CN112105704A - Particulate ultraviolet absorber and resin composition - Google Patents

Abstract

The granular ultraviolet absorber of the present invention is a granular ultraviolet absorber containing a given triazine compound, and satisfies the following particle size distribution calculated in accordance with the procedure for measuring the amount of a given sieve-remaining component: the amount of the screen residue on a screen having a screen opening of 4.0mm is 0.3 to 1.5 wt%, the amount of the screen residue on a screen having a screen opening of 2.8mm is 5.0 to 25.0 wt%, the amount of the screen residue on a screen having a screen opening of 2.0mm is 25.0 to 35.0 wt%, and the amount of the screen residue on a screen having a screen opening of 1.0mm is 35.0 to 55.0 wt%.

Description

Particulate ultraviolet absorber and resin composition

Technical Field

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

Background

Various developments have been made to ultraviolet absorbers so far. As such a technique, for example, the technique described in patent document 1 is known. Patent document 1 describes the use of a triazine compound obtained by crystallization as an ultraviolet absorber (paragraph 0102 of patent document 1, etc.).

Documents of the prior art

Patent document

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

Disclosure of Invention

Problems to be solved by the invention

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

Means for solving the problems

The present inventors have further conducted studies and, as a result, have found that the powder characteristics of a particulate ultraviolet absorber containing a triazine compound can be appropriately controlled by using the particle size distribution based on sieving as a guide. As a result of further intensive studies based on such findings, it was found that the powdery properties of the above-mentioned granular ultraviolet absorbers can be improved by controlling the amounts of the residual components in each of the sieves having a mesh size of 4.0mm, a mesh size of 2.8mm, a mesh size of 2.0mm and a mesh size of 1.0mm within given numerical ranges, respectively, and the present invention was completed.

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

the granular ultraviolet absorber satisfies the following particle size distribution calculated according to the following procedure for measuring the amount of the screen residue:

the amount of the screen residue on a screen having a screen opening of 4.0mm is 0.3 to 1.5% by weight,

the amount of the screen residue on the screen having a screen opening of 2.8mm is 5.0 to 25.0 wt%,

the amount of the screen residue on the screen having a screen opening of 2.0mm is 25.0 to 35.0 wt%,

the amount of the screen residue on a screen having a screen opening of 1.0mm is 35.0 to 55.0 wt%,

(measurement of amount of residual component on Screen)

A predetermined amount of the granular ultraviolet absorber was sieved using a sieve having a mesh size of 4.0mm, a sieve having a mesh size of 2.8mm, a sieve having a mesh size of 2.0mm and a sieve having a mesh size of 1.0mm in this order, the residual weight of the granular ultraviolet absorber remaining on each sieve was measured, and the weight ratio of the residual weight to the predetermined amount was calculated as the amount of the sieve residue, wherein the unit of the weight of the granular ultraviolet absorber was gram and the unit of the amount of the sieve residue was weight%.

Further, the present invention provides a resin composition containing the above particulate ultraviolet absorber.

Effects of the invention

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

Description of the drawings

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

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

FIG. 2 is an X-ray diffraction chart of the particulate ultraviolet absorber of comparative example 1.

Detailed Description

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

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

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

[ chemical formula 1]

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

R¹represents a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a substituent represented by the following general formula (II),

R²and R³Each independently represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or-O-R, wherein R represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,

R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹and R¹²Each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted, linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkenyl group having 2 to 8 carbon atoms,

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

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

[ chemical formula 2]

In the above-mentioned general formula (II),

R²¹and R²²Each independently represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or-O-R, wherein R represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,

R²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、R³⁰and R³¹Each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted, linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkenyl group having 2 to 8 carbon atoms,

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

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

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

L¹Is a straight-chain or branched alkylene group having 1 to 8 carbon atoms,

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

represents R bonded to the compound of formula (I)¹The site of the attached oxygen atom.

