CN112004905A

CN112004905A - Particulate ultraviolet absorber and resin composition

Info

Publication number: CN112004905A
Application number: CN201980024359.3A
Authority: CN
Inventors: 石间洋辅; 大森宏平
Original assignee: Adeka Corp
Current assignee: Adeka Corp
Priority date: 2018-03-30
Filing date: 2019-03-25
Publication date: 2020-11-27
Anticipated expiration: 2039-03-25
Also published as: JP2021050348A; CN112004905B; JP2024036406A; JP6837148B2; KR20200136006A; TWI818002B; TW201942228A; WO2019188958A1; CN117143396A; JPWO2019188958A1; KR102705591B1

Abstract

The particulate ultraviolet absorber of the present invention is a particulate ultraviolet absorber containing a triazine compound, and the cumulative 10% particle diameter of the particulate ultraviolet absorber in a volume-based particle diameter distribution measured by a wet laser diffraction particle size distribution measuring method is represented by D₁₀(. mu.m), the cumulative 90% particle diameter is denoted as D₉₀In the case of (. mu.m), D₁₀/D₉₀In 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

Various developments have been made to ultraviolet absorbers so far. As such a technique, for example, the 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 of patent document 1, etc.).

Documents of the prior art

Patent document

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

Disclosure of Invention

Problems to be solved by the invention

However, as a result of 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 conducted studies 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 as an index a particle size distribution by a wet laser diffraction particle size distribution measurement method. Further studies were conducted based on these findings, and as a result, it was found that by accumulating 10% of the particle diameter D₁₀Cumulative 90% particle diameter D₉₀Within the given numerical range, the powder characteristics of the above-mentioned particulate ultraviolet absorber can be improved, and the completion of 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 a wet laser diffraction particle size distribution measuring method was denoted as D₁₀(. mu.m), the cumulative 90% particle diameter is denoted as D₉₀At (mum) time，

D₁₀/D₉₀In the range of 0.01 to 0.25.

Further, the present invention provides a resin composition containing the above 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 same.

Drawings

The above objects, other objects, features and advantages will be further explained by the preferred embodiments described below and the following drawings.

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

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

FIG. 3 is an X-ray diffraction chart of the particulate 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-based compound.

[ chemical formula 1]

In the above-mentioned general formula (I),

R¹represents 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 the following general formula (II) tableThe substituents shown in the above formula (I) are,

R²and R³Each independently represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or-O-R, wherein R represents a substituted or unsubstituted linear 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,

R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹and R¹²Each 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,

R¹³and R¹⁴Each independently represents a hydrogen atom or a hydroxyl group.

Wherein R is¹、R²、R³And R represents a substituted or unsubstituted, linear or branched alkyl group having 1 to 20 carbon atoms, R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹And R¹²The methylene group in the substituted or unsubstituted, linear or branched alkyl group having 1 to 8 carbon atoms may be selected from the group consisting of an oxygen atom, a sulfur atom, a carbon-carbon double bond, -CO-O-, -OC-O-, -CO-NH-, -NH-CO-, -CR⁰¹N-and-N-CR⁰²At least one structural substitution of R in the above structure⁰¹And R⁰²Each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms.

[ chemical formula 2]

In the above-mentioned general formula (II),

R²¹and R²²Each independently represents a hydrogen atom, a substituted or unsubstituted, linear 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,

R²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、R³⁰and R³¹Each 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,

R³²and R³³Each independently represents a hydrogen atom or a hydroxyl group,

X¹represents a substituted or unsubstituted straight-chain or branched alkylene group having 8 to 30 carbon atoms,

Y¹and Y²Each independently represents-CO-O-, -O-CO-, -L¹-、-O-L¹O-、-O-L¹-、-L¹-O-CO-、-L¹-CO-O-、-CO-CH＝CH-、-CH＝CH-CO-、-CH＝CH-CO-O-、-CH＝CH-O-CO-、-CO-O-CH＝CH-，

L¹Is 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)¹The site of the attached oxygen atom.

Wherein R is²¹、R²²And R represents a substituted or unsubstituted, linear or branched alkyl group having 1 to 20 carbon atoms, R²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、R³⁰And R³¹A substituted or unsubstituted, linear or branched C1-8 alkyl group and X¹The methylene group in the linear or branched C8-30 alkylene group may be selected from the group consisting of an oxygen atom, a sulfur atom, a carbon-carbon double bond, -CO-O-, -OC-O-, -CO-NH-, -NH-CO-, -CR⁰³N-and-N-CR⁰⁴At least one structural substitution of，R⁰³And R⁰⁴Each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms.

As R in the above general formula (I)¹、R²、R³R in the above general formula (II)²¹、R²²And R represents a substituted or unsubstituted, linear or branched alkyl group having 1 to 20 carbon atoms, and examples thereof include a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a tert-pentyl group, a hexyl group, a heptyl group, an n-octyl group, an isooctyl group, a tert-octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an undecyl group, and a dodecyl.

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

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

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

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

As R in the above general formula (I)⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹And R¹²And R in the above general formula (II)²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、R³⁰And R³¹Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

As R in the above general formula (I)⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹And R¹²And R in the above general formula (II)²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、R³⁰And R³¹Examples 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. 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、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹And R¹²And R in the above general formula (II)²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、R³⁰And R³¹Examples 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, and the position of the unsaturated bond is not limited.

As X in the above general formula (II)¹The substituted or unsubstituted straight-chain or branched alkylene group having 8 to 30 carbon atoms is an alkylene group in which 8 to 30 methylene groups are bonded,Or an alkylene group in which a part of hydrogen atoms of methylene groups is 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)¹Examples of the straight-chain or branched alkylene group having 1 to 8 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, isopropylene, butylene, isobutylene and pentylene.

The triazine compound may contain R in the general formula (I)⁵、R⁶、R⁸、R⁹、R¹¹And R¹²Is 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).

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

[ chemical formula 3]

In the above-mentioned general formula (A),

R^A1represents 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^A2and R^A3The same or different from each other, represents 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^A10the same or different, represent a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched carbon atom3 to 8 alkenyl groups, each of which is a linear or branched alkenyl group,

R^A13and R^A17Identical to or different from each other, represent a hydrogen atom or a hydroxyl group,

wherein R is^A1、R^A2And R^A3A straight-chain or branched alkyl group having 1 to 12 carbon atoms, R^A2And R^A3The methylene group in the straight-chain or branched alkoxy group having 1 to 12 carbon atoms may be selected from the group consisting of an oxygen atom, a sulfur atom, a carbon-carbon double bond, -CO-O-, -OC-O-, -CO-NH-, -NH-CO-, -CR⁰⁵N-and-N-CR⁰⁶At least one structural substitution of R in said structure⁰⁵And R⁰⁶Each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms.

