyrene, vinyl toluene, etc.; copolymers of the above alkyl methacrylate with vinyl nitrile compounds such as acrylonitrile and methacrylonitrile, and the like.

Examples of the flame retardant and the flame retardant auxiliary include the following triazine ring-containing compound, metal hydroxide, other inorganic phosphorus, halogen-based flame retardant, silicone-based flame retardant, phosphate-based flame retardant, condensed phosphate-based flame retardant, intumescent flame retardant, antimony oxide such as antimony trioxide, other inorganic flame retardant auxiliary, organic flame retardant auxiliary, and the like.

Examples of the triazine ring-containing compound include melamine, melamine diamide (ameline), benzoguanamine, acetoguanamine, benzodiguanidine, melamine cyanurate, melamine pyrophosphate, butene diguanidine, norbornene diguanidine, methylene diguanidine, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, and 1, 3-hexene dimelamine.

Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, and KISUMA 5A (magnesium hydroxide: manufactured by Kyowa Kagaku Co., ltd.).

Examples of the phosphate flame retardant include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris (dichloropropyl) phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tri (xylyl) phosphate, octyl diphenyl phosphate, xylyl diphenyl phosphate, triisopropyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis (t-butylphenyl) phenyl phosphate, tris (t-butylphenyl) phosphate, isopropylphenyl diphenyl phosphate, bis (isopropylphenyl) diphenyl phosphate, and tri (isopropylphenyl) phosphate.

Examples of the condensed phosphate flame retardant include 1, 3-phenylene bis (diphenyl phosphate), 1, 3-phenylene bis (xylyl phosphate), bisphenol a bis (diphenyl phosphate), and the like, and examples of the intumescent flame retardant include ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, ammonium pyrophosphate, melamine pyrophosphate, piperazine pyrophosphate, and other (poly) ammonium phosphate salts or amine salts thereof.

Examples of the other inorganic flame retardant auxiliary include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, and talc, and surface-treated products thereof, and various commercially available products such as TI PAQUE R-680 (titanium oxide: manufactured by Shichen Co., ltd.), kyowa MAG150 (magnesium oxide: manufactured by Kyowa chemical Co., ltd.).

Further, as other organic flame retardant aids, pentaerythritol, dipentaerythritol, and the like can be mentioned.

The zeolite compound is an aluminosilicate of an alkali metal or alkaline earth metal having a unique three-dimensional zeolite crystal structure, and typical examples thereof include a type a, type X, type Y and type P zeolite, mordenite (mordinite), analcite, sodalite family aluminosilicate, clinoptilolite (clinoptilolite), erionite, chabazite and the like, and may be an aqueous substance having crystal water (so-called zeolite water) of these zeolite compounds or an anhydrous substance obtained by removing crystal water, and may use a substance having a particle diameter of 0.1 to 50 μm, particularly preferably a substance having a particle diameter of 0.5 to 10 μm.

Examples of the blowing agent include decomposed organic blowing agents such as azodicarbonamide, azodiisobutyronitrile, p '-oxybisbenzenesulfonyl hydrazide, n' -dinitroso pentamethylene tetramine, p-toluenesulfonyl semicarbazide, and trihydrazinol triazine, and decomposed inorganic blowing agents such as sodium hydrogencarbonate, ammonium carbonate, ammonium hydrogencarbonate, ammonium nitrite, azide, and sodium borohydride.

Examples of the (heavy) metal deactivator include salicylamide-1, 2, 4-triazol-3-yl, bis-salicylic acid hydrazide, dodecanedioic acid bis (2- (2-hydroxybenzoyl) hydrazide), bis (3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionic acid hydrazide, and the like.

Examples of the crosslinking agent include benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne, 1, 3-bis (t-butylperoxyisopropyl) benzene-t-butyl hydroperoxide, cumene hydroperoxide, polysulfone azide, azidoformate, tetramethyl isophthaloyl di-t-butyl hydroperoxide, tetramethyl isophthaloyl dicumyl peroxide, alkanolamines such as diethanolamine and triethanolamine, hexamethylenediamine, 4' -diaminodiphenylmethane and the like.

