JP2021050345A - Granular ultraviolet absorber and resin composition - Google Patents

Abstract

To provide a granular ultraviolet absorber having excellent powder characteristics.SOLUTION: A granular ultraviolet absorber according to the present invention is a granular ultraviolet absorber that contains a triazine-based compound and that satisfies a particle size distribution, wherein: the amount of residue on a sieve having 4.0 mm openings is 0.3-1.5 wt.%; the amount of residue on a sieve having 2.8 mm openings is 5.0-25.0 wt.%; the amount of residue on a sieve having 2.0 mm openings is 25.0-35.0 wt.%; and the amount of residue on a sieve having 1.0 mm openings is 35.0-55.0 wt.%, the amounts of residue being calculated on the basis of a prescribed procedure for measuring the amount of residue.SELECTED DRAWING: None

Description

The present invention relates to granular UV absorbers and resin compositions.

So far, various developments have been made in UV absorbers. As a technique of this kind, for example, the technique described in Patent Document 1 is known. Patent Document 1 describes that a triazine-based compound obtained by crystallization is used as an ultraviolet absorber (paragraph 0102 of Patent Document 1, etc.).

Japanese Unexamined Patent Publication No. 2011-6517

However, as a result of the examination by the present inventor, it has been found that there is room for improvement in the powder characteristics of the ultraviolet absorber described in Patent Document 1.

As a result of further studies, the present inventor has found that the powder characteristics of the granular ultraviolet absorber containing a triazine-based compound can be appropriately controlled by using the particle size distribution based on the sieve as a guideline. As a result of further diligent research based on these findings, the residual amount of each sieve of 4.0 mm mesh sieve, 2.8 mm mesh sieve, 2.0 mm mesh sieve, and 1.0 mm mesh sieve is within a predetermined numerical range. It has been found that the powder properties of the above-mentioned granular ultraviolet absorber are improved by setting the content to the inside, and the present invention has been completed.

According to the present invention
A granular UV absorber containing a triazine compound.
Calculated based on the following procedure for measuring the amount of sieve residue,
The residual amount of the sieve on the sieve having a mesh size of 4.0 mm is 0.3 wt% or more and 1.5 wt% or less.
The residual amount of the sieve on the sieve having a mesh size of 2.8 mm is 5.0 wt% or more and 25.0 wt% or less.
The amount of sieve residue on the sieve having a mesh size of 2.0 mm is 25.0 wt% or more and 35.0 wt% or less.
Provided is a granular ultraviolet absorber that satisfies a particle size distribution in which the amount of residual sieve residue on a sieve having a mesh size of 1.0 mm is 35.0 wt% or more and 55.0 wt% or less.
(Measurement procedure for sieve residue)
A predetermined amount (g) of the granular ultraviolet absorber is sieved in this order using a 4.0 mm mesh sieve, a 2.8 mm mesh sieve, a 2.0 mm mesh sieve, and a 1.0 mm mesh sieve. Is performed, the residual weight (g) of the granular ultraviolet absorber remaining on each sieve is measured, and the weight ratio (wt%) of the residual weight to the predetermined amount is calculated as the sieve residual amount.

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

According to the present invention, a granular ultraviolet absorber having excellent powder properties and a resin composition using the same are provided.

The above-mentioned objectives and other objectives, features and advantages will be further clarified by the preferred embodiments described below and the accompanying drawings below.

It is an X-ray diffraction pattern of the granular ultraviolet absorber of Example 1. It is an X-ray diffraction pattern of the granular ultraviolet absorber of Comparative Example 1.

The granular ultraviolet absorber of the present embodiment contains a triazine-based compound.
The triazine-based compound preferably contains a compound represented by the following general formula (I). These may be used alone or in combination of two or more.
The granular ultraviolet absorber may be composed only of the following triazine compounds.

In the above general formula (I),
R ¹ is 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, and 7 carbon atoms. Represents an alkylaryl group of ~ 20, an arylalkyl group having 7 to 20 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a substituent represented by the following general formula (II).
R ² and R ³ independently represent a hydrogen atom, a substituted or unsubstituted, linear or branched alkyl group having 1 to 20 carbon atoms, or −OR, and this R is substituted or absent. Substituent linear or branched alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, alkylaryl groups with 7 to 20 carbon atoms, Alternatively, it represents an arylalkyl group having 7 to 20 carbon atoms.
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are independently hydrogen atoms, halogen atoms, substituted or unsubstituted, linear or branched carbons, respectively. Represents an alkyl group with 1 to 8 atoms or a linear or branched alkenyl group with 2 to 8 carbon atoms.
R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a hydroxy group.

However, substituted or unsubstituted, linear or branched alkyl groups having 1 to 20 carbon atoms represented by ^{R 1} , R ² , R ^{3 and R, R 4} , R ⁵ , R ⁶ , R ⁷ , R. The methylene groups in the substituted or unsubstituted, linear or branched alkyl groups having 1 to 8 carbon atoms represented by ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 are oxygen atoms, sulfur atoms, and carbon atoms.} -Carbon double bond, -CO-, -CO-O-, -OC-O-, -CO-NH-, -NH-CO-, -CR ⁰¹ = N- and -N = CR ^02- It may be substituted with at least one structure, and R ⁰¹ and R ⁰² in the structure each independently represent a linear or branched alkyl group having 1 to 8 carbon atoms.

In the above general formula (II),
R ²¹ and R ²² independently represent a hydrogen atom, a substituted or unsubstituted, linear or branched alkyl group having 1 to 20 carbon atoms, or −OR, and this R is substituted or absent. Substituent linear or branched alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, alkylaryl groups with 7 to 20 carbon atoms, Alternatively, it represents an arylalkyl group having 7 to 20 carbon atoms.
R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are independently hydrogen atoms, halogen atoms, substituted or unsubstituted, linear or branched carbons, respectively. Represents an alkyl group with 1 to 8 atoms, or a linear or branched alkenyl group with 2 to 8 carbon atoms.
R ³² and R ³³ independently represent a hydrogen atom or a hydroxy group, respectively.
X ¹ represents a substituted or unsubstituted, linear or branched alkylene group having 8 or more and 30 or less carbon atoms.
Y ¹ and ^{Y 2} each ^{independently, -CO-O -, - O} -CO -, - L 1 -, - O-L 1 O -, - O-L 1 -, - L 1 -O-CO -, -L ^1- CO-O-, -CO-CH = CH-, -CH = CH-CO-, -CH = CH-CO-O-, -CH = CH-O-CO-, -CO- Represents O-CH = CH-
L ¹ is a linear or branched alkylene group having 1 to 8 carbon atoms.
m and n each independently represent an integer from 0 to 8.
* Represents a bond with an oxygen atom connected to ^{R 1} in the formula (I).

However, substituted or unsubstituted, linear or branched alkyl groups having 1 to 20 carbon atoms represented by ^{R 21} , R ^{22 and R, R 23} , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R. ²⁸ , R ²⁹ , R ³⁰ and R ³¹ substituted or unsubstituted, linear or branched alkyl groups having 1 to 8 carbon atoms and linear or branched alkyl groups ^{represented by X 1} having 8 carbon atoms. The methylene groups in the above 30 or less alkylene groups are oxygen atom, sulfur atom, carbon-carbon double bond, -CO-, -CO-O-, -OC-O-, -CO-NH-, -NH-. It may be substituted with at least one structure selected from CO-, -CR ⁰³ = N- and -N = CR ^{04- , where R 03} and R ⁰⁴ are independently linear or branched carbons, respectively. Represents an alkyl group having 1 to 8 atoms.

Substituent or unsubstituted, linear or branched carbon atoms represented by R ¹ , R ² , R ^{3 in} the general formula (I) and R ²¹ , R ^{22 and R in the general formula (II).} Examples of the alkyl group of number 1 to 20 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, n-octyl, isooctyl, and the like. Examples thereof include linear or branched alkyl groups such as tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl and dodecyl.

Examples of the cycloalkyl group having 3 to 20 carbon atoms represented by ^{R 1} and R in the general formula (I) include cyclopropyl, cyclopentyl, cyclohexyl, and cycloheptyl.

The general formula (I) are represented in the ^{R 1} and R, the aryl group having 6 to 20 carbon atoms, e.g., phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-Vinylphenyl, 3-isopropylphenyl, 4-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- Examples thereof include amylphenyl, 2,5-di-tert-octylphenyl, biphenyl, 2,4,5-trimethylphenyl and the like.

The general formula (I) are represented in the ^{R 1} and R, the aryl alkyl group having 7 to 20 carbon atoms, e.g., benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl and the like can be mentioned Be done.

The general formula (I) are represented in the R ¹ and R, examples of the alkyl aryl group having 7 to 20 carbon atoms, groups in which one hydrogen atom is substituted by an aryl group of the above alkyl group, and Examples of the aryl group include phenyl, cresyl, xsilyl, 2,6-xsilyl, 2,4,6-trimethylphenyl, butylphenyl, nonylphenyl, biphenyl, naphthyl, anthracenyl and the like.