Wherein R is²¹、R²²And R represents a substituted or unsubstituted, linear or branched alkyl group having 1 to 20 carbon atoms, R²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、R³⁰And R³¹A substituted or unsubstituted, linear or branched C1-8 alkyl group and X¹The methylene group in the linear or branched C8-30 alkylene group may be selected from the group consisting of an oxygen atom, a sulfur atom, a carbon-carbon double bond, -CO-O-, -OC-O-, -CO-NH-, -NH-CO-, -CR⁰³N-and-N-CR⁰⁴At least one structural substitution of⁰³And R⁰⁴Each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms.

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

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

As R in the above general formula (I)¹And the aryl group having 6 to 20 carbon atoms represented by R, and examples thereof include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-vinylphenyl group and a 3-isopropylphenyl group4-isopropylphenyl group, 4-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-octylphenyl group, 4- (2-ethylhexyl) phenyl group, 2, 3-dimethylphenyl group, 2, 4-dimethylphenyl group, 2, 5-dimethylphenyl group, 2, 6-dimethylphenyl group, 3, 4-dimethylphenyl group, 3, 5-dimethylphenyl group, 2, 4-di-tert-butylphenyl group, 2, 5-di-tert-butylphenyl group, 2, 6-di-tert-butylphenyl group, 2, 4-di-tert-pentylphenyl group, 2, 5-di-tert-octylphenyl group, biphenyl group, 2,4, 5-trimethylphenyl group and the like.

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

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

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

As R in the above general formula (I)⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹And R¹²And R in the above general formula (II)²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、R³⁰And R³¹Examples of the substituted or unsubstituted, straight-chain or branched alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and,Isopentyl, tert-pentyl, hexyl, heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, and the like. In the particulate ultraviolet absorber of the present embodiment, an alkyl group having 1 to 8 carbon atoms is preferable.

As R in the above general formula (I)¹、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹And R¹²And R in the above general formula (II)²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、R³⁰And R³¹Examples of the straight-chain or branched alkenyl group having 2 to 8 carbon atoms include straight-chain and branched propenyl, butenyl, pentenyl, hexenyl, heptenyl and octenyl, and the position of the unsaturated bond is not limited.

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

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

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

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

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

[ chemical formula 3]

In the above-mentioned general formula (A),

R^A1represents a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a linear or branched alkenyl group having 3 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms or an arylalkyl group having 7 to 18 carbon atoms,

R^A2and R^A3The same or different from each other, represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched alkoxy group having 1 to 12 carbon atoms,

R^A4、R^A7、R^A10the same or different from each other, represent a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkenyl group having 3 to 8 carbon atoms,

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

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

As R in the above general formula (A)^A1、R^A2And R^A3Examples of the straight-chain or branched alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, n-octyl, isooctyl, tert-octyl, and 2-ethylhexylAnd linear or branched alkyl groups such as nonyl, isononyl, decyl, undecyl, and dodecyl.

As R in the above general formula (A)^A2And R^A3Examples of the straight-chain or branched alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, isobutoxy, pentoxy, isopentoxy, tert-pentoxy, hexoxy, 2-hexoxy, 3-hexoxy, cyclohexoxy, 4-methylcyclohexoxy, heptoxy, 2-heptoxy, 3-heptoxy, isoheptoxy, tert-heptoxy, 1-octoxy, isooctyloxy and tert-octoxy.

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

As R in the above general formula (A)^A1Examples of the aryl group having 6 to 18 carbon atoms or the alkylaryl group having 7 to 18 carbon atoms include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 2, 3-dimethylphenyl, 2, 4-dimethylphenyl, 2, 5-dimethylphenyl, 2, 6-dimethylphenyl, 3, 4-dimethylphenyl, 3, 5-dimethylphenyl, 2, 4-di-tert-butylphenyl, 2, 5-di-tert-butylphenyl, 2-isobutyl, 4-butylphenyl, 4-tert-butylphenyl, 4, 2, 6-di-t-butylphenyl, 