Examples of the epoxy stabilizer include compounds having an aliphatic, aromatic, alicyclic, aromatic aliphatic or heterocyclic structure and having an epoxy group as a side chain. The epoxy group is preferably bound as a glycidyl group to the residue of the molecule via an ether or ester bond, or it may be an N-glycidyl derivative of a heterocyclic amine, amide or imide. Specific examples thereof include epoxidized soybean oil, epoxidized linseed oil, and epoxidized monoesters. As the commercial products of the epoxy stabilizer, for example, the product names "ADK CIZER O-130P", "ADK CIZER O-180A", "ADK CIZER D-32", "ADK CIZER EP-13" and "ADK CIZER FEP-13" of ADEKA of Kyowa Co., ltd.

As the matting agent, silica fine particles are preferable. Examples of the fine particles of silica include AEROSIL R972, R972V, R974, R812, 200V, 300, R202, OX50, and TT600 (manufactured by AEROSIL corporation, japan), and AEROSIL200V, AEROSIL R972V, and AEROSIL R812 are preferable in terms of their large effect of reducing the friction coefficient while keeping the haze of the film low.

Examples of the antifogging agent include glycerin fatty acid ester, alkyl diethanolamine, and alkyl diethanolamine fatty acid ester.

Examples of the precipitation inhibitor include silica and alkylene oxide adducts of saponified ethylene-saturated carboxylic acid vinyl ester copolymers as active ingredients.

As the surface treatment agent, for example, a surface treatment agent containing one or more of an aminosilane compound and an epoxy resin is preferably used.

Examples of the aminosilane compound include gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, and gamma- (2-aminoethyl) aminopropyl trimethoxysilane.

Examples of the epoxy resin contained in the surface treating agent include novolak type epoxy resins and bisphenol type epoxy resins, and novolak type epoxy resins are preferably used. Examples of the novolak type epoxy resin include polyfunctional epoxy resins such as phenol novolak type epoxy resins and cresol novolak type epoxy resins.

In addition, the surface treating agent may contain components such as urethane resin, acrylic resin, antistatic agent, lubricant, and water repellent, in addition to the aminosilane compound and the epoxy resin, as far as the performance is not impaired. Further, examples of the other surface treatment agent include epoxy resins other than novolak type and bisphenol type, coupling agents, and the like.

The fluorescent whitening agent is a compound which absorbs ultraviolet rays of sunlight and artificial light, converts the ultraviolet rays into visible light of violet to blue, and emits fluorescent light to promote whiteness and bluish properties of the molded article. As fluorescent whitening agents, benzoxazole compounds C.I.Fluorescent Brightner 184; coumarin compound c.i. fluorescent bright 52; diaminostyrene disulfonic acid compounds c.i Fluorescent Brightner, 85, 71, etc.

Examples of the antifungal agent include organic antifungal agents such as nitrogen-containing and sulfur-containing compounds, organic bromides, nitrogen-containing compounds and arsenic-containing compounds, and inorganic antifungal agents such as silver compounds.

Examples of the antibacterial agent include organic antibacterial agents such as chlorine-based, phenol-based, imidazole-based or thiazole-based compounds and quaternary ammonium compounds, and inorganic antibacterial agents such as zeolite-based, apatite-based, silica alumina-based, ceramic-based, zirconium phosphate-based, silica gel-based, hydroxyapatite-based or calcium silicate-based, which contain metals such as silver and zinc.

Examples of the release agent include sodium montanate, potassium montanate, calcium montanate, and magnesium montanate.

The method for producing the resin composition of the present embodiment is not particularly limited, and any conventionally known method can be used.

Examples of the method for producing the resin composition include a method in which the particulate ultraviolet absorber of the present embodiment, the synthetic resin, and other optional additives are premixed in various mixers such as a roll mixer and a henschel mixer, and then melt-kneaded using a banbury mixer, a roll, a brabender mixer, a single-shaft kneading extruder, a twin-shaft kneading extruder, a kneader, or the like.