R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 in the} general formula (I) and R ²³ , R ²⁴ , R in the general formula (II). ^{Examples of the halogen atom represented by 25} , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ include fluorine, chlorine, bromine and iodine.

R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 in the} general formula (I) and R ²³ , R ²⁴ , R in the general formula (II). Examples of the substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms represented by ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ and R ^{31 include methyl.} Examples thereof include ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, n-octyl, isooctyl, tert-octyl and 2-ethylhexyl. In the granular ultraviolet absorber of the present embodiment, an alkyl group having 1 to 8 carbon atoms is preferable.

R ¹ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 in the} general formula (I) and R ²³ , R in the general formula (II) Examples of linear or branched alkenyl groups having 2 to 8 carbon atoms represented by ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ and R ^{31 include linear and branched alkenyl groups.} Propenyl, butenyl, pentenyl, hexenyl, heptenyl, and octenyl are listed regardless of the position of the unsaturated bond.

Represented by X ¹ in the general formula (II), a substituted or unsubstituted alkylene group as a straight-chain or branched alkylene group having 8 to 30 carbon atoms, and the methylene linked with 8 to 30 Alternatively, it represents an alkylene group in which some methylene hydrogen atoms are substituted with an alkyl group. In the granular ultraviolet absorber of the present embodiment, an alkylene group having 8 to 20 carbon atoms is preferable.

In the above general formula (II), examples of the linear or branched alkylene group having 1 to 8 carbon atoms represented by ^{L 1 include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, isopropylene and butylene.} , Isobutylene, pentylene and the like.

The triazine-based compound may contain a compound in which R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹¹ and R ¹² are hydrogen atoms in the above general formula (I).
Further, as an example of the triazine-based compound represented by the general formula (I), a compound represented by the following general formula (A) or a compound represented by the following general formula (B) can be mentioned.

Further, as the granular 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 two or more.

In the above general formula (A),
^RA1 is 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, and 6 to 6 carbon atoms. Represents an aryl group of 18, an alkylaryl group having 7 to 18 carbon atoms or an arylalkyl group having 7 to 18 carbon atoms.
^RA2 and ^RA3 may be the same or different from each other, and may be 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. Represents
^RA4 , ^RA7 , and ^RA10 may be the same as or different from each other, and are hydrogen atoms, linear or branched alkyl groups having 1 to 8 carbon atoms, or linear or branched alkenyl having 3 to 8 carbon atoms. Represents a group.
^RA13 and ^RA17 may be the same and different from each other and represent a hydrogen atom or a hydroxy group.
^However, R ^{A1, R A2} and linear or branched alkyl group having 1 to 12 carbon atoms represented by ^{R A3,} a linear or branched carbon atoms having 1 to 12 of the represented by ^{R A2} and ^{R A3} The methylene group in the alkoxy group is an oxygen atom, a sulfur atom, a carbon-carbon double bond, -CO-, -CO-O-, -OC-O-, -CO-NH-, -NH-CO-,-. It may be substituted with at least one structure selected from CR ⁰⁵ = N − and −N = CR ⁰⁶ −, and R ^{05 and R 06} in the structure are independently linear or branched carbons, respectively. Represents an alkyl group having 1 to 8 atoms.

The linear or branched alkyl group having 1 to 12 carbon atoms represented by ^{R A1, R A2} and ^{R A3} in the general formula (A), for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Linear or branched such as sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl, dodecyl, etc. Alkyl groups can be mentioned.

The linear or branched alkoxy group having 1 to 12 carbon atoms represented by ^{R A2} and ^{R A3} in the general formula (A), for example, methyloxy, ethyloxy, isopropyloxy, butyloxy, sec- butyloxy, tert -Butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, Examples thereof include isoheptyloxy, tert-heptyloxy, 1-octyloxy, isooctyloxy, tert-octyloxy and the like.

The cycloalkyl group having 3 to 8 carbon atoms represented by R ^A1 in general formula (A), for example, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.

The represented by the general formula ^{R A1} of (A), the alkyl aryl aryl group or a carbon atom 7 to 18 6 to 18 carbon atoms, e.g., phenyl, naphthyl, 2-methylphenyl, 3-methyl Phenyl, 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-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-amylphenyl, 2,5-di-tert-octylphenyl, biphenyl, 2,4,5-trimethylphenyl and the like. Examples of the arylalkyl group having 7 to 18 carbon atoms include, for example. Examples thereof include benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl and the like.

The general formula ^(A), the alkenyl group ^{R A1, R A4, R A7} , and ^{R A10} few straight or branched carbon atoms represented by 3-8, for example, linear and branched propenyl, Butenyl, pentenyl, hexenyl, heptenyl, and octenyl are listed regardless of the position of the unsaturated bond.

The general formula ^(A), as the R ^A4, R ^A7, a linear or branched alkyl group having 1 to 8 carbon atoms represented by ^{R A10,} for example, methyl, ethyl, propyl, isopropyl, butyl, sec -Butyl, tert-butyl, isobutyl, amyl, tert-amyl, octyl, tert-octyl and the like can be mentioned. Of these, the methyl group is preferable because it has an excellent ability to absorb ultraviolet rays.

The triazine-based compound represented by the general formula (A) has the following compound No. From 1A, compound No. It preferably contains one or more triazine compounds represented by any of 5A.

In addition, the triazine-based compound represented by the above general formula (A) has the following compound No. 6A ~ Compound No. It preferably contains one or more triazine compounds represented by any of 8A.

Further, as the granular ultraviolet absorber of the present embodiment, a compound represented by the following general formula (B) can be used. These may be used alone or in combination of two or more.

In the above general formula (B),
R ^B4 , R ^B5 , R ^{B7 to} R ^B9 , R ^{B10 to} R ^B12 , R ^B23 , R ^B24 , R ^{B26 to} R ^B28 , and R ^{B29 to} R ^B31 are independent hydrogen atoms, hydroxy groups, and halogen atoms, respectively. , Linear or branched alkyl group with 1 to 8 carbon atoms, linear or branched alkenyl group with 2 to 8 carbon atoms, linear or branched alkoxy group with 1 to 20 carbon atoms, 6 carbon atoms Represents an aryl group of ~ 20, and n represents an integer of 8-14. However, of the three benzene rings connected to the triazine ring, the para-position of the two benzene rings is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched carbon atom. It represents the number 1 to 20 alkoxy groups, and one of the ortho positions represents a hydrogen atom or a hydroxy group. )

In the general formula ^(B), as the halogen atom represented by ^{R B4, R B5, R B7} ~R B9, R B10 ~R B12, R B23, R B24, R B26 ~R B28, R B29 ~R B31 For example, a fluorine atom, a chlorine atom, a bromine atom and the like can be mentioned.

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

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

In the general formula ^{(B), R B4, R} B5, R B7 ~R B9, R B10 ~R B12, R B23, R B24, R B26 ~R B28, R B29 linear represented by ^{to R B31} or Examples of the branched alkoxy group having 1 to 20 carbon atoms include methyloxy, ethyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, and 2 -Hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, isoheptyloxy, tert-heptyloxy, 1-octyloxy, isooctyloxy, tert − Examples include octyloxy.

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

In addition, the triazine-based compound represented by the above general formula (B) has the following compound No. From 1B, compound No. It preferably contains one or more triazine compounds represented by any of 4B.

The above compound No. From 1B, compound No. In 4B, ^RA1 , ^RA2 , ^RB1 , ^RB2 , ^RC1 , ^RC2 , ^RD1 and ^RD2 may be the same or different from each other, and have 1 to 4 hydrogen atoms, linear or branched carbon atoms. Represents an alkyl group of 1 or an alkoxy group having 1 to 4 carbon atoms in a straight chain or branched.

The above-mentioned method for synthesizing a triazine-based compound is not particularly limited, and may be any of the synthetic methods usually used for synthesizing a compound having a triazine structure. For example, a method of adding a phenol derivative or a resorcinol derivative to cyanuric chloride using aluminum trichloride can be mentioned. The substituent contained in the benzene ring linked to the triazine ring by a single bond may be introduced after forming the triazine structure, or may be introduced into the phenol compound or resorcinol derivative before forming the triazine structure.

As an example of the method for synthesizing the above triazine compound, for example, 2- [2-hydroxy-4- (2-hydroxyethyloxy) phenyl] -4,6-diphenyl-1,3,5-triazine is added as an alcohol component. Examples thereof include an esterification reaction or an ester exchange reaction with the corresponding ester-inducible compound (carboxylic acid, carboxylic acid halide, carboxylic acid ester), and these reactions may be sequential reactions or batch reactions.
Examples of the alcohol component include a monovalent carboxylic acid ester-inducible compound (monovalent carboxylic acid, monovalent carboxylic acid halide or monovalent carboxylic acid ester), and a divalent carboxylic acid ester-inducible compound (divalent carboxylic acid, divalent). Examples thereof include valent carboxylic acid halides and esters of divalent carboxylic acids.

The triazine compound can be purified after synthesis. As a purification method, distillation, recrystallization, reprecipitation, a method using a filter agent / adsorbent, or the like can be appropriately used. These may be used alone or in combination of two or more.