As R in the above general formula (A)^A1、R^A2And R^A3Examples 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.

As R in the above general formula (A)^A2And R^A3Examples 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, cyclohexoxy, 4-methylcyclohexoxy, heptoxy, 2-heptoxy, 3-heptoxy, isoheptoxy, tert-heptoxy, 1-octoxy, isooctyloxy and tert-octoxy.

As R in the above general formula (A)^A1Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclopentyl, cyclohexyl and cycloheptyl.

As R in the above general formula (A)^A1Examples of the aryl group having 6 to 18 carbon atoms or the alkylaryl group having 7 to 18 carbon atoms include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, methyl-substituted phenyl, ethyl-substituted,4-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, 2, 3-isobutylphenyl, 4-isobutylphenyl, 2, 4-di-butylphenyl, 2, 5-dimethylphenyl, biphenyl, 2,4, 5-trimethylphenyl and the like, and examples of the alkylaryl group having 7 to 18 carbon atoms include benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl and the like.

As R in the above general formula (A)^A1、R^A4、R^A7And R^A10Examples 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, and the position of the unsaturated bond is not limited.

As R in the above general formula (A)^A4、R^A7And R^A10Examples 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, and tert-octyl. Among them, methyl is preferable because of its 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 compound nos. 1A to 5A.

[ chemical formula 4]

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

[ chemical formula 5]

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

[ 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^B31each 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. Wherein, among 3 benzene rings linked to the triazine ring, 2 benzene rings represent, in the para-position, 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 above 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^B31Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

In the above 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^B31Examples 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.

In the above 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^B31Examples 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-butenyl, 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 above 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^B31Examples 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, and tert-octyloxy.

In the above 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^B31Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, indenyl, 2-methylphenyl, 3-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl and 4-butylphenylPhenyl 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-pentylphenyl group, 2, 4-dicumylphenyl group, 4-cyclohexylphenyl group, (1,1' -biphenyl) -4-yl group, 2,4, 5-trimethylphenyl, ferrocenyl and the like.

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

[ chemical formula 7]

In the above-mentioned Compound No.1B to Compound No.4B, R^A1、R^A2、R^B1、R^B2、R^C1、R^C2、R^D1And R^D2The alkyl groups may be the same or different and each 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 method for synthesizing the triazine-based compound is not particularly limited, and any synthesis method commonly used for synthesizing a compound having a triazine structure may be used. For example, a method of causing an addition reaction of a phenol derivative or a resorcinol derivative with cyanuric chloride using aluminum trichloride is mentioned. The substituent group on the benzene ring bonded to the triazine ring by a single bond may be introduced after the triazine structure is formed, or may be introduced into the phenol compound or the resorcinol derivative before the triazine structure is formed.

An example of the method for synthesizing the triazine compound is a method in which 2- [ 2-hydroxy-4- (2-hydroxyethyloxy) phenyl ] -4, 6-diphenyl-1, 3, 5-triazine is used as an alcohol component, and the alcohol component is subjected to an esterification reaction or an ester exchange reaction with a corresponding ester-derived compound (carboxylic acid, carboxylic acid halide, carboxylic acid ester), and these reactions may be sequential reactions or may be a one-shot reaction.

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

The triazine compound can be purified after synthesis. As a purification method, distillation, recrystallization, reprecipitation, a method using a filter/adsorbent, or 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, melt-solidification, and the like after purification. These treatments may be used alone or in combination of 2 or more. Thereby, the desired powder properties of the particulate triazine compound can be obtained.

The granular form of the granular ultraviolet absorber of the present embodiment means a powdery form or a granular form. The granular ultraviolet absorber can be used in the form of powder or granule, or processed into granule (ペレット), block, tablet, etc.

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 was measured by a wet laser diffraction particle size distribution measurement method, the cumulative 10% particle size in the particle size distribution based on volume was regarded as D₁₀(. mu.m), the cumulative 90% particle diameter is denoted as D₉₀(. mu.m), and the cumulative 98% particle diameter in the volume-based particle diameter distribution is denoted as D₉₈(μm), the volume average particle diameter in the volume-based particle size distribution is referred to as MV (μm), and the number average particle diameter is referred to as MN (μm).

The inventors found that the wet condition allows the particle size distribution to be measured more stably than the dry condition even for a powder having a relatively wide particle size distribution and containing fine particles.

In the present embodiment, D₁₀/D₉₀For example, the content is in the range of 0.01 to 0.25, preferably 0.02 to 0.20, and more preferably 0.03 to 0.15. By making D₁₀/D₉₀The particle size distribution can be widened in a relatively wide range to be equal to or less than the upper limit, whereby the compression pelletizability and the melt kneadability can be improved. Therefore, a particulate ultraviolet absorber having excellent powder characteristics can be realized. In addition, by making D₁₀/D₉₀When the amount is not less than the lower limit, it is possible to obtain a granular ultraviolet absorber having excellent melt kneadability and excellent production stability.

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

In the present embodiment, D₉₈/D₉₀For example, the range is 1.70 to 5.00, preferably 1.80 to 4.50, and more preferably 1.90 to 4.00. By setting this value within such a numerical range, a particulate ultraviolet absorber having excellent powder characteristics and ultraviolet absorption characteristics can be realized.

In the present embodiment, D₁₀For example, in the range of 8.0 to 22.0. mu.m, preferably 9.0 to 20.0. mu.m, and more preferably 10.0 to 18.0. mu.m. By setting it within such a numerical range, the powder characteristics can be improved.

In the present embodiment, D₉₀For example, in the range of 120.0 to 500.0. mu.m, preferably 125.0 to 450.0. mu.m, and more preferably 130.0 to 400.0. mu.m. 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 or more and 30.0 or less, preferably in the range of 8.0 or more and 28.0 or less, and more preferably in the range of 10.0 or more and 25.0 or less. By setting this value within such a numerical range, a particulate ultraviolet absorber having excellent powder characteristics and ultraviolet absorption characteristics can be realized.