Further, the resin composition may be produced by feeding the components into an extruder using a feeder without or with only a part of the components being mixed in advance, and melt-kneading the components. Further, the resin composition may be produced by mixing a part of the components in advance and supplying them to an extruder and melt-kneading them, taking the obtained resin composition as a master batch, and then mixing them with other components again and melt-kneading them.

The synthetic resin used in the mixing and kneading step may have a predetermined shape such as powder, pellet, or fiber.

The resin composition of the present embodiment may be solid at room temperature, and may have a constant shape such as a powder, a pellet, a block, a tablet, or a sheet shape as a shape.

The resin composition of the present embodiment can be molded to obtain a molded article.

The molding method is not particularly limited, and examples thereof include injection molding, extrusion molding, blow molding, rotational molding, vacuum molding, inflation molding, calendaring, slush molding, dip molding, foam molding, and the like.

The molded article may have various forms depending on the application, and may have various shapes such as a resin plate, a sheet, a film, a container (bottle, tray, bag), a fiber, and various molded articles.

The resin composition of the present embodiment can be prepared by dissolving each component such as the particulate ultraviolet absorber of the present embodiment, the synthetic resin described above as a binder resin, and other additive components as needed in a solvent to prepare a varnish resin (varnish-like resin composition that is liquid at room temperature). As the solvent, an organic solvent or an aqueous solvent can be used. If necessary, an emulsifier may be used, and the resin varnish may be used in the form of an emulsion in which a powdery ultraviolet absorber is dispersed.

The method for producing the resin varnish is not particularly limited in the order of mixing the components, and all the components may be mixed at the same time, or the particulate ultraviolet absorber and other additive components of the present embodiment may be mixed in advance, and then the resultant mixture may be mixed with the synthetic resin, or a plurality of components prepared in advance may be mixed with other components, or a plurality of components prepared in advance may be further mixed with each other.

The resin varnish may be processed into a film or sheet by a casting film method, for example. In addition, the above resin varnish can also be used as a coating material for coating on a given substrate.

The resin composition of the present embodiment can be used in a wide variety of industrial fields such as electric/electronic/communication, agriculture, forestry and fishery, mining, construction, food, fiber, clothing, medical treatment, coal, petroleum, rubber, leather, automobiles, precision equipment, wood, construction materials, civil engineering, furniture, printing, musical instruments, and the like.

More specific applications include printers, personal computers, word processors, keyboards, PDAs (personal digital assistants), telephones, copiers, facsimile machines, ECR (electronic cash registers), calculators, electronic notebooks, cards, holders, transactions such as stationery, office automation equipment, washing machines, refrigerators, cleaners, microwave ovens, lighting equipment, game machines, irons, household appliances such as stoves, televisions, video recorders, video cameras, radio recorders, mini-discs, CD players, speakers, AV equipment such as liquid crystal displays, connectors, relays, capacitors, switches, printed boards, coil frames, semiconductor packages, LED packages, wires, cables, transformers, deflection coils, power boards, electronic parts and communication equipment such as clocks, automotive interior and exterior materials, platemaking films, adhesive films, bottles, food containers, food packaging films, pharmaceutical/medicinal packaging films, product packaging films, agricultural sheets, greenhouse films, and the like.

Specific applications include various applications such as seats (fillers, exterior materials, etc.), safety belts, ceilings, compatible roofs, armrests, door trims, rear seal trays, carpets, mats, sun visors, wheel covers, mattress covers, airbags, insulating materials, hand tabs, hand belts, wire coating materials, electric insulating materials, paints, coating materials, covering materials, floor materials, corners, carpets, wallpaper, wall materials, exterior materials, interior materials, roofing materials, deck materials, wall materials, pillar materials, floors, fence materials, frames and decorative materials, windows and door materials, floor panels, wall panels, terraces, balconies, soundproof panels, heat insulation panels, window materials, and the like automobiles, vehicles, ships, airplanes, buildings, house and building materials, civil engineering materials, clothing, curtains, bed sheets, nonwoven fabrics, plywood, synthetic fiber sheets, carpets, entrance mats, sheets, water tanks, hoses, containers, spectacles, bags, boxes, goggles, sleevelets, tents, musical instruments, and the like. In addition to these, paint, cosmetics, and the like can be cited.