If necessary, the triazine-based compound can be subjected to processing such as pulverization, granulation, classification, and melt solidification after purification. These may be used alone or in combination of two or more. Thereby, the powder properties of the desired granular triazine compound can be obtained.

The granules of the granular ultraviolet absorber of the present embodiment are meant to be in the form of granules. This granular ultraviolet absorber may be used as it is in the form of granules, but it can also be used after being processed into a fixed shape such as pellets, briquettes, and tablets.

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

For the granular ultraviolet absorber of the present embodiment, the sieve residue amount on each sieve can be calculated based on the following measurement procedure.
A predetermined amount (g) of the granular ultraviolet absorber is sieved in this order using a 4.0 mm mesh sieve, a 2.8 mm mesh sieve, a 2.0 mm mesh sieve, and a 1.0 mm mesh sieve. Is performed, the residual weight (g) of the granular ultraviolet absorber remaining on each sieve is measured, and the weight ratio (wt%) of the residual weight to a predetermined amount is calculated as the sieve residual amount.

According to the findings of the present inventor, by adopting a sieving condition using a plurality of sieves having appropriate openings, the particle size distribution is wide to some extent and stable even for powders containing relatively large particles. It was found that it is possible to measure the particle size distribution.

In the present embodiment, the sieve residue amount of the 4.0 mm mesh sieve is, for example, 0.3 wt% or more and 1.5 wt% or less, preferably 0.4 wt% or more and 1.4 wt% or less, more preferably 0.4 wt%. It is 1.3 wt% or less.
The amount of residual sieve residue on a sieve having an opening of 2.8 mm is, for example, 5.0 wt% or more and 25.0 wt% or less, preferably 5.5 wt% or more and 24.5 wt% or less, and more preferably 6.0 wt% or more. It is 24.0 wt% or less.
The amount of the sieve residue on the sieve having a mesh size of 2.0 mm is, for example, 25.0 wt% or more and 35.0 wt% or less, preferably 25.5 wt% or more and 34.0 wt% or less, more preferably 26.0 wt% or more. It is 33.0 wt% or less.
The amount of the sieve residue on the sieve having a mesh opening of 1.0 mm is, for example, 35.0 wt% or more and 55.0 wt% or less, preferably 36.0 wt% or more and 54.0 wt% or less, more preferably 37.0 wt% or more. It is 53.0 wt% or less.
By setting the amount of the sieve residue of each sieve within the above numerical range, it has an appropriate particle size distribution in the range of 1 mm or more, so that dustiness, fluidity and melt-kneadability can be improved. Therefore, a granular ultraviolet absorber having excellent powder characteristics can be realized.

Further, in the granular ultraviolet absorber of the present embodiment, the amount of non-passing material when passed through a 5.0 mm mesh sieve can be configured to be 0 wt%. By cutting the coarse particles in this way, it is possible to realize a granular ultraviolet absorber having excellent powder characteristics and ultraviolet absorption characteristics. In addition, the melt-kneadability can be improved.

Further, in the granular ultraviolet absorber of the present embodiment, the amount of passage through the 1.0 mm mesh sieve is, for example, 1.0 wt% or more and 15.0 wt% or less, preferably 2.0 wt% or more and 14.5 wt% or less. It is preferably 3.0 wt% or more and 14.0 wt% or less. By setting the value to the above upper limit or less, dustiness and fluidity can be enhanced.

In the granular ultraviolet absorber of the present embodiment, the total value of the sieve residue amount of the above-mentioned 4.0 mm mesh sieve, 2.8 mm mesh sieve, 2.0 mm mesh sieve, and 1.0 mm mesh sieve is 100 wt. It is configured to be less than or equal to%. Further, the total value of the remaining amount of the sieve of the above-mentioned 4.0 mm mesh sieve, 2.8 mm mesh sieve, 2.0 mm mesh sieve, and 1.0 mm mesh sieve and the total value of the passing amount of the 1 mm mesh sieve. Can be configured to be 100 wt%.

In the present embodiment, it is possible to control the sieve residue amount of each of the above sieves by appropriately selecting, for example, the type and shape of the triazine-based compound, the method for preparing the triazine-based compound, and the like. Among these, for example, appropriately adopting processing conditions for triazine compounds such as melt solidification, pulverization, and classification are cited as factors for setting the sieve residue amount of each of the above sieves to a desired numerical range. Be done.

Further, the present inventor has found that the powder characteristics of the triazine compound and the granular ultraviolet absorber using the triazine compound can be appropriately controlled by using the X-ray diffraction analysis pattern as a guideline. As a result of further diligent research based on such findings, by setting the diffraction angle 2θ at which the maximum peak exists in the powder X-ray diffraction analysis pattern within a predetermined numerical range, the above-mentioned triazine-based compound and granular ultraviolet rays using it are set. It has been found that the powder properties of the absorbent are improved.

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

The triazine compound of the present embodiment has a maximum peak in the powder X-ray diffraction analysis pattern within a range of 5.00 ° or more and 6.50 ° or less, preferably 5.20 ° or more and 6.00 ° or less. , More preferably 5.40 ° or more and 5.80 ° or less. As a result, the feedability and the compression granulation property can be improved, so that a triazine-based compound or a granular ultraviolet absorber having excellent powder properties can be realized.
Here, the maximum peak means the maximum peak intensity in the X-ray diffraction pattern obtained within the scanning range (for example, diffraction angle 2θ = 3 ° to 60 ° or 3 ° to 90 °) in the powder X-ray diffraction measurement. Have.

Further, in the powder X-ray diffraction analysis pattern of the triazine compound, the half width at the maximum peak is, for example, 0.05 ° or more and 0.20 ° or less, preferably 0.10 ° or more and 0.19 ° or less. It is preferably 0.15 ° or more and 0.18 ° or less. By appropriately setting the peak width of the maximum peak (maximum peak) so as to be within such a numerical range, a granular ultraviolet absorber having excellent powder characteristics and ultraviolet absorption characteristics can be realized.

Further, in the powder X-ray diffraction analysis pattern of the triazine compound, when the relative intensity of the maximum peak is 100, the diffraction angle 2θ is within the range of 3.0 ° or more and 45.0 ° or less, for example, the relative intensity. It is configured so that there are no diffraction peaks having a relative intensity of 30 or more and 60 or less, preferably a relative intensity of 25 or more and 60 or less, and more preferably a relative intensity of 22 or more and 60 or less. That is, by making the peak intensity of the maximum peak value relatively high, it is possible to realize a granular ultraviolet absorber having excellent powder characteristics and ultraviolet absorption characteristics.

Further, in the powder X-ray diffraction analysis pattern of the triazine compound, when the relative intensity of the maximum peak is 100, the diffraction peak having a relative intensity of 1 or more and 5 or less is, for example, a diffraction angle 2θ of more than 45.0 ° 60. It is configured so that it does not exist within the range of 0.0 ° or less, preferably more than 45.0 ° and 90.0 ° or less. That is, a granular ultraviolet absorber having excellent powder characteristics and ultraviolet absorption characteristics can be realized by setting a region in which a slight intensity peak does not exist within an appropriate numerical range.

In the present embodiment, for example, by appropriately selecting the type and shape of the triazine compound, the method for preparing the triazine compound, etc., the powder X-ray diffraction analysis pattern such as the diffraction angle 2θ of the maximum peak and the half width of the maximum peak It is possible to control. Among these, for example, appropriate adoption of processing conditions for triazine compounds such as melt solidification, pulverization and classification is a powder X-ray diffraction analysis of the maximum peak diffraction angle 2θ, maximum peak half width, etc. It is mentioned as an element for setting a pattern into a desired numerical range.

The resin composition of this embodiment will be described.

The resin composition contains the granular ultraviolet absorber. This resin composition may contain a synthetic resin. As a result, desired resin properties according to various uses can be obtained.

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

Specific examples of the synthetic resin include the following.
Examples of the thermoplastic resin include α-olefin polymers such as polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, crosslinked polyethylene, ultrahigh-molecular-weight polyethylene, polybutene-1, poly-3-methylpentene, and the like. Polyethylenes such as ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, and ethylene-propylene copolymers and their copolymers, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, and polyfluoride. Vinylidene, rubber chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate ternary copolymer, vinyl chloride-acrylic acid Halogen-containing resins such as ester copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-cyclohexylmaleimide copolymers; petroleum resin, kumaron resin, polystyrene, polyvinyl acetate, acrylic resin, polymethylmethacrylate, polyvinyl alcohol , Polyvinylformal, Polyvinylbutyral; Aromatic polyesters such as polyethylene terephthalates, polybutylene terephthalates, polyalkylene terephthalates such as polycyclohexanedimethylene terephthalates, polyalkylene naphthalates such as polyethylene naphthalates and polybutylene naphthalates, and polytetramethylene terephthalates, etc. Straight chain polyesters; degradable aliphatic polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid resin, polyapple acid, polyglycolic acid, polydioxane, poly (2-oxetanone); Examples thereof include polyamides such as polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide, polycarbonates, branched polycarbonates, polyacetals, polyphenylene sulfides, polyurethanes, and fibrous resins.