In the present embodiment, D above can be controlled by appropriately selecting, for example, the kind or shape of the triazine compound, the method for producing the triazine compound, and the like₁₀/D₉₀、D₉₈/D₉₀And MV/MN. Wherein, as D₁₀/D₉₀、D₉₈/D₉₀And the MV/MN ratio is controlled to be within a desired range, and examples thereof include processing conditions and the like in which a triazine compound is appropriately used, such as melt-solidification, pulverization, and classification.

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

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

The triazine compound of the present embodiment may have a maximum intensity peak in a powder X-ray diffraction analysis chart in a range of a diffraction angle 2 θ of 5.00 ° to 6.50 °, preferably 5.20 ° to 6.00 °, and more preferably 5.40 ° to 5.80 °. Thereby, the feeding property and the compression pelletizability can be improved, and thus, the triazine compound and the particulate ultraviolet absorber having excellent powder characteristics can be realized.

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

In the powder X-ray diffraction analysis chart of the triazine compound, the full width at half maximum of the maximum intensity peak is, for example, 0.05 ° to 0.20 °, preferably 0.10 ° to 0.19 °, and more preferably 0.15 ° to 0.18 °. By appropriately setting the peak width of the strongest peak (maximum peak) within such a numerical range, a particulate ultraviolet absorber having excellent 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 maximum intensity peak is 100, no diffraction peak having a relative intensity of, for example, 30 or more and 60 or less, preferably 25 or more and 60 or less, more preferably 22 or more and 60 or less, is present in the range having a diffraction angle 2 θ of 3.0 ° or more and 45.0 ° or less. That is, by relatively increasing the peak intensity of the strongest peak, a particulate ultraviolet absorber having excellent 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 set to 100, a diffraction peak having a relative intensity of 1 or more and 5 or less is not present in a range where the diffraction angle 2 θ is, for example, greater than 45.0 ° and 60.0 ° or less, and preferably greater than 45.0 ° and 90.0 ° or less. That is, by setting the region where the fine intensity peak does not exist within an appropriate numerical range, a particulate ultraviolet absorber having excellent powder characteristics and ultraviolet absorption characteristics can be realized.

In the present embodiment, for example, by appropriately selecting the type and shape of the triazine-based compound, the method for producing the triazine-based compound, and the like, the powder X-ray diffraction analysis chart such as the diffraction angle 2 θ of the maximum intensity peak, the full width at half maximum of the maximum intensity peak, and the like can be controlled. Among them, for example, as an element for setting a powder X-ray diffraction analysis pattern such as the diffraction angle 2 θ of the maximum intensity peak and the full width at half maximum of the maximum intensity peak in a desired numerical range, processing conditions such as melt solidification, pulverization, and fractionation, which are appropriately employed for the triazine compound, are exemplified.

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

The resin composition contains the particulate ultraviolet absorber. The resin composition may also contain a synthetic resin. Thereby, desired resin characteristics can be obtained according to various uses.

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 polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, crosslinked polyethylene, ultrahigh molecular weight polyethylene, α -olefin polymers such as polybutene-1 and poly-3-methylpentene, ethylene-vinyl acetate copolymers, polyolefins such as ethylene-ethyl acrylate copolymers and ethylene-propylene copolymers, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylene copolymers, vinyl chloride-vinylidene chloride-vinyl acetate terpolymers, vinyl chloride-acrylic acid ester copolymers, vinyl chloride-maleic acid ester copolymers, polyethylene, halogen-containing resins such as vinyl chloride-cyclohexylmaleimide copolymers; petroleum resin, coumarone resin, polystyrene, polyvinyl acetate, acrylic resin, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral; polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, and polycyclohexanedimethanol terephthalate, aromatic polyesters such as polyalkylene naphthalates such as polyethylene naphthalate and 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, polydioxan, and poly (2-oxetanone); polyamides such as polyphenylene ether, polycaprolactam and polyhexamethylene adipamide, polycarbonates, branched polycarbonates, polyacetals, polyphenylene sulfides, polyurethanes, fiber-based resins, and the like.

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

Examples of the elastomer include fluororesins, silicone resins, silicone rubbers, polyethersulfones, polysulfones, polyphenylene oxides, polyether ketones, polyether ether ketones, and liquid crystal polymers. Further, isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluorine rubber, silicone rubber, and the like can be cited.

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

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

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

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

The amount of the particulate ultraviolet absorber incorporated 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, per 100 parts by mass of the synthetic resin. When the content is not less than the lower limit, a sufficient effect of the particulate ultraviolet absorber can be obtained. When the amount is not more than the above upper limit, desired resin physical properties can be achieved while enhancing the effect of adding the particulate ultraviolet absorber.

In this specification, "to" means to include an upper limit value and a lower limit value unless otherwise specified.

The resin composition of the present embodiment may contain other additive components than 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 (transparentizing agents), 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, delusterants, antifogging agents, precipitation inhibitors, surface treatment agents, fluorescent brighteners, antifungal agents, antibacterial agents, mold release agents, and the like.

Examples of the antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant.

Examples of the phenolic antioxidant 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' -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, 2-tert-butylidenebis (4-methyl-4-hydroxy-5-t-butylbenzyl) isocyanurate, Stearyl (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid methyl ester ] methane, thiodiethylene glycol bis [ (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 1, 6-hexamethylenebis [ (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], bis [3, 3-bis (4-hydroxy-3-tert-butylphenyl) butanoic acid ] ethylene glycol ester, bis [ 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl ] terephthalate, 1,3, 5-tris [ (3, 5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl isocyanurate, 3, 9-bis [1, 1-dimethyl-2- { (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy } ethyl ] -2,4,8, 10-tetraoxaspiro [5,5] undecane, triethylene glycol bis [ (3-t-butyl-4-hydroxy-5-methylphenyl) propionate ], and the like.