Further, the following uses can be mentioned: medicine containers for pharmaceuticals, vitamins, beverages, eye drops, etc.; cosmetic containers such as lotions, emulsions, sunscreens, and the like; beverage containers such as food containers, wine, beer, fruit juice, soft drink, tea, black tea, coffee, and the like; and the daily necessities such as shampoo, hair conditioner, mouthwash, toothpaste, disinfectant and the like.

The resin composition of the present embodiment is not particularly limited, and can be suitably used as an optical material such as an optical film or an optical sheet by molding into a sheet or a film. As the optical material, for example, an optical film or an optical sheet used in an image display device such as a liquid crystal display device (LCD), a Plasma Display Panel (PDP), an electroluminescence display (ELD), a cathode ray tube display device (CRT), a fluorescent display tube, or an electric field emission display is useful, and in particular, an optical film such as an optical correction film or a light-emitting protective film of a liquid crystal display device or an organic EL display using an organic material having poor ultraviolet resistance as a display element is useful. Examples of applications of the liquid crystal display device include a polarizing plate protective film or protective sheet, a retardation film, a viewing angle expanding film, an antiglare film, a brightness enhancement film, a light diffusion film and a light diffusion sheet, a lens film and a lens sheet, an antifogging film, an antistatic film, an optical correction film, an antireflection film, a color tone adjusting film, a light guide plate, and the like, and in particular, the liquid crystal display device can be suitably applied to an optical film or optical sheet provided on an outer surface side of a polarizing plate in contact with a liquid crystal display element, or a polarizing plate protective film or optical sheet.

While the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above may be adopted.

Examples

The present invention will be described in detail with reference to examples, but the present invention is not limited to the description of these examples.

[ preparation of particulate ultraviolet absorbent ]

Example 1

2,4, 6-tris [ 2-hydroxy-3-methyl-4-hexyloxyphenyl ] triazine was synthesized by the following procedure.

In a 300ml four-necked flask, 10.00g of 2,4, 6-tris (2, 4-dihydroxy-3-methylphenyl) triazine, 22.68g of sodium hydroxide, 80.00g of dimethylformamide and 11.07g of 1-bromohexane were charged, the temperature was raised to 80℃and the reaction was allowed to proceed for 9 hours. After neutralization with hydrochloric acid, washing with water and desolventizing under reduced pressure were performed, and the residue was recrystallized from toluene/isopropanol=1:1, whereby crystals were obtained. Then, the melted target (crystal) is dropped onto a metal plate and cooled, thereby obtaining a sheet (melt solidification treatment). By pulverizing the obtained flakes in a mortar, 11.89g (yield: 76%) of pale yellow powder having a melting point of 145℃was obtained.

The obtained compound (pale yellow powder) was subjected to ¹ H-NMR measurement. The pale yellow powder identified as obtained was a powdery compound (particulate ultraviolet absorber) represented by the following formula No.1, according to the following analysis results.

[ chemical formula 8]

Examples 2 to 10

In the same manner as in example 1, different batches of powdery compound No.1 (particulate ultraviolet absorber) represented by the above formula No.1 were obtained.

Example 11

2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -3-hydroxyphenoxy) ethyl 2-ethylhexanoate was synthesized by the following steps.

Into a 300ml four-necked flask, 10.00g of 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- (2-hydroxyethoxy) phenol, 0.25g of p-toluenesulfonic acid monohydrate, 70.00g of toluene and 4.12g of 2-ethylhexanoic acid were charged, and reacted under reflux for 10 hours. Washed with water, and recrystallized from toluene: isopropanol=1:2, thereby obtaining crystals. Then, the melted target (crystal) is dropped onto a metal plate and cooled, thereby obtaining a sheet (melt solidification treatment). The obtained flakes were crushed in a mortar to obtain 9.56g (yield: 72%) of pale yellow powder having a melting point of 108 ℃.