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

Examples of the elastomer include fluororesins, silicone resins, silicone rubber polyether sulfones, polysulfones, polyphenylene ethers, polyetherketones, polyetheretherketones, liquid crystal polymers, and the like. Further, isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, silicone rubber and the like can be mentioned.
More specific elastomers include, for example, olefin-based thermoplastic elastomers, styrene-based thermoplastic elastomers, polyester-based thermoplastic elastomers, nitrile-based thermoplastic elastomers, nylon-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, and polyamide-based thermals. Examples thereof include plastic elastomers and polyurethane-based thermoplastic elastomers.

Examples of synthetic resins having excellent transparency include polyethylene, polypropylene, polystyrene, copolymers of polyethylene and cycloolefins such as norbornene, polyvinylic acid, polyvinylidene ester, vinyl acetate, polyacrylonitrile, and poly. Vinyl compounds such as vinyl chloride and polyvinyl chloride and addition polymers of vinyl compounds, polymethacrylic acid, polymethacrylic acid ester, polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene chloride, vinylidene fluoride / trifluoroethylene copolymer, foot Vinylidene chloride / tetrafluoroethylene copolymer, vinyl compound such as vinylidene cyanide / vinyl acetate copolymer, copolymer of fluorine-based compound, fluorine such as polytrifluoroethylene, polytetrafluoroethylene, polyhexafluoropropylene, etc. Containing compounds, polyamides such as nylon 6, nylon 66, polyimides, polyurethanes, polypeptides, polybutylene terephthalates, polyesters such as polyethylene terephthalates, polyethers such as polycarbonate, polyoxymethylene, polyethylene oxide, polypropylene oxide, epoxy resins, polyvinyl alcohol , Polyvinylidene chloride and the like.

Further, 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 above synthetic resins may be used alone, in combination of two or more, or may be alloyed.

The blending amount of the granular ultraviolet absorber in the above resin composition is, for example, preferably 0.001 part by mass to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and 0. 1 to 5 parts by mass is even more preferable. By setting it to the above lower limit value or more, a sufficient effect of the granular ultraviolet absorber can be obtained. Further, by setting the value to the upper limit or less, the desired resin physical properties can be realized while improving the effect of adding the granular ultraviolet absorber.
In the present specification, "~" means that an upper limit value and a lower limit value are included unless otherwise specified.

The resin composition of the present embodiment may contain additive components other than the above-mentioned components, if necessary. Other additive components include, for example, an antioxidant, an ultraviolet absorber other than the triazine compound according to the present embodiment, a hindered amine-based light stabilizer, a near-infrared absorber, a nucleating agent (clearing agent), and an antioxidant. , Lubricants, plasticizers, light-absorbing dyes, fillers, pigments, dyes, metal soaps, processing aids, flame retardants, flame retardant aids, zeolite compounds, foaming agents, (heavy) metal inactivating agents , Cross-linking agent, epoxy-based stabilizer, matting agent, antifogging agent, plate-out inhibitor, surface treatment agent, fluorescent whitening agent, antifungal agent, antibacterial agent, mold release agent and the like.

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

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and distearyl (3,5-di-tert-butyl). -4-Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-) m-cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (6- tert-butyl-m-cresol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4-sec-butyl-6-tert-butylphenol), 1 , 1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-Tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocia Nurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) ) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-di-) tert-Butyl-4-hydroxyphenyl) propionate, tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) methyl propionate] methane, thiodiethylene glycolbis [(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) Butyric acid] 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-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9 -Bis [1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] Examples thereof include undecane and triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

Examples of the phosphorus-based antioxidant include trisnonylphenyl phosphite and tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl]. Phosphite, tridecylphosphite, triisodecylphosphite, trilaurylphosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) 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, tetra (tridecyl) isopropyridendiphenol diphosphite, tetra (tridecyl)- 4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) Butantriphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6-tert-butylphenyl) -octadecylphosphite, 2,2'-ethylidenebis (4,6--) Di-tert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakiss-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepine-6) Examples thereof include phosphite of −yl) oxy] ethyl) amine, 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol.

Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra (β-alkylthiopropionic acid). Esters can be mentioned.

Examples of the ultraviolet absorber other than the triazine compound according to the present embodiment include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5. 2-Hydroxybenzophenones such as'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5 '-Di-tert-butylphenyl) -5-chlorobenzotriazol, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazol, 2- (2'-Hydroxy-5'-tert-octylphenyl) benzotriazol, 2- (2'-hydroxy-3', 5'-dicumylphenyl) benzotriazol, 2,2'-methylenebis (4) 2-(2'-Hydroxyphenyl) such as -tert-octyl-6- (benzotriazolyl) phenol), 2- (2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl) benzotriazole, etc. Bentotriazoles; phenylsalicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl-3, Benzoates such as 5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy- Substituted oxanilides such as 4'-dodecyloxanilide; cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate Can be mentioned.

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-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-tetramethyl-4-piperidyl) Sevacate, Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) Sevacate, Tetrax (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4 -Butan tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate, bis (2,2,6,6-tetramethyl) -4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1, 2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4-hydroxy) Benzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl polycondensate succinate, 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-triazine-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (2,4-bis) N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-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-triazine-6-yl] aminoundecane, 1,6 , 11-Tris [2,4-bis (N-butyl-N) -(1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6-yl] Hindered amine compounds such as aminoundecane can be mentioned.

Examples of the near-infrared absorber include polymethine dyes (cyanine dyes), indolinocyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, naphthol metal complex dyes, squarylium dyes, triazo dyes, and dithiol metal complex salt dyes. , Pyrylium pigments, thiapyrylium pigments, indian aniline pigments, azoanthraquinone pigments, naphthoquinone pigments, anthraquinone pigments, bis (dithiolene) pigments, triphenylmethane pigments, aminium (aluminum) pigments, diimonium pigments, etc. In addition, inorganic near-infrared absorbers may be used, such as carbon black, antimony oxide or indium oxide doped tin oxide, oxides of metals belonging to Periodic Tables 4A, 5A or 6A, carbides or boros. Azo is mentioned.

Examples of the nucleating agent include metal salts of benzoic acids such as p-tert-aluminum benzoate and sodium benzoate, sodium bis (2,4-di-tert-butylphenyl) phosphate, and methylenebis (2,). 4-Di-tert-butylphenyl) sodium phosphate, bis [methylenebis (2,4-di-tert-butylphenyl) phosphate] Aromatic phosphate metal salts such as hydroxyaluminum and aromatic phosphates Mixtures of metal salts and alkali metal compounds, dibenzylene sorbitols such as dibenzylene sorbitol, bis (methylbenzylene) sorbitol, bis (p-ethylbenzylene) sorbitol, bis (dimethylbenzylene sorbitol), amino acid metal salts, loginate metal salts , N, N', N "-tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide, N, N', N" -tricyclohexyl-1,3,5-benzenetricarboxamide, N, Examples thereof include amide compounds such as N'-dicyclohexylnaphthalenedicarboxamide and 1,3,5-tri (dimethylisopropoylamino) benzene.

Examples of the antistatic agent include cationic antistatic agents such as a quaternary ammonium ion salt of a fatty acid and a quaternary polyamine salt; a higher alcohol phosphate ester salt, a higher alcohol EO adduct, a polyethylene glycol fatty acid ester, and an anion type. Anionic antistatic agents such as alkyl sulfonates, higher alcohol sulfates, higher alcohol ethylene oxide adducts sulfates, higher alcohol ethylene oxide adduct phosphates; polyhydric alcohol fatty acid esters, polyglycol phosphates, poly Nonionic antistatic agent such as oxyethylene alkylallyl ether; contains amphoteric alkyl betaine such as alkyldimethylaminoacetic acid betaine, amphoteric antistatic agent such as imidazoline amphoteric agent, and block polymer having ionomer or polyethylene glycol as a hydrophilic part. Examples include high molecular weight antistatic agents.

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

Examples of the plasticizer include phthalates, dibasic acids, chlorinated paraffins, polyesters, epoxidized esters, phosphoric acids, trimellitic acids and the like.

Examples of the light-absorbing dye include cyanine-based, quinoline-based, coumarin-based, thiazole-based, oxonor-based, azulene-based, squarylium-based, azomethine-based, azo-based, benzylidene-based, xanthene-based, phthalocyanine-based, and dithiol metal complex-based. Examples include compounds.

Examples of the filler include calcium carbonate, calcium oxide, calcium hydroxide, zinc hydroxide, zinc carbonate, zinc sulfide, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, sodium alumina silicate, and the like. Hydrocarbamite, aluminum silicate, magnesium silicate, calcium silicate, metal silicates such as zeolite, active white clay, talc, clay, red iron oxide, asbestos, antimony trioxide, silica, glass beads, mica, sericite, glass Flake, asbestos, wolastonite, potassium titanate, PMF (mineral fiber), gypsum fiber, zonolite, MOS (Magnesium Hydroxide Sulfate Hydrate, fibrous magnesium compound), phosphate fiber, glass fiber, carbon fiber, aramid fiber, cellulose nano Examples include fiber.