Examples of the phosphorus-based antioxidant include trisnonylphenyl phosphite, tris [ 2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylsulfanyl) -5-methylphenyl]Phosphite, tridecyl phosphite, triisodecyl phosphite, trilauryl phosphite, octyldiphenyl phosphite, didecyl monophenyl phosphite, ditridecyl pentaerythritol diphosphite, dinonylphenyl pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4, 6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, tetratridecyl isopropylidenediphenol diphosphite, tetratridecyl-4, 4 '-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, tetradecyl phosphite, ditridecyl-4, 4' -n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, and mixtures thereof, Hexa (tridecyl) -1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2, 4-di-tert-butylphenyl) biphenyl diphosphonite, 9, 10-dihydro-l-9-oxa-10-phosphaphenanthrene-10-oxide, 2' -methylenebis (4, 6-tert-butylphenyl) -2-ethylhexyl phosphite, 2' -methylenebis (4, 6-tert-butylphenyl) -octadecyl phosphite, 2' -ethylenebis (4, 6-di-tert-butylphenyl) fluorophosphite, tris (2- [ (2,4,8, 10-tetra-tert-butylbenzo [ d, f ] dibenzo [ d, f ] s][1,3,2]Dioxaphosphanes

-6-yl) oxy]Ethyl) amine, 2-ethyl-2-butylpropanediol, and 2,4, 6-tri-tert-butylphenol.

Examples of the sulfur-based antioxidant include dialkyl thiodipropionate esters such as dilauryl thiodipropionate, dimyristyl thiodipropionate and distearyl thiodipropionate, and pentaerythritol tetrakis (. beta. -alkylthiopropionic acid) esters.

Examples of the ultraviolet absorbers other than the triazine compounds of the present embodiment include 2-hydroxybenzophenones such as 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, and 5, 5' -methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 2- (2 '-hydroxy-3', 5 '-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, 2- (2 '-hydroxyphenyl) benzotriazoles such as 2- (2' -hydroxy-3 ',5' -dicumylphenyl) benzotriazole, 2 '-methylenebis (4-tert-octyl-6- (benzotriazolyl) phenol), and 2- (2' -hydroxy-3 '-tert-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-amylphenyl-3, 5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate; substituted oxalanilides such as 2-ethyl-2 '-ethoxyoxalanilide and 2-ethoxy-4' -dodecyloxalanilide; cyanoacrylates such as ethyl- α -cyano- β, β -diphenylacrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

Examples of the hindered amine-based light stabilizer include 2,2,6, 6-tetramethyl-4-piperidyl stearate, 1,2,2,6, 6-pentamethyl-4-piperidyl stearate, 2,2,6, 6-tetramethyl-4-piperidyl benzoate, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6, 6-tetramethyl-4-piperidyl) -1,2,3, 4-butane tetracarboxylate, tetrakis (1,2,2,6, 6-pentamethyl-4-piperidinyl) -1,2,3, 4-butanetetracarboxylate, bis (2,2,6, 6-tetramethyl-4-piperidinyl) -ditridecyl-1, 2,3, 4-butanetetracarboxylate, bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) -ditridecyl-1, 2,3, 4-butanetetracarboxylate, bis (1,2,2,4, 4-pentamethyl-4-piperidinyl) -2-butyl-2- (3, 5-di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6, 6-tetramethyl-4-piperidinol/diethyl succinate polycondensate, 1, 6-bis (2,2,6,6) -tetramethyl-4-piperidylamino) hexane/2, 4-dichloro-6-morpholino-s-triazine polycondensate, 1, 6-bis (2,2,6, 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- (2,2,6, 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl ] -1,5,8, 12-tetraazadodecane, 1,5,8, 12-tetrakis [2, 4-bis (N-butyl-N- (1, hindered amine compounds such as 2,2,6, 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl ] -1,5, 8-12-tetraazadodecane, 1,6, 11-tris [2, 4-bis (N-butyl-N- (2,2,6, 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl ] aminoundecane, and 1,6, 11-tris [2, 4-bis (N-butyl-N- (1,2,2,6, 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl ] aminoundecane.

Examples of the near-infrared absorber include polymethine dyes (cyanine dyes), indocyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, naphthol metal complex dyes, squarylium dyes, trisazo dyes, dithiol metal complex salt dyes, pyrylium dyes, thiopyrylium dyes, indoaniline dyes, azoanthraquinone dyes, naphthoquinone dyes, anthraquinone dyes, bis (dithioene) dyes, triphenylmethane dyes, aluminum (aluminum) dyes, and diimmonium dyes. Further, an inorganic near-infrared absorber can 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, metal salts of aromatic phosphates such as sodium bis (2, 4-di-tert-butylphenyl) phosphate, sodium methylenebis (2, 4-di-tert-butylphenyl) phosphate, and aluminum bis [ methylenebis (2, 4-di-tert-butylphenyl) phosphate ] hydroxy, metal salts of aromatic phosphates, dibenzylidene sorbitols such as alkali metal compounds, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, and bis (dimethylbenzylidene sorbitol), metal salts of amino acids, metal salts of rosin, N '-tris [ 2-methylcyclohexyl ] -1,2, 3-propanetricarboxylic acid amide, N' -tricyclohexyl-1, amide compounds such as 3, 5-benzenetricarboxylic acid amide, N' -dicyclohexylnaphthalimide, and 1,3, 5-tris (dimethylisopropylamido) benzene.

Examples of the antistatic agent include cationic antistatic agents such as fatty acid quaternary ammonium salt and polyammonium quaternary salt; anionic antistatic agents such as higher alcohol phosphate ester salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anionic alkyl sulfonates, higher alcohol sulfate ester salts, higher alcohol ethylene oxide adduct sulfate ester salts, and higher alcohol ethylene oxide adduct phosphate ester salts; nonionic antistatic agents such as polyol fatty acid esters, polyethylene glycol phosphate esters and polyoxyethylene alkyl allyl ethers; amphoteric alkylbetaines such as alkyldimethylaminoacetic acid betaine, amphoteric antistatic agents such as imidazoline-type amphoteric activators, and polymeric antistatic agents containing block polymers having an ionomer or polyethylene glycol as a hydrophilic portion.

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 bis stearic acid amide, and ethylene stearic acid amide; metal soap lubricants such as calcium stearate, zinc stearate, magnesium stearate, lead stearate, aluminum stearate, barium stearate/zinc stearate complex, and zinc stearate/calcium stearate complex; hardened fats and oils, glycerin monostearate, butyl stearate, pentaerythritol stearate, stearyl stearate and other ester lubricants.

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

Examples of the light-absorbing pigment include cyanine compounds, quinoline compounds, coumarin compounds, thiazole compounds, cyanine compounds (オキソノール series), azulene compounds, squarylium compounds, azomethine compounds, azo compounds, benzylidene compounds, xanthene compounds, phthalocyanine compounds, and dithiol metal complex compounds.