The obtained compound (pale yellow powder) was subjected to ¹ H-NMR measurement. The pale yellow powder obtained was identified as a powdery compound (particulate ultraviolet absorber) represented by the following formula No.2, based on the following analysis results.

[ chemical formula 9]

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Comparative example 1

The crystals obtained in example 1 were pulverized in a mortar without melt-curing treatment to obtain a powdery compound (particulate ultraviolet absorber) represented by the above formula No. 1.

Comparative examples 2 to 5

In the same manner as in comparative example 1, different batches of the powdery compound (particulate ultraviolet absorber) represented by the above formula No.1 were obtained.

Comparative example 6

The flake obtained in example 11 was coarsely pulverized to obtain a granular compound (granular ultraviolet absorber) represented by the above formula No. 2.

The granular ultraviolet absorber obtained in the above manner was evaluated based on the following evaluation items. The evaluation results are shown in table 1.

TABLE 1

(particle size distribution)

The obtained granular ultraviolet absorber was mixed with methanol, and the mixed solution was subjected to ultrasonic dispersion and measurement under wet conditions using a laser diffraction particle size distribution measuring apparatus (Microtrac MT3000 II) to obtain a cumulative 10% particle diameter D ₁₀ Cumulative 90% particle diameter D ₉₀ Cumulative 98% particle diameter D ₉₈ Volume average particle diameter MV and number average particle diameter MN.

(compression granulation property)

The obtained granular ultraviolet absorber was subjected to compression granulation using a briquetting machine, and formed into almond-shaped pellets. The appearance of the obtained briquette was observed, and the compression granulation property was evaluated based on the following evaluation criteria.

O: lamination (breaking up of the agglomerates into layers) does not occur.

X: lamination occurs partially or fully.

(melt kneading Property)

The obtained particulate ultraviolet absorber was blended into 100 parts by mass of an acrylic resin in an amount of 1 part by mass, and melt kneaded and pelletized at 250 ℃ using a biaxial extruder (L/d=30), to obtain particles. Particles were observed when the discharge amount was set to 0.3kg/h, and melt-kneadability was evaluated based on the following evaluation criteria.

O: the resin and the particulate ultraviolet absorber are uniformly dispersed and melt kneaded.

Delta: the resin and the particulate ultraviolet absorber are slightly separated but may be melt kneaded.

X: the resin and the particulate ultraviolet absorber are separated and cannot be melt kneaded.

The obtained granular ultraviolet absorbers of examples 1 and 11 and comparative example 1 were subjected to X-ray diffraction analysis. The evaluation results are shown in tables 2 to 5.

TABLE 2

(X-ray diffraction)

The obtained granular ultraviolet absorber was subjected to powder X-ray diffraction measurement under the following measurement conditions using a Ultima IV (Rigaku, co., ltd.).

(measurement conditions)

X-ray tube ball: cuK alpha ray [ ]

Not removed cukα2

Tube voltage/tube current: 40kV/40mA

Accessories: multifunctional film sample rack

Monochromator: fixing

And (3) a filter: without any means for

Divergence slit: 2/3 degree

Divergent vertical confinement slit: 10mm of

Scattering slit: 1.17mm

Light receiving slit: 0.3 mm

Scan type: continuous scanning

Scanning speed: 4 DEG/min

Sampling width: 0.02 degree

Scanning axis 2 theta/omega

Scanning range: =3° to 90 °

The results of powder X-ray diffraction analysis of the granular ultraviolet absorber of example 1 are shown in fig. 1. The diffraction angles 2θ, d values, relative intensities corresponding to the peaks in fig. 1 are shown in table 3. In Table 3, deg represents the angle, and the threshold value of the peak intensity is set to 1/100 of the strongest peak.