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

Examples of the above dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acrydin dyes, stillben dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, and oxazine dyes. , Dyes such as phthalocyanine dyes and cyanine dyes.

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

The processing aid can be appropriately selected from known processing aids, but acrylic acid-based processing aids are preferable. Examples of processing aids include homopolymers or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; the alkyl methacrylate and alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate. Copolymer; Copolymer of the alkyl methacrylate and an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene; the copolymerization of the alkyl methacrylate and a vinyl cyan compound such as acrylonitrile and methacrylonitrile. Coalescence etc. can be mentioned.

Examples of the flame retardant and the flame retardant aid include the following triazine ring-containing compound, metal hydroxide, other inorganic phosphorus, halogen-based flame retardant, silicone-based flame retardant, phosphoric acid ester-based flame retardant, condensed phosphoric acid. Examples thereof include ester-based flame retardants, intomescent-based flame retardants, antimony oxides such as antimony trioxide, other inorganic flame retardants, and organic flame retardants.

Examples of the triazine ring-containing compound include melamine, ammeline, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylene guanamine, norbornene diguanamine, methylene diguanamine, ethylene dimeramine, and trimethylene. Examples thereof include dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, and 1,3-hexylene melamine.

Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, Kismer 5A (magnesium hydroxide: manufactured by Kyowa Chemical Industry Co., Ltd.) and the like.

Examples of the above-mentioned phosphoric acid ester flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, and cresyldiphenyl. Phenyl phosphate, trixylenyl phosphate, octyldiphenyl phosphate, xylenyldiphenyl phosphate, trisisopropylphenyl phosphate, 2-ethylhexyldiphenyl phosphate, tert-butylphenyldiphenyl phosphate, bis- (tert-butylphenyl) phenyl phosphate, tris- (tert) -Butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate and the like can be mentioned.

Examples of the condensed phosphoric acid ester flame retardant include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like. Examples of the mescent flame retardant include ammonium salts and amine salts of (poly) phosphoric acid 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. For example, TIPAQUE R-680 (titanium oxide: Ishihara Sangyo). Various commercially available products such as Kyowa Mug 150 (magnesium oxide: manufactured by Kyowa Kagaku Kogyo Co., Ltd.) can be used.

Examples of other organic flame retardant aids include pentaerythritol and dipentaerythritol.

The above-mentioned zeolite compound is an alkaline or alkaline earth metal aluminosilicate having a unique three-dimensional zeolite crystal structure, and typical examples thereof are A-type, X-type, Y-type and P-type zeolite, monodenite, and anal. Sights, sodalite aluminosilicates, clinobtyrolites, erionites, chavasites, etc. can be mentioned, and hydrates having crystalline water (so-called zeolite water) of these zeolite compounds or alkalis from which crystalline water has been removed. Any of these may be used, and those having a particle size of 0.1 to 50 μm can be used, and those having a particle size of 0.5 to 10 μm are particularly preferable.

Examples of the foaming agent include azodicarboxylic amide, azobisisobutyronitrile, p, p'-oxybisbenzenesulfonyl hydrazide, n, n'-dinitrosopentamethylenetetramine, p-toluenesulfonyl semicarbazide, and trihydrazo. Examples thereof include decomposition-type organic foaming agents such as triazine and decomposition-type inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, azide compounds, and sodium borohydride.

Examples of the (heavy) metal inactivating agent include salicylamide-1,2,4-triazole-3-yl, bissalicylic acid hydrazide, dodecandioil bis (2- (2-hydroxybenzoyl) hydrazide), and bis (3). -(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid) hydrazide and the like.

Examples of the cross-linking agent include benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, and 2,5-dimethyl-2,5-di. (Tart-butylperoxy) hexin, 1,3-bis (tert-butylperoxyisopropyl) benzene-tert-butyl-hydroperoxide, cumene hydroperoxide, polysulfone azide, azidoformate, tetramethylisophthalyldi-tert-butyl bisperoxide, Examples thereof include alkanolamines such as tetramethylisophthalyl dicumyl bisperoxide, diethanolamine and triethanolamine, hexamethylenediamine, and 4,4'-diaminodiphenylmethane.

Examples of the epoxy-based stabilizer include compounds having an aliphatic, aromatic, alicyclic, aromatic aliphatic or heterocyclic structure and having an epoxy group as a side chain. The epoxy group is preferably attached as a glycidyl group to a residue of the molecule by an ether or ester bond, or may be an N-glycidyl derivative of a heterocyclic amine, amide or imide. Specific examples include epoxidized soybean oil, epoxidized linseed oil, and epoxidized monoester. Examples of commercially available epoxy stabilizers include ADEKA Corporation product names "ADEKA CORPORATION O-130P", "ADEKA CORPORATION O-180A", "ADEKA CORPORATION D-32", "ADEKA CORPORATION EP-13", and "ADEKA CORPORATION". ADEKA Sizer FEP-13 ”and the like.

As the matting agent, fine particles of silicon dioxide are preferable. Examples of fine particles of silicon dioxide include Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, and TT600 (all manufactured by Nippon Aerosil Co., Ltd.), which are rubbed while keeping the haze of the film low. Aerosil 200V, Aerosil R972V, and Aerosil R812 are preferable because they have a large effect of lowering the coefficient.

Examples of the antifogging agent include glycerin fatty acid ester, alkyldiethanolamine, and alkyldiethanolamine fatty acid ester.
Examples of the plate-out inhibitor include those containing silicon dioxide and an alkylene oxide adduct of an ethylene-saturated vinyl ester copolymer saponified product as an active ingredient.

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 novolac type epoxy resin and bisphenol type epoxy resin, and novolak type epoxy resin is preferably used. Examples of the novolak type epoxy resin include polyfunctional epoxy resins such as phenol novolac type epoxy resin and cresol novolak type epoxy resin.

In addition to the aminosilane compound and epoxy resin, the surface treatment agent may contain components such as urethane resin, acrylic resin, antistatic agent, lubricant, and water repellent as long as the properties are not impaired. .. Further, as other surface treatment agents, epoxy resins other than novolak type and bisphenol type, coupling agents and the like can be mentioned.

The fluorescent whitening agent is a compound that absorbs ultraviolet rays of sunlight or artificial light, converts them into purple to blue visible light, and radiates the ultraviolet rays to promote the whiteness and bluish tint of the molded product. .. Examples of the fluorescent whitening agent include benzoxazole compounds C.I. I. Fluorescent Fluorescent 184; Coumarin-based compound C.I. I. Fluorescent Fluorescent 52; diaminostilbene disulphonic acid-based compound C.I. I. Fluorescent Fluorescenter 24, 85, 71 and the like can be mentioned.

Examples of the antifungal agent include organic antifungal agents such as nitrogen-containing sulfur-containing, organic bromine-based, nitrogen-containing, and arsenic-based 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, zeolite-based agents containing metals such as silver and zinc, and apatite. Examples thereof include inorganic antibacterial agents such as based, silica-alumina-based, ceramic-based, zirconium phosphate-based, silica gel-based, hydroxyapatite-based, and calcium silicate-based.

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

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

As an example of the method for producing the above resin composition, each component such as the granular ultraviolet absorber of the present embodiment, the above-mentioned synthetic resin, and other additive components as required is mixed with various mixers such as a tumbler and a Henschel mixer. A method of melt-kneading with a Banbury mixer, a roll, a brabender, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader or the like can be mentioned.
Further, each component may not be mixed in advance, or only a part of the components may be mixed in advance, supplied to an extruder using a feeder, and melt-kneaded to produce a resin composition. Further, a resin composition obtained by mixing some components in advance, supplying them to an extruder, and melt-kneading them into a masterbatch is used as a masterbatch, and the resin composition is manufactured by mixing with other components and melt-kneading again. You can also do it.
Further, the synthetic resin used in the above 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 fixed shape such as powder, granules, pellets, briquettes, tablets, or a sheet.

A molded product can be obtained by molding the resin composition of the present embodiment.
The molding method is not particularly limited, and is an injection molding method, an extrusion molding method, a blow molding method, a rotary molding, a vacuum molding method, an inflation molding method, a calendar molding method, a slash molding method, a dip molding method, and a foam molding method. Law etc. can be mentioned.

The molded product can have various forms depending on the intended use, and has various shapes such as a resin plate, a sheet, a film, a container (bottle, tray, bag), a fiber, and various molded products. obtain.

Further, in the resin composition of the present embodiment, each component such as the granular ultraviolet absorber of the present embodiment, the above-mentioned synthetic resin used as a binder resin, and if necessary, other additive components are dissolved in a solvent to make a varnish resin. (A varnish-like resin composition that is liquid at room temperature) may be used. As the solvent, an organic solvent or an aqueous solvent can be used. If necessary, a resin varnish may be used as an emulsion in which a powdered UV absorber is dispersed using an emulsifier.