Examples of the filler include 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, metal silicates such as 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.

As the pigment, commercially available pigments can be used, examples thereof 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, 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 dyes include azo dyes, anthraquinone dyes, indigoid 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.

Examples of the metal soap include salts of metals such as lithium, sodium, potassium, magnesium, calcium, aluminum hydroxide, barium, and zinc, and saturated or unsaturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid.

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 or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; copolymers of the above-mentioned alkyl methacrylate with alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate; copolymers of the above-mentioned alkyl methacrylates with aromatic vinyl compounds such as styrene, α -methylstyrene, vinyltoluene and the like; copolymers of the above alkyl methacrylates with vinyl nitrile compounds such as acrylonitrile and methacrylonitrile.

Examples of the flame retardant and the flame retardant aid include antimony oxides such as triazine ring-containing compounds, metal hydroxides, other inorganic phosphorus, halogen flame retardants, silicone flame retardants, phosphate flame retardants, condensed phosphate flame retardants, intumescent flame retardants, and antimony trioxide, other inorganic flame retardant aids, and organic flame retardant aids.

Examples of the triazine ring-containing compound include melamine, melamine diamide (Ammeline), benzoguanamine, acetoguanamine, orthophthalguanamine, melamine cyanurate, melamine pyrophosphate, butenediguanamine, norbornenediguanamine, methylenebiguanamine, ethylenedimelamine, trimethylenedimelamine, tetramethylenedimelamine, hexamethylenedimelamine, 1, 3-hexenedimelamine, and the like.

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

Examples of the phosphate flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris (dichloropropyl) phosphate, triphenyl phosphate, tricresyl phosphate, tolyldiphenyl phosphate, trixylyl phosphate, octyldiphenyl phosphate, ditolyl diphenyl phosphate, triisopropylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tert-butylphenyl diphenyl phosphate, bis (tert-butylphenyl) phenyl phosphate, tris (tert-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 (ditolyl phosphate), and bisphenol a bis (diphenyl phosphate), and examples of the intumescent flame retardant include ammonium (poly) phosphate salts or amine salts such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, ammonium pyrophosphate, melamine pyrophosphate, and piperazine pyrophosphate.

Examples of the other inorganic flame retardant aid 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 Shikugaku Kogyo Co., Ltd.) and KYOWAMAG150 (magnesium oxide: manufactured by Kyowa Kagaku Co., Ltd.) can be used.

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

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

Examples of the blowing agent include decomposition type organic blowing agents such as azodicarbonamide, azobisisobutyronitrile, p '-oxybisbenzenesulfonylhydrazide, n' -dinitrosopentamethylenetetramine, p-toluenesulfonyl semicarbazide, and trihydrazinotriazine, and decomposition type 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, disalicylic acid hydrazide, dodecanedioic acid bis (2- (2-hydroxybenzoyl) hydrazide), bis (3- (3, 5-di-tert-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, tetramethylisophthaloyl di-t-butyl hydroperoxide, tetramethylisophthaloyl dicumyl hydroperoxide, alkanolamines such as diethanolamine and triethanolamine, hexamethylenediamine, 4' -diaminodiphenylmethane and the like.

Examples of the epoxy-based stabilizer include compounds having an aliphatic, aromatic, alicyclic, araliphatic or heterocyclic structure and an epoxy group as a side chain. The epoxy group is preferably bonded 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 monoester. Commercially available epoxy stabilizers include, for example, those available under the product names "ADK CIZER O-130P", "ADK CIZER O-180A", "ADK CIZER D-32", "ADK CIZER EP-13" and "ADK CIZER FEP-13" from ADEKA, Inc.

The matting agent is preferably silica fine particles. Examples of the fine particles of silica include AEROSIL R972, R972V, R974, R812, 200V, 300, R202, OX50, and TT600 (manufactured by AEROSIL co., ltd.), and from the viewpoint of a large effect of reducing the friction coefficient while keeping the haze of the film low, AEROSIL200V, AEROSIL R972V, and AEROSIL R812 are preferable.

Examples of the antifogging agent include glycerin fatty acid esters, alkyl diethanolamines, and alkyl diethanolamines fatty acid esters.

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 γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, and γ - (2-aminoethyl) aminopropyltrimethoxysilane.

Examples of the epoxy resin contained in the surface treatment agent include a novolak type epoxy resin and a bisphenol type epoxy resin, and a novolak type epoxy resin is 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 treatment agent may contain components such as a urethane resin, an acrylic resin, an antistatic agent, a lubricant, and a water repellent within a range not impairing the performance, in addition to the above aminosilane compound and epoxy resin. Further, examples of the other surface-treating agent include epoxy resins other than novolak type and bisphenol type, coupling agents, and the like.

The fluorescent whitening agent is a compound that absorbs ultraviolet rays of sunlight or artificial light, converts the ultraviolet rays into violet to blue visible light, and then emits the visible light to promote the whiteness and bluish property of the molded article. Examples of the fluorescent whitening agent include benzoxazole compounds C.I. fluorescent brightener Brightner 184; coumarin-based compound c.i. fluorescent Brightner 52; diaminostyrene disulfonic acid compounds c.i Fluorescent Brightner24, 85, 71, etc.

Examples of the antifungal agent include organic antifungal agents such as nitrogen-and sulfur-containing, organic bromine-containing, nitrogen-containing, and arsenic-containing agents, 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 and calcium silicate-based agents containing 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.

As an example of the method for producing the resin composition, there can be mentioned a method in which the respective components such as the granular ultraviolet absorber of the present embodiment, the synthetic resin, and other additive components as needed are premixed in various mixers such as a drum mixer and a henschel mixer, and then melt-kneaded using a banbury mixer, a roll, a brabender mixer, a uniaxial kneader, a biaxial kneader, a kneader, or the like.

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

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

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

A molded article can be obtained by molding the resin composition of the present embodiment.

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

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

In the resin composition of the present embodiment, the particulate ultraviolet absorber of the present embodiment, the synthetic resin used as the binder resin, and other additive components as necessary are dissolved 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. The resin varnish may be used in the form of an emulsion in which a powdery ultraviolet absorber is dispersed, using an emulsifier, if necessary.