TABLE 3

TABLE 3 Table 3

No.	2θ(deg)	d(A)	Relative intensity
				1	5.58	15.81	100
2	7.23	12.21	3
				3	10.79	8.19	2
4	12.06	7.33	2
				5	12.34	7.17	2
6	14.35	6.17	2
				7	15.53	5.70	8
8	15.88	5.57	3
				9	16.18	5.47	3
10	16.62	5.33	2
				11	17.12	5.17	5
12	20.11	4.41	3
				13	20.82	4.26	2
14	21.69	4.09	7
				15	22.10	4.02	18
16	23.23	3.83	2
				17	23.79	3.74	7
18	24.41	3.64	8
				19	26.11	3.41	3
20	26.80	3.32	3
				21	28.09	3.17	4

The results of powder X-ray diffraction analysis of the granular ultraviolet absorber of example 11 are shown in fig. 2. The diffraction angles 2θ, d values, relative intensities corresponding to the peaks in fig. 2 are shown in table 4. In Table 4, deg represents the angle, and the threshold value of the peak intensity is set to 1/100 of the strongest peak.

The measurement conditions for the powder X-ray diffraction measurement of example 11 were the same as those of example 1 except that the following conditions were used.

Divergence slit: 1/2 degree

Divergent vertical confinement slit: 10mm of

Scattering slit: 0.93mm

Scanning range: =2° to 60 °

TABLE 4

TABLE 4 Table 4

No	2θ(deg)	d(A)	Relative intensity
				1	5.74	15.39	100
2	9.62	9.19	2
				3	9.98	8.85	2
4	10.87	8.13	26
				5	11.69	7.56	8
6	12.61	7.02	2
				7	15.01	5.90	11
8	16.16	5.48	25
				9	17.34	5.11	20
10	18.40	4.82	9
				11	19.03	4.66	9
12	19.49	4.55	11
				13	20.07	4.42	3
14	21.81	4.07	6
				15	22.28	3.99	11
16	23.37	3.80	3
				17	23.78	3.74	8
18	24.26	3.67	10
				19	25.15	3.54	25
20	26.29	3.39	21
				21	27.33	3.26	2
22	27.72	3.22	7
				23	28.06	3.18	2
24	29.44	3.03	3

The results of powder X-ray diffraction analysis of the granular ultraviolet absorber of comparative example 1 are shown in fig. 3. The diffraction angles 2θ, d values, relative intensities corresponding to the peaks in fig. 3 are shown in table 5. In Table 5, the threshold value of the peak intensity is set to 1/100 of the strongest peak.

TABLE 5

TABLE 5

No	2θ(deg)	d(A)	Relative intensity
				1	5.78	15.26	52
2	6.73	13.12	100
				3	10.55	8.38	15
4	11.52	7.67	19
				5	12.07	7.33	16
6	12.99	6.81	3
				7	14.51	6.10	10
8	15.28	5.79	3
				9	15.60	5.67	12
10	15.93	5.56	9
				11	16.37	5.41	11
12	16.68	5.31	15
				13	17.39	5.10	3
14	17.89	4.95	17
				15	19.45	4.56	11
16	20.05	4.42	3
				17	20.90	4.25	25
18	21.43	4.14	24
				19	22.58	3.93	3
20	23.53	3.78	11
				21	24.08	3.69	12
22	24.95	3.57	7
				23	25.40	3.50	2
24	26.40	3.37	8
				25	27.20	3.28	23
26	27.69	3.22	5
				27	28.43	3.14	4
28	31.52	2.84	3

(feeding property)

1kg of the obtained granular ultraviolet absorber was charged into a hopper, and a twin screw type (twin screw type) (manufactured by K-TRON Co., ltd., longitudinal: 25 cm. Times. Outer diameter: 1.4cm, groove width: 2.0cm, groove depth: 0.3 cm) was used to discharge the ultraviolet absorber from the hopper: the material was discharged for 30 minutes at 0.3kg/h (feed test).

Quantitative nature

The amount discharged from the gravimetric feeder (feed amount) was measured every 10 minutes. When the variation in the feed amount was small, the evaluation was "o" and when the variation in the feed amount was large, the evaluation was "x".

Long-term nature

The above feed test was performed in the same manner except that the discharge time condition was changed from 30 minutes to 3 hours. The discharge was continued for 3 hours marked with o and the stop of the operation was performed 3 hours before the lapse of x.