As a method for preparing the resin varnish, the order of mixing each component is not particularly limited, and all the components may be mixed at the same time, or the granular ultraviolet absorber of the present embodiment and other additive components are mixed in advance. The synthetic resin may be mixed with the mixture obtained in the above process, a plurality of pre-prepared components may be mixed with other components, or a plurality of pre-prepared components may be mixed. They may be further mixed with each other.
The resin varnish can also be processed into a film or sheet by using, for example, a cast film method. The resin varnish can also be used as a coating material for coating on a predetermined base material.

The resin composition of the present embodiment includes electricity / electronics / communication, agriculture, forestry and fisheries, mining, construction, food, textiles, clothing, medical care, coal, petroleum, rubber, leather, automobiles, precision equipment, wood, building materials, civil engineering, and furniture. Can be used in a wide range of industrial fields such as printing and musical instruments.

More specific applications include, for example, printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, copiers, facsimiles, ECRs (electronic money registration machines), calculators, electronic notebooks, cards, holders, etc. Office work such as stationery, OA equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, household appliances such as kotatsu, TVs, VTRs, video cameras, radio cassette recorders, tape recorders, mini discs, CD players , Speakers, AV equipment such as liquid crystal displays, connectors, relays, capacitors, switches, printed boards, coil bobbins, semiconductor encapsulation materials, LED encapsulation materials, electric wires, cables, transformers, deflection yokes, distribution boards, clocks, etc.・ Electronic parts and communication equipment, interior / exterior materials for automobiles, plate-making films, adhesive films, bottles, food containers, food packaging films, pharmaceutical / pharmaceutical wrap films, product packaging films, agricultural films, agricultural sheets, Examples include greenhouse films.

In addition, specific applications include seats (filling, outer material, etc.), belts, ceilings, compatible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, foil covers, mattress covers, airbags, insulation. Materials, hanging hands, hanging hand bands, wire covering materials, electrical insulation materials, paints, coating materials, upholstery materials, flooring materials, corner walls, carpets, wallpaper, wall covering materials, exterior materials, interior materials, roofing materials, decks Automobiles, vehicles, ships such as materials, wall materials, pillar materials, floor boards, wall materials, skeletons and lead shapes, window and door shapes, moss boards, siding, terraces, balconies, soundproof boards, heat insulating boards, window materials, etc. , Aircraft, buildings, housing and building materials and civil engineering materials, clothing, curtains, sheets, non-woven fabrics, plywood, synthetic fiber boards, rugs, entrance mats, sheets, buckets, hoses, containers, glasses, bags, cases, goggles, ski boards. , Rackets, tents, daily necessities such as musical instruments, various uses such as sporting goods. In addition, paints, cosmetics and the like can be mentioned.
Also, chemical containers for medicines, vitamins, drinks, eye drops, etc .; cosmetic containers for lotions, emulsions, sunscreens, etc .; food containers, liquor, wine, beer, fruit juices, soft drinks, tea, tea, coffee, etc. Beverage containers: Applications such as daily necessities containers for shampoo, conditioner, mouthwash, toothpaste, disinfectant, etc.

Further, the resin composition of the present embodiment is not particularly limited, but can be suitably used as an optical material such as an optical film or an optical sheet by molding into a sheet or a film. As the optical material, for example, it is used for 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, and an electric field radiation type display. It is useful as an optical film or an optical sheet, and is particularly useful as an optical film such as a liquid crystal display device using an organic material having inferior ultraviolet resistance for a display element, an optical correction film for an organic EL display, and a light emitter protective film. Applications of liquid crystal display devices include polarizing plate protective films or protective sheets, retardation films, viewing angle enlargement films, antiglare films, brightness improving films, light diffusing films and light diffusing sheets, lens films and lens sheets, and antifogging films. Examples thereof include antistatic film, optical correction film, antireflection film, color tone adjusting film, light guide plate, etc., and in particular, an optical film or optical sheet installed on the outer surface side of a polarizing plate in contact with a liquid crystal display element, or polarization. It can be suitably used for a plate protective film or an optical sheet.

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

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

[Preparation of granular UV absorber]
(Example 1)
2,4,6-tris [2-hydroxy-3-methyl-4-hexyloxyphenyl] triazine was synthesized by the following procedure.
10.00 g of 2,4,6-tris (2,4-dihydroxy-3-methylphenyl) triazine, 22.68 g of sodium hydroxide, 80.00 g of dimethylformamide, 1-bromo in a 300 ml four-necked flask. 11.07 g of hexane was added, the temperature was raised to 80 ° C., and the reaction was carried out for 9 hours. After neutralization treatment with hydrochloric acid, washing with water and desolvation under reduced pressure were performed, and the residue was recrystallized from toluene: isopropyl alcohol = 1: 1 to obtain crystals. Then, the molten object (crystal) was dropped onto a metal plate and cooled to obtain flakes (melting and solidifying treatment). The obtained flakes were roughly pulverized and classified to obtain 11.89 g (yield 76%) of pale yellow granules having a melting point of 145 ° C.
The obtained compound (pale yellow granules) was subjected to ^{1 1} H-NMR measurement. The pale yellow granules obtained by the following analysis results were obtained by the following formula No. It was identified as a granular compound (granular ultraviolet absorber) represented by 1.

(Examples 2 to 5)
In the same manner as in Example 1, different lots of granular compound No. 1 (granular ultraviolet absorber) was obtained.

(Comparative Example 1)
The crystals obtained in Example 1 were crushed in a mortar without performing a melt-solidification treatment to obtain the above formula No. A powdery compound (granular ultraviolet absorber) represented by 1 was obtained.

(Comparative Example 2)
In Example 1, compounds having a coarse particle size obtained during classification were collected to obtain a granular ultraviolet absorber.

The granular ultraviolet absorbers obtained as described above were evaluated based on the following evaluation items. The evaluation results are shown in Table 1.

(Particle size distribution)
The particle size distribution of the obtained granular ultraviolet absorber was sieved using a plurality of sieves, and the residual ratio was calculated from the weight of what remained on each sieve. Specifically, it is as follows.
First, about 200 g (total amount) of the obtained granular ultraviolet absorber is put into the uppermost sieve, and a vibration sieving device (manufactured by Lecce, AS300) equipped with a sieve is used under the conditions of the following open mesh sieve and amplitude. And shaken for 3 minutes (sieving operation). The weight (g) of the granular ultraviolet absorber remaining on each sieve was measured, and the weight ratio (wt%) to the total amount introduced was calculated as the sieve residual amount.
・ Opening: 4.0 mm, 2.8 mm, 2.0 mm, 1.0 mm (set in this order from the top)
・ Amplitude: 1.00 mm, 3 min

In Table 1, the sieve residue amount indicates the weight ratio of the granular ultraviolet absorber remaining on the sieve by the sieving operation. The amount passed indicates the weight ratio of the granular ultraviolet absorber that has passed (passed) through a sieve having a mesh size of 1.0 mm.
Table 1 shows the results of the residual amount (wt%) of the sieve residue on the 5.0 mm mesh sieve when the obtained granular ultraviolet absorber was sieved using a 5.0 mm mesh sieve.

(Dustiness)
-Handling property A mixture of 0.2 parts by mass of the obtained granular ultraviolet absorber with 100 parts by mass of a polycarbonate resin was mixed with a Henschel mixer for 10 minutes to obtain a mixture. The handleability was evaluated based on the following evaluation criteria.
◯: Almost no powdering was observed.
X: A large amount of powder was observed.
-Working environment The obtained granular UV absorber was dropped on a saucer from 30 cm above, and the amount placed on the saucer was measured. The work environment was evaluated based on the following evaluation criteria.
◯: The amount remaining in the saucer is relatively large.
X: The amount remaining in the saucer was relatively small, and most of it protruded from the saucer.

(Liquidity)
0.2 parts by mass of the obtained granular ultraviolet absorber was mixed with 100 parts by mass of the polycarbonate resin, mixed with a Henschel mixer for 10 minutes, and the obtained mixture was supplied from the hopper of the extruder to the extruder. did. Liquidity in the hopper was evaluated based on the following evaluation criteria.
⊚: The fluidity of the mixture was good and no defective preparation occurred. ◯: The mixture was relatively fluid and no defective preparation occurred within a range where there was no practical problem.
X: The fluidity of the mixture was lowered, and poor preparation occurred.

(Melting kneading property)
The obtained granular ultraviolet absorber was blended in an amount of 1 part by mass with respect to 100 parts by mass of the acrylic resin, and melt-kneaded at 250 ° C. using a twin-screw extruder (L / D = 30). Granulation was performed to obtain pellets. The pellets were observed when the discharge rate was set to 0.3 kg / h, and the melt-kneadability was evaluated based on the following evaluation criteria.
◯: The resin and the granular ultraviolet absorber were uniformly dispersed, and melt-kneading was possible.
Δ: The resin and the granular ultraviolet absorber were slightly separated, but melt-kneading was possible.
X: The resin and the granular ultraviolet absorber were separated and could not be melt-kneaded.

In addition, the obtained granular ultraviolet absorbers of Example 1 and Comparative Example 1 were subjected to X-ray diffraction analysis. The evaluation results are shown in Tables 2-4.