The method for producing the resin varnish is not particularly limited, and all the components may be mixed at the same time, or the particulate ultraviolet absorber of the present embodiment and other additional components may be mixed in advance, and the resulting 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 cast film method, for example. In addition, the above resin varnish may 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 range of industrial fields such as electric/electronic/communication, agriculture, forestry and fisheries, mining, construction, food, fiber, clothing, medical treatment, coal, petroleum, rubber, leather, automobiles, precision equipment, wood, building materials, civil engineering, furniture, printing, musical instruments, and the like.

More specific examples of the applications include printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, copiers, facsimiles, ECRs (electronic cash registers), calculators, electronic notepads, cards, holders, office automation equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, home appliances such as home ovens, televisions, video recorders, video cameras, radio cassette recorders, audio recorders, mini-discs, CD players, speakers, AV equipment such as liquid crystal displays, connectors, relays, capacitors, switches, printed boards, coil frames, semiconductor packaging materials, LED packaging materials, electric wires, cables, transformers, deflection coils, distribution boards, electric and electronic parts and communication equipment such as clocks, interior and exterior materials for automobiles, films for plate making, adhesive films, exterior materials for automobiles, and exterior materials for automobiles, Bottles, food containers, food packaging films, pharmaceutical/medicinal packaging films, product packaging films, agricultural sheets, greenhouse films, and the like.

Specific applications include seats (fillers, exterior materials, etc.), seat belts, ceilings, compatible covers, armrests, door trims, rear seal trays, carpets, mats, sun visors, wheel covers, mattress covers, airbags, insulating materials, hand pull rings, hand pull tapes, wire coating materials, electrical insulating materials, paints, coating materials, covering materials, floor materials, corners, carpets, wallpaper, wall materials, exterior materials, interior materials, roof materials, deck materials, wall materials, column materials, floors, barrier materials, frames and decorative materials, window and door-shaped materials, sidings, terraces, balconies, sound-proof panels, heat-insulating panels, window materials, automobiles such as vehicles, ships, airplanes, buildings, houses and building materials, civil engineering materials, clothing, curtains, bed sheets, non-woven fabrics, plywood, wood materials, and the like, Synthetic fiber boards, carpets, entrance mats, sheets, buckets, hoses, containers, glasses, cases, goggles, ski boards, rackets, tents, articles of daily use such as musical instruments, sporting goods, and the like. In addition to these, paints, cosmetics, and the like can be cited.

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

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 being molded into a sheet or a film. The optical material is useful as 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 a field emission display, and particularly useful as an optical film such as an optical correction film or a light emitter protective film of a liquid crystal display device or an organic EL display using an organic material having poor ultraviolet resistance in a display element. Examples of applications of the liquid crystal display device include a polarizing plate protective film or 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 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 particularly, the liquid crystal display device is suitably applied to an optical film or sheet provided on the outer surface side of a polarizing plate in contact with a liquid crystal display element, or a polarizing plate protective film or 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-described configurations may be adopted.

Examples

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

[ preparation of particulate ultraviolet absorber ]

(example 1)

2,4, 6-tris [ 2-hydroxy-3-methyl-4-hexyloxyphenyl ] triazine is 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, the reaction mixture was washed with water, desolventized under reduced pressure, and the residue was recrystallized from toluene/isopropanol at a ratio of 1: 1, whereby crystals were obtained. Then, the molten object (crystal) is dropped onto a metal plate and cooled to obtain a sheet (melt-solidification process). By crushing the obtained flakes in a mortar, 11.89g (yield: 76%) of a pale yellow powder having a melting point of 145 ℃ was obtained.

The compound obtained (pale yellow powder) was subjected to¹H-NMR measurement. The pale yellow powder obtained was identified as a powdery compound (granular 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 the powdery compound No.1 (granular ultraviolet absorber) represented by the above formula No.1 were obtained.

(example 11)

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

A300 ml four-necked flask was charged with 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, and reacted at reflux for 10 hours. Washed with water, and recrystallized from toluene and isopropanol 1:2, thereby obtaining crystals. Then, the molten object (crystal) is dropped onto a metal plate and cooled, thereby obtaining a thin sheet (melt-solidification process). The obtained flakes were crushed in a mortar to obtain 9.56g (yield: 72%) of a pale yellow powder having a melting point of 108 ℃.

The compound obtained (pale yellow powder) was subjected to¹H-NMR measurement. The pale yellow powder obtained was identified as a powdery compound (granular ultraviolet absorber) represented by the following formula No.2 according to the following analysis results.

[ chemical formula 9]

Comparative example 1

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

Comparative example 6

The flakes obtained in example 11 were coarsely pulverized to obtain a particulate compound (particulate ultraviolet absorber) represented by the above formula No. 2.

The granular ultraviolet absorbers obtained in the above manner were 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 added to methanol and mixed, and the mixed solution was subjected to ultrasonic dispersion and measurement under wet conditions using a laser diffraction particle size distribution measuring apparatus (Microtrac MT3000II), thereby obtaining a cumulative 10% particle diameter D₁₀Cumulative 90% particle diameter D₉₀Cumulative 98% particle diameter D₉₈Volume average particle diameter MV and number average particle diameter MN.

(compression granulation Property)

The obtained granular ultraviolet absorber was compressed and granulated by a briquetting machine to form almond-shaped briquettes. The appearance of the resulting agglomerate was observed, and compression pelletizability was evaluated based on the following evaluation criteria.

O: no lamination (phenomenon of breaking up of agglomerates into layers) occurred.

X: some or all of the lamination occurs.

(melt kneading Property)

The obtained granular ultraviolet absorber was mixed with 100 parts by mass of an acrylic resin in an amount of 1 part by mass, and melt-kneaded at 250 ℃ using a twin-screw extruder (L/D30) to obtain granules. The pellets when the discharge amount was set to 0.3kg/h were observed, and melt-kneadability was evaluated based on the following evaluation criteria.

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

And (delta): the resin and the particulate ultraviolet absorber are slightly separated but may be melt kneaded.

X: the resin and the granular 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 using Ultima IV (Rigaku, ltd.) under the following measurement conditions.