[ preparation of resin composition ]

(production of film)

A mixture obtained by compounding 0.2 part by mass of the obtained particulate ultraviolet absorber of each example with 100 parts by mass of a synthetic resin (polycarbonate resin: manufactured by mitsubishi engineering plastics limited, trade name E-2000) was dissolved in 230 parts by mass of a solvent (toluene/cyclohexane=9/1), thereby preparing a resin composition. A film of 40 μm thickness was produced from the obtained resin composition by a casting method, thereby obtaining a square film test piece having a side length of 2 cm.

After 240 hours, 360 hours and 480 hours, the total light transmittance (%) of the obtained film test piece was measured with a solar climater (83 ℃, no rain, light source carbon arc) and evaluated for light resistance.

From the results of showing high values of the retention (%) after 240 hours, 360 hours and 480 hours, it is understood that excellent light resistance can be achieved by using the particulate ultraviolet light absorber of each example.

It is also known that excellent light resistance can be similarly achieved when a methacrylic resin, a norbornene resin, a polyethylene terephthalate resin, or a polystyrene resin is used as the synthetic resin instead of the polycarbonate resin.

(manufacture of container)

To 100 parts by mass of polyethylene terephthalate (intrinsic viscosity: 0.8 dL/g), 0.3 parts by mass of the obtained particulate ultraviolet absorber of each example was added and mixed, thereby obtaining a resin composition. The obtained resin composition was dried in a gear oven at 160℃for 4 hours, and then, molded into a preform (outer diameter 25mm, weight: 23 g) by an injection molding machine at a molding temperature of 280 ℃. Then, the obtained preform was biaxially stretch blow molded at a mold temperature of 130℃to prepare a plastic bottle having a capacity of 500mL and a thickness of 0.7 mm. The obtained plastic bottle was measured for transmittance of visible light having a wavelength of 500nm and transmittance of ultraviolet light having a wavelength of 400 nm. From the results of high transmittance at a wavelength of 500nm and low transmittance at a wavelength of 400nm, it is known that the obtained plastic bottle (container) can efficiently absorb ultraviolet rays and can sufficiently secure the transmittance of visible light.

(preparation of coating)

Ultraviolet absorbing layer

To 100 parts by mass of a norbornene resin (manufactured by JSR corporation, trade name: ARTON F5023), 0.5 parts by mass of the obtained granular ultraviolet absorber of each example and 2000 parts by mass of methylene chloride as a solvent were mixed to obtain a resin solution (resin composition). The obtained resin solution was cast onto a surface-polished glass plate using a bar coater, preliminary dried at 50℃for 20 minutes, and dried at 90℃for 30 minutes to produce a film having a thickness of 80 to 90. Mu.m, and then a square film test piece (ultraviolet absorbing layer) having a side length of 2cm was obtained.

Fabrication of NIR absorbing layer

A resin solution composed of 100 parts by mass of norbornene resin (product name: ARTON F5023, manufactured by JSR Co., ltd.), 0.3 parts by mass of a diimine compound (product name: IRG-068, manufactured by Japanese Kagaku Co., ltd.) as a near infrared ray absorber, and 2000 parts by mass of methylene chloride as a solvent was cast on a surface-polished glass plate using a bar coater, and was preliminarily dried at 50℃for 20 minutes and dried at 90℃for 30 minutes to prepare a film having a thickness of 50 to 60. Mu.m, and thereafter, a square film test piece having a side length of 2cm was obtained.

The obtained test piece was superimposed with the NIR absorbing layer and the uv absorbing layer, and the uv absorbing layer side was exposed to light for 360 (or 540) hours by a solar climater (Suga Testing Machine, ltd; 83 ℃ C., no rain, light source carbon arc). The transmittance at the maximum wavelength (NIR absorbing layer: 1100 nm) in the NIR region before and after the light fastness test was measured, and the light fastness was evaluated by the attenuation rate of the transmittance (Deltatransmittance).

In each example, it was confirmed from the result that the Δ transmissivity could be reduced that it was effective for photodegradation of the near infrared ray absorber. From this, it is found that the near infrared ray absorber in the near infrared ray absorbing layer is excellent in preventing photodegradation.