(X-ray diffraction)
Powder X-ray diffraction measurement was carried out on the obtained granular ultraviolet absorber using Ultima IV (Rigaku Co., Ltd.) under the following measurement conditions.
(Measurement condition)
X-ray tube: CuKα ray (CuKα1 = 1.540562Å, CuKα2 = 1.5444398Å, without CuKα2 removal)
Tube voltage / tube current: 40kV / 40mA
Attachment: Multipurpose thin film sample stand Monochromator: Fixed filter: None Diffuse slit: 2/3 °
Divergence vertical restriction slit: 10 mm
Scattering slit: 1.17 mm
Light receiving slit: 0.3 mm
Scan type: Continuous scan Scan speed: 4 ° / min
Sampling width: 0.02 °
Scanning axis: 2θ / ω
Scanning range: = 3 ° to 90 °

The result of the powder X-ray diffraction analysis in the granular ultraviolet absorber of Example 1 is shown in FIG. Table 3 shows the diffraction angles 2θ, d values, and relative intensities corresponding to each peak in FIG. In Table 3, deg represents ° and the threshold of peak intensity was set to 1/100 of the maximum peak.

The result of the powder X-ray diffraction analysis in the granular ultraviolet absorber of Comparative Example 1 is shown in FIG. Table 4 shows the diffraction angles 2θ, d values, and relative intensities corresponding to each peak in FIG. In Table 4, the peak intensity threshold was set to 1/100.

(Feedability)
1 kg of the obtained granular ultraviolet absorber was put into a hopper, and a heavy-duty feeder (manufactured by K-Tron, length: 25 cm x outer diameter: 1.4 cm, groove width: 2.0 cm, groove depth: 0. Using a 3 cm Twin spiral type biaxial screw), the feeder was discharged for 30 minutes under the condition of a feeder discharge amount of 0.3 kg / h (feedability test).
-Quantitative The amount discharged from the heavy-duty feeder (feeder amount) was measured over time at 10-minute intervals. The case where the variation in the feed amount was small was evaluated as ◯, and the case where the variation in the feed amount was large was evaluated as x.
-Long-run property The above feed test was carried out in the same manner except that the condition of the discharge time was changed from 30 minutes to 3 hours. The case where the discharge was continued for 3 hours was marked with ◯, and the case where the operation was stopped before the lapse of 3 hours was marked with x.

(Compression granulation property)
Using a roller compactor (Hosokawa Micron Co., Ltd., granulator M-25 type), the obtained granular ultraviolet absorber was compression-granulated under the conditions of roll gap: 3.2 mm and roll rotation speed: 14 rpm to form a plate. Plate-shaped granules having a thickness of 4 mm were obtained. The obtained plate-shaped granules were crushed, coarse powder was removed with a 5-mesh vibrating sieve, and then fine powder was removed with a 24-mesh vibrating sieve (grain size), and then remained on the 24-mesh vibrating comb. A plate-shaped granule was obtained.
The appearance of the obtained granulated product was observed, and the degree of disintegration of the granulated product was evaluated based on the following criteria.
In 10 out of 10 granules, no disintegration was observed, and in 10 out of 10, 1 or more and 4 or less granules, in which some disintegration was observed, were marked with Δ. Those in which partial or total collapse of 5 or more granules was observed were marked with x.

[Preparation of resin composition]
(Production of film)
A mixture of 100 parts by mass of a synthetic resin (polycarbonate resin: manufactured by Mitsubishi Engineering Plastics Co., Ltd., product name E-2000) and 0.2 parts by mass of the obtained granular ultraviolet absorbers of each example was prepared. A resin composition was prepared by dissolving in 230 parts by mass of a solvent (toluene / cyclohexane = 9/1). From the obtained resin composition, a film having a thickness of 40 μm was prepared by a casting method, and a square film test piece having a side of 2 cm was obtained.
The obtained film test piece was measured with a sunshine weather meter (83 ° C., no rain, light source carbon arc) to measure the retention rate (%) of the total light transmittance (%) after 240, 360 and 480 hours. , Light resistance was evaluated.
From the results showing high retention rates (%) after 240, 360 and 480 hours, it was found that excellent light resistance can be realized by using the granular ultraviolet absorbers of each example.
Further, it was found that even 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, similarly excellent light resistance can be realized.

(Making a container)
To 100 parts by mass of polyethylene terephthalate (intrinsic viscosity: 0.8 dL / g), 0.3 parts by mass of the obtained granular ultraviolet absorbers of each example were added and mixed to obtain a resin composition. The obtained resin composition was dried in a gear oven at 160 ° C. for 4 hours, and then a preform (outer diameter 25 mm, weight 23 g) was molded by an injection molding machine at a molding temperature of 280 ° C. Next, the obtained preform was biaxially stretched and blow-molded at a mold temperature of 130 ° C. to prepare a plastic bottle having a capacity of 500 mL and a thickness of 0.7 mm. With respect to the obtained plastic bottle, the transmittance of visible light having a wavelength of 500 nm and the transmittance of ultraviolet rays having a wavelength of 400 nm were measured. From the results that the transmittance at a wavelength of 500 nm is high and the transmittance at a wavelength of 400 nm is low, the obtained plastic bottle (container) efficiently absorbs ultraviolet rays and sufficiently secures the transmittance of visible light. I found out.

(Preparation of coating material)
-Ultraviolet absorbing layer 0.5 parts by mass of the obtained granular ultraviolet absorber of each example and 2000 parts by mass of dichloromethane as a solvent with respect to 100 parts by mass of norbornene resin (manufactured by JSR Co., Ltd., product name: ARTON F5023). The parts were mixed to obtain a resin solution (resin composition). The obtained resin solution was cast on a surface-polished glass plate using a bar coater, pre-dried at 50 ° C. for 20 minutes, dried at 90 ° C. for 30 minutes, and then a film having a thickness of 80 to 90 μm was formed. After preparation, a square film test piece (ultraviolet absorbing layer) having a side of 2 cm was obtained.
-Preparation of NIR absorption layer A diimonium compound (manufactured by Nippon Kayaku Co., Ltd., product name: IRG-) as a near-infrared absorber with respect to 100 parts by mass of a solvent resin (manufactured by JSR Co., Ltd., product name: ARTON F5023). 068) A resin solution consisting of 0.3 parts by mass and 2000 parts by mass of dichloromethane as a solvent was cast on a surface-polished glass plate using a bar coater, pre-dried at 50 ° C. for 20 minutes, and pre-dried at 90 ° C. for 30 minutes. After drying to prepare a film having a thickness of 50 to 60 μm, a square film test piece having a side of 2 cm was obtained.
The obtained test piece in which the NIR absorption layer and the ultraviolet absorption layer were overlapped was subjected to test light from the ultraviolet absorption layer side with a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd .; 83 ° C, no rain, light source carbon arc). It was exposed for 360 (or 540) hours so as to hit. The transmittance at the maximum wavelength (NIR absorption layer: 1100 nm) in the NIR region before and after the light resistance test was measured, and the light resistance was evaluated by the attenuation rate (Δ transmittance) of the transmittance.
From the result that the Δ transmittance could be reduced in each example, it was confirmed that the near-infrared absorber was effective against photodegradation. As a result, it was found that the near-infrared absorbing layer is excellent in preventing photodegradation of the near-infrared absorbing agent.

The granular ultraviolet absorbers of Examples 1 to 5 are excellent in dustiness and fluidity as compared with Comparative Example 1, and are excellent in melt-kneading property as compared with Comparative Example 2, and therefore exhibit good powder characteristics. I found out. Further, it was found that the compounds of Examples 1 to 5 can be suitably used as an ultraviolet absorber because they are excellent in ultraviolet absorption characteristics.

This application claims priority based on Japanese application Japanese Patent Application No. 2018-067812 filed on March 30, 2018 and Japanese application Japanese Patent Application No. 2018-067830 filed on March 30, 2018. , All of its disclosures are taken here.

Claims (14)

A granular UV absorber containing a triazine compound.
Calculated based on the following procedure for measuring the amount of sieve residue,
The residual amount of the sieve on the sieve having a mesh size of 4.0 mm is 0.3 wt% or more and 1.5 wt% or less.
The residual amount of the sieve on the sieve having a mesh size of 2.8 mm is 5.0 wt% or more and 25.0 wt% or less.
The amount of sieve residue on the sieve having a mesh size of 2.0 mm is 25.0 wt% or more and 35.0 wt% or less.
A granular ultraviolet absorber that satisfies a particle size distribution in which the amount of residual sieve residue on a sieve having a mesh size of 1.0 mm is 35.0 wt% or more and 55.0 wt% or less.
(Measurement procedure for sieve residue)
A predetermined amount (g) of the granular ultraviolet absorber is sieved in this order using a 4.0 mm mesh sieve, a 2.8 mm mesh sieve, a 2.0 mm mesh sieve, and a 1.0 mm mesh sieve. Is performed, the residual weight (g) of the granular ultraviolet absorber remaining on each sieve is measured, and the weight ratio (wt%) of the residual weight to the predetermined amount is calculated as the sieve residual amount. The granular ultraviolet absorber according to claim 1.
A granular ultraviolet absorber, wherein the triazine-based compound contains a compound represented by the following general formula (I).