(measurement conditions)

X-ray tube ball: CuK alpha ray (C:

without removal of CuK α 2)

Tube voltage/tube current: 40kV/40mA

Accessories: multifunctional film sample holder

A monochromator: fixing

A filter: is free of

Divergent slit: 2/3 degree

Divergent vertical restriction slit: 10mm

Scattering slit: 1.17mm

Light receiving slit: 0.3 mm

The scanning type is as follows: continuous scanning

Scanning speed: 4 °/min

Sampling width: 0.02 degree

Scanning axis 2 theta/omega

Scanning range: 3-90 °

Fig. 1 shows the results of the powder X-ray diffraction analysis of the particulate ultraviolet absorber of example 1. Diffraction angle 2 θ, d value, and relative intensity corresponding to each peak in fig. 1 are shown in table 3. In table 3, deg represents °, and the threshold value of the peak intensity is set to 1/100 of the strongest peak.

[ Table 3]

TABLE 3

No.	2θ(deg)	d(A)	Relative strength
				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

Fig. 2 shows the results of the powder X-ray diffraction analysis of the particulate ultraviolet absorber of example 11. Table 4 shows diffraction angle 2 θ, d value, and relative intensity corresponding to each peak in fig. 2. In table 4, deg represents °, 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.

Divergent slit: 1/2 degree

Divergent vertical restriction slit: 10mm

Scattering slit: 0.93mm

Scanning range: 2-60 degree

[ Table 4]

TABLE 4

No	2θ(deg)	d(A)	Relative strength
				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

Fig. 3 shows the results of the powder X-ray diffraction analysis of the particulate ultraviolet absorber of comparative example 1. Table 5 shows diffraction angle 2 θ, d value, and relative intensity corresponding to each peak in fig. 3. 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 strength
				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 gravimetric feeder (a double-screw type twin-screw manufactured by K-TRON, longitudinal: 25 cm. times. outer diameter: 1.4cm, groove width: 2.0cm, and groove depth: 0.3 cm) was used to discharge: the material was discharged at 0.3kg/h for 30 minutes (feeding test).

Quantitative Property

The amount discharged from the gravimetric feeder (feed amount) was measured every 10 minutes over time. 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 property

The above-described feeding test was performed in the same manner except that the discharge time condition was changed from 30 minutes to 3 hours. The case where the discharge continued for 3 hours was marked with ∘ and the case where the operation was stopped before 3 hours elapsed was marked with x.

[ preparation of resin composition ]

(production of film)

A resin composition was prepared by dissolving 0.2 parts by mass of the obtained granular ultraviolet absorber of each example in 230 parts by mass of a solvent (toluene/cyclohexane ═ 9/1) relative to 100 parts by mass of a synthetic resin (polycarbonate resin: manufactured by mitsubishi engineering plastics co., ltd., trade name E-2000). From the obtained resin composition, a film having a thickness of 40 μm was produced by a casting method, thereby obtaining a square film test piece having a side of 2 cm.

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

As is apparent from the results that the retention (%) after 240 hours, 360 hours, and 480 hours showed high values, excellent light resistance can be achieved by using the particulate ultraviolet absorbers of the respective examples.

It is also found that 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, excellent light resistance can be similarly achieved.

(production of Container)

To 100 parts by mass of polyethylene terephthalate (intrinsic viscosity: 0.8dL/g), 0.3 part by mass of the obtained granular ultraviolet absorbers of each example was added and mixed to obtain 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: 23g) by an injection molding machine at a molding temperature of an injection temperature of 280 ℃. Next, the preform obtained was subjected to biaxial stretch blow molding at a mold temperature of 130 ℃, to produce a plastic bottle having a capacity of 500mL and a thickness of 0.7 mm. The transmittance of visible light having a wavelength of 500nm and the transmittance of ultraviolet light having a wavelength of 400nm were measured for the obtained plastic bottles. From the results that the transmittance at a wavelength of 500nm was high and the transmittance at a wavelength of 400nm was low, it was found that the obtained plastic bottle (container) can efficiently absorb ultraviolet rays and can sufficiently ensure the transmittance of visible light.

(preparation of coating Material)

Ultraviolet absorbing layer

To 100 parts by mass of norbornene resin (product name: ARTON F5023, manufactured by JSR corporation), 0.5 parts by mass of the obtained granular ultraviolet absorbers of each example and 2000 parts by mass of dichloromethane as a solvent were mixed to obtain a resin solution (resin composition). The obtained resin solution was cast on a glass plate with a polished surface using a bar coater, preliminarily dried at 50 ℃ for 20 minutes and at 90 ℃ for 30 minutes to prepare a film having a thickness of 80 to 90 μm, and then a square film test piece (ultraviolet absorbing layer) having a side length of 2cm was obtained.

Preparation of NIR-absorbing layers

A resin solution composed of 100 parts by mass of norbornene resin (manufactured by JSR corporation, trade name: ARTON F5023), 0.3 parts by mass of diimine compound (manufactured by Nippon chemical Co., Ltd., trade name: IRG-068) as a near infrared ray absorber, and 2000 parts by mass of methylene chloride as a solvent was cast on a glass plate having a polished surface using a bar coater, 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 μm, and thereafter, a square film test piece having a side length of 2cm was obtained.

The test piece obtained by stacking the obtained NIR absorbing layer and the ultraviolet absorbing layer was exposed to test light from the ultraviolet absorbing layer side for 360 (or 540) hours by a heliometer (dega Testing Machine, 83 ℃, no rain, light source carbon arc). Transmittance at the maximum wavelength (NIR absorbing layer: 1100nm) in the NIR region before and after the light resistance test was measured, and the light resistance was evaluated by the attenuation ratio of transmittance (Δ transmittance).

In each of the examples, it was confirmed from the result that the Δ transmittance can be reduced that the effect on the light deterioration of the near infrared ray absorber was obtained. From this, it is found that the near-infrared absorbent in the near-infrared absorbing layer is excellent in preventing the photo-deterioration.

The granular ultraviolet absorbers of examples 1 to 11 were excellent in melt kneadability and compression pelletizability as compared with comparative examples 1 to 5, and were excellent in melt kneadability as compared with comparative example 6, and thus, they were found to exhibit good powder characteristics. In addition, the compounds of examples 1 to 11 have excellent ultraviolet absorption characteristics, and thus can be suitably used as ultraviolet absorbers.

The present application claims priority based on japanese application laid-open No. 2018-067822 filed on 3/30/2018 and japanese application laid-open No. 2018-067830 filed on 3/30/2018, the entire disclosures of which are incorporated herein.