The granular ultraviolet absorbers of examples 1 to 11 were excellent in melt-kneading property and compression granulation property as compared with comparative examples 1 to 5, and were excellent in melt-kneading property as compared with comparative example 6, and thus were found to exhibit good powder properties. Further, the compounds of examples 1 to 11 are excellent in ultraviolet absorption characteristics, and therefore can be suitably used as an ultraviolet absorber.

The present application claims priority based on japanese patent application publication nos. 2018-067822, filed 3/30/2018 and 2018, 3/30, the disclosures of which are incorporated herein in their entireties.

Claims (10)

1. A granular ultraviolet absorber comprising a triazine compound, characterized in that,

the triazine compound comprises one or more compounds represented by any one of the following compounds No.1A to No.8A,

the cumulative 10% particle diameter of the particulate ultraviolet absorber in the volume-based particle diameter distribution measured by the wet laser diffraction particle size distribution measurement method is denoted as D ₁₀ The cumulative 90% particle size was designated D ₉₀ In the time-course of which the first and second contact surfaces,

D ₁₀ /D ₉₀ in the range of 0.01 to 0.25,

wherein D is ₁₀ 、D ₉₀ The units of (a) are all μm,

2. a granular ultraviolet absorber comprising a triazine compound, characterized in that,

the triazine compound comprises one or more compounds represented by any one of the following compounds No.1B to No.4B,

the cumulative 10% particle diameter of the particulate ultraviolet absorber in the volume-based particle diameter distribution measured by the wet laser diffraction particle size distribution measurement method is denoted as D ₁₀ The cumulative 90% particle size was designated D ₉₀ In the time-course of which the first and second contact surfaces,

D ₁₀ /D ₉₀ in the range of 0.01 to 0.25,

wherein D is ₁₀ 、D ₉₀ The units of (a) are all μm,

in the compound No. 1B-compound No.4B, R ^A1 、R ^A2 、R ^B1 、R ^B2 、R ^C1 、R ^C2 、R ^D1 And R is ^D2 Are identical or different from each other and represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched alkoxy group having 1 to 4 carbon atoms.

3. The particulate ultraviolet light absorber according to claim 1 or 2, wherein when a volume average particle diameter of the particulate ultraviolet light absorber in a particle diameter distribution based on a volume measured by a wet laser diffraction particle size distribution measurement method is represented as MV and a number average particle diameter thereof is represented as MN,

MV/MN is in the range of 5.0 to 30.0,

wherein the units of MV and MN are μm.

4. The particulate ultraviolet absorber according to claim 1 or 2, wherein a cumulative 98% particle diameter in a particle diameter distribution on a volume basis of the particulate ultraviolet absorber measured by a wet laser diffraction particle size distribution measurement method is denoted as D ₉₈ At time D ₉₈ /D ₉₀ In the range of 1.70 to 5.00,

wherein D is ₉₈ In μm.

5. The particulate ultraviolet absorber according to claim 1 or 2, wherein the triazine compound has a strongest peak in a range of a diffraction angle 2Θ of 5.00 ° or more and 6.50 ° or less in a powder X-ray diffraction analysis chart.

6. The particulate ultraviolet absorber according to claim 5, wherein the maximum width at half maximum of the triazine compound is 0.05 ° or more and 0.20 ° or less.

7. The particulate ultraviolet absorber according to claim 5, wherein when the relative intensity of the strongest peak of the triazine compound is 100, there is no diffraction peak having a relative intensity of 30 to 60 inclusive in a range of 3.0 ° to 45.0 ° in terms of diffraction angle 2θ.

8. The particulate ultraviolet absorber according to claim 5, wherein when the relative intensity of the strongest peak of the triazine compound is 100, there is no diffraction peak having a relative intensity of 1 to 5 inclusive in a range in which the diffraction angle 2θ exceeds 45.0 ° to 60.0 °.

9. A resin composition comprising the granular ultraviolet absorber according to any one of claims 1 to 8.

10. The resin composition according to claim 9, wherein the resin composition contains a synthetic resin.