[In the above general formula (I),
R ¹ is 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, and 7 carbon atoms. Represents an alkylaryl group of ~ 20, an arylalkyl group having 7 to 20 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a substituent represented by the following general formula (II).
R ² and R ³ independently represent a hydrogen atom, a substituted or unsubstituted, linear or branched alkyl group having 1 to 20 carbon atoms, or −OR, and this R is substituted or absent. Substituent linear or branched alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, alkylaryl groups with 7 to 20 carbon atoms, Alternatively, it represents an arylalkyl group having 7 to 20 carbon atoms.
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are independently hydrogen atoms, halogen atoms, substituted or unsubstituted, linear or branched carbons, respectively. Represents an alkyl group with 1 to 8 atoms or a linear or branched alkenyl group with 2 to 8 carbon atoms.
R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a hydroxy group.
However, substituted or unsubstituted, linear or branched alkyl groups having 1 to 20 carbon atoms represented by ^{R 1} , R ² , R ^{3 and R, R 4} , R ⁵ , R ⁶ , R ⁷ , R. The methylene groups in the substituted or unsubstituted, linear or branched alkyl groups having 1 to 8 carbon atoms represented by ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 are oxygen atoms, sulfur atoms, and carbon atoms.} -Carbon double bond, -CO-, -CO-O-, -OC-O-, -CO-NH-, -NH-CO-, -CR ⁰¹ = N- and -N = CR ^02- It may be substituted with at least one structure, and R ⁰¹ and R ⁰² in the structure each independently represent a linear or branched alkyl group having 1 to 8 carbon atoms. ]

[In the above general formula (II),
R ²¹ and R ²² independently represent a hydrogen atom, a substituted or unsubstituted, linear or branched alkyl group having 1 to 20 carbon atoms, or −OR, and this R is substituted or substituted. Unsubstituted, linear or branched alkyl group with 1 to 20 carbon atoms, cycloalkyl group with 3 to 20 carbon atoms, aryl group with 6 to 20 carbon atoms, alkylaryl group with 7 to 20 carbon atoms , Or an arylalkyl group having 7 to 20 carbon atoms.
R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ and R ³¹ are independently hydrogen atoms, halogen atoms, substituted or unsubstituted, linear or branched carbons, respectively. Represents an alkyl group with 1 to 8 atoms, or a linear or branched alkenyl group with 2 to 8 carbon atoms.
R ³² and R ³³ independently represent a hydrogen atom or a hydroxy group, respectively.
X ¹ represents a substituted or unsubstituted, linear or branched alkylene group having 8 or more and 30 or less carbon atoms.
Y ¹ and ^{Y 2} each ^{independently, -CO-O -, - O} -CO -, - L 1 -, - O-L 1 O -, - O-L 1 -, - L 1 -O-CO -, -L ^1- CO-O-, -CO-CH = CH-, -CH = CH-CO-, -CH = CH-CO-O-, -CH = CH-O-CO-, -CO- Represents O-CH = CH-
L ¹ is a linear or branched alkylene group having 1 to 8 carbon atoms.
m and n each independently represent an integer from 0 to 8.
* Represents a bond with an oxygen atom connected to ^{R 1} in the formula (I).
However, substituted or unsubstituted, linear or branched alkyl groups having 1 to 20 carbon atoms represented by ^{R 21} , R ^{22 and R, R 23} , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R. ^{28, R 29, R 30} and the substituted or unsubstituted represented by ^{R 31,} a straight-chain or straight-chain or branched carbon atoms represented by branched alkyl group and ^{X 1} of 1 to 8 carbon atoms The methylene group in the alkylene group of 8 or more and 30 or less is an oxygen atom, a sulfur atom, a carbon-carbon double bond, -CO-, -CO-O-, -OC-O-, -CO-NH-, -NH. It may be substituted with at least one structure selected from −CO−, −CR ⁰³ = N− and −N = CR ^{04− , where R 03} and R ⁰⁴ are independently linear or branched, respectively. Represents an alkyl group having 1 to 8 carbon atoms. ] The granular ultraviolet absorber according to claim 1 or 2.
A granular ultraviolet absorber, wherein the triazine-based compound contains a compound represented by the following general formula (A).

(In the above general formula (A),
^RA1 is 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, and 6 to 6 carbon atoms. Represents an aryl group of 18, an alkylaryl group having 7 to 18 carbon atoms or an arylalkyl group having 7 to 18 carbon atoms.
^RA2 and ^RA3 may be the same or different from each other, and may be 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. Represents
^RA4 , ^RA7 , and ^RA10 may be the same as or different from each other, and are hydrogen atoms, linear or branched alkyl groups having 1 to 8 carbon atoms, or linear or branched alkenyl having 3 to 8 carbon atoms. Represents the group
^RA13 and ^RA17 may be the same and different from each other and represent a hydrogen atom or a hydroxy group.
^However, R ^{A1, R A2} and linear or branched alkyl group having 1 to 12 carbon atoms represented by ^{R A3,} a linear or branched carbon atoms having 1 to 12 of the represented by ^{R A2} and ^{R A3} The methylene group in the alkoxy group is an oxygen atom, a sulfur atom, a carbon-carbon double bond, -CO-, -CO-O-, -OC-O-, -CO-NH-, -NH-CO-,-. It may be substituted with at least one structure selected from CR ⁰⁵ = N − and −N = CR ⁰⁶ −, and R ^{05 and R 06} in the structure are independently linear or branched carbons, respectively. Represents an alkyl group having 1 to 8 atoms. ) The granular ultraviolet absorber according to claim 1 or 2.
The triazine-based compound is the following compound No. From 1A, compound No. A granular UV absorber comprising one or more compounds represented by any of 8A.

The granular ultraviolet absorber according to claim 1 or 2.
A granular ultraviolet absorber, wherein the triazine-based compound contains a compound represented by the following general formula (B).

(In the above general formula (B), R ^B4 , R ^B5 , R ^{B7 to} R ^B9 , R ^{B10 to} R ^B12 , R ^B23 , R ^B24 , R ^{B26 to} R ^B28 , and R ^{B29 to} R ^B31 are independent of each other. , Hydrogen atom, hydroxy group, halogen atom, alkyl group with 1 to 20 carbon atoms, alkenyl group with 2 to 20 carbon atoms, alkoxy group with 1 to 20 carbon atoms, aryl group with 6 to 20 carbon atoms. Representing, n represents an integer of 8 to 14. However, the para position of two benzene rings among the three benzene rings connected to the triazine ring is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or the number of carbon atoms. It represents 1 to 20 alkoxy groups, and one of the ortho positions represents a hydrogen atom or a hydroxy group.) The granular ultraviolet absorber according to claim 5.
The triazine-based compound is the following compound No. From 1B, compound No. A granular UV absorber comprising one or more compounds represented by any of 4B.

(The compound No.4B from the compound ^{No.1B, R A1, R A2,} R B1, R B2, R C1, R C2, R D1 and ^{R D2,} which may be the same or different, a hydrogen atom, a straight It represents an alkyl group having 1 to 4 carbon atoms in a chain or a branch, or an alkoxy group having 1 to 4 carbon atoms in a straight chain or a branch.) The granular ultraviolet absorber according to any one of claims 1 to 6.
A granular ultraviolet absorber having a non-passing amount of 0 wt% when the granular ultraviolet absorber is passed through a 5.0 mm sieve. The granular ultraviolet absorber according to any one of claims 1 to 7.
When the above-mentioned procedure for measuring the residual amount of the sieve is carried out, the granular ultraviolet absorber having a mesh opening of the granular ultraviolet absorber having a diameter of 1.0 mm and a passing amount of 1.0 wt% or more and 15.0 wt% or less. The granular ultraviolet absorber according to any one of claims 2 to 4.
A granular ultraviolet absorber, wherein the triazine compound has a maximum peak in a diffraction angle 2θ of 5.00 ° or more and 6.50 ° or less in a powder X-ray diffraction analysis pattern. The granular ultraviolet absorber according to claim 9.
A granular ultraviolet absorber having a half-value width of a maximum peak of the triazine compound of 0.05 ° or more and 0.20 ° or less. The granular ultraviolet absorber according to claim 9 or 10.
When the relative intensity of the maximum peak of the triazine compound is 100, the diffraction peak having a relative intensity of 30 or more and 60 or less does not exist in the range where the diffraction angle 2θ is 3.0 ° or more and 45.0 ° or less. A characteristic granular UV absorber. The granular ultraviolet absorber according to any one of claims 9 to 11.
Claim When the relative intensity of the maximum peak of the triazine compound is 100, the diffraction peak having a relative intensity of 1 or more and 5 or less does not exist within the range where the diffraction angle 2θ is more than 45.0 ° and 60.0 ° or less. A granular UV absorber characterized by. A resin composition containing the granular ultraviolet absorber according to any one of claims 1 to 12. The resin composition according to claim 13, which contains a synthetic resin.

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