Claims

1. 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 a wet laser diffraction particle size distribution measuring method was denoted as D₁₀The cumulative 90% particle diameter was designated as D₉₀When the temperature of the water is higher than the set temperature,

D₁₀/D₉₀in the range of 0.01 to 0.25 inclusive,

wherein D is₁₀、D₉₀The units of (A) are all mum.

2. The particulate ultraviolet absorber according to claim 1, wherein the triazine compound comprises a compound represented by the following general formula (I),

in the general formula (I), the compound (I),

R¹represents 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),

R²and R³Each independently represents a hydrogen atom, a substituted or unsubstituted, linear or branched alkyl group having 1 to 20 carbon atoms, or-O-RR 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,

R¹³and R¹⁴Each independently represents a hydrogen atom or a hydroxyl group,

wherein R is¹、R²、R³And R represents a substituted or unsubstituted, linear or branched alkyl group having 1 to 20 carbon atoms, R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹And R¹²The methylene group in the substituted or unsubstituted, linear or branched alkyl group having 1 to 8 carbon atoms is selected from the group consisting of an oxygen atom, a sulfur atom, a carbon-carbon double bond, -CO-O-, -OC-O-, -CO-NH-, -NH-CO-, -CR⁰¹N-and-N-CR⁰²At least one or more of the structures (A) to (B) in which R is substituted or unsubstituted⁰¹And R⁰²Each independently represents a straight-chain or branched alkyl group having 1 to 8 carbon atoms,

in the general formula (II) described above,

R²¹and R²²Each independently represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or-O-R, wherein R represents a substituted or unsubstituted linear 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,

L¹Is 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)¹The site of the attached oxygen atom(s),

wherein R is²¹、R²²And R represents a substituted or unsubstituted, linear or branched alkyl group having 1 to 20 carbon atoms, R²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、R³⁰And R³¹A substituted or unsubstituted, linear or branched C1-8 alkyl group and X¹The methylene group in the straight chain or branched alkylene group having 8 to 30 carbon atoms is selected from the group consisting of an oxygen atom, a sulfur atom, a carbon-carbon double bond, -CO-O-, -OC-O-, -CO-NH-, -NH-CO-, -CR⁰³N-and-N-CR⁰⁴At least one or more of the structures of-substituted or unsubstituted, R⁰³And R⁰⁴Each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms.

3. The particulate ultraviolet absorber according to claim 1 or 2, wherein the triazine compound comprises a compound represented by the following general formula (A),

in the general formula (A) described above,

R^A4、R^A7、R^A10the same or different from each other, 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,

wherein R is^A1、R^A2And R^A3A straight-chain or branched alkyl group having 1 to 12 carbon atoms, R^A2And R^A3The methylene group in the straight-chain or branched alkoxy group having 1 to 12 carbon atoms is selected from the group consisting of an oxygen atom, a sulfur atom, a carbon-carbon double bond, -CO-O-, -OC-O-, -CO-NH-, -NH-CO-, -CR⁰⁵N-and-N-CR⁰⁶At least one or more of the structures (A) to (B) in which R is substituted or unsubstituted⁰⁵And R⁰⁶Each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms.

4. The particulate ultraviolet absorber according to claim 1 or 2, wherein the triazine-based compound comprises one or more compounds represented by any one of the following compounds No.1A to No.8A,

5. the particulate ultraviolet absorber according to claim 1 or 2, wherein the triazine compound comprises a compound represented by the following general formula (B),

in the general formula (B) described above,

R^B4、R^B5、R^B7～R^B9、R^B10～R^B12、R^B23、R^B24、R^B26～R^B28、R^B29～R^B31each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and n represents an integer of 8 to 14; wherein, in 3 benzene rings connected with the triazine ring, para positions of 2 benzene rings represent a hydrogen atom, an alkyl group having 1-20 carbon atoms or an alkoxy group having 1-20 carbon atoms, and one of ortho positions represents a hydrogen atom or a hydroxyl group.

6. The particulate ultraviolet absorber according to claim 5, wherein the triazine-based compound comprises one or more compounds represented by any one of the following compounds No.1B to No.4B,

in the compounds No.1B to No.4B, R is^A1、R^A2、R^B1、R^B2、R^C1、R^C2、R^D1And R^D2The alkyl groups are the same or different and each represents 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.

7. The particulate ultraviolet absorber according to any one of claims 1 to 6, wherein when a volume average particle diameter and a number average particle diameter of the particulate ultraviolet absorber in a volume-based particle diameter distribution measured by a wet laser diffraction particle size distribution measurement method are MV and MN, respectively,

MV/MN is in the range of 5.0 or more and 30.0 or less,

wherein the unit of MV and MN is μm.

8. The particulate ultraviolet absorber according to any one of claims 1 to 7, wherein a cumulative 98% particle diameter in a volume-based particle diameter distribution of the particulate ultraviolet absorber measured by a wet laser diffraction particle size distribution measurement method is represented by D₉₈When D is₉₈/D₉₀In the range of 1.70 to 5.00 inclusive,

wherein D is₉₈In μm.

9. The particulate ultraviolet absorber according to any one of claims 2 to 4, wherein the triazine compound has a maximum intensity peak in a powder X-ray diffraction analysis chart in a range where a diffraction angle 2 θ is 5.00 ° or more and 6.50 ° or less.

10. The particulate ultraviolet absorber according to claim 9, wherein the full width at half maximum of the strongest peak of the triazine-based compound is 0.05 ° or more and 0.20 ° or less.

11. The particulate ultraviolet absorber according to claim 9 or 10, wherein a diffraction peak having a relative intensity of 30 or more and 60 or less is absent in a range where a diffraction angle 2 θ is 3.0 ° or more and 45.0 ° or less, assuming that the relative intensity of the strongest peak of the triazine-based compound is 100.

12. The particulate ultraviolet absorber according to any one of claims 9 to 11, wherein, assuming that the relative intensity of the strongest peak of the triazine-based compound is 100, no diffraction peak having a relative intensity of 1 or more and 5 or less is present in a range in which the diffraction angle 2 θ is more than 45.0 ° and 60.0 ° or less.

13. A resin composition comprising the particulate ultraviolet absorber as defined in any one of claims 1 to 12.

14. The resin composition according to claim 13, wherein the resin composition contains a synthetic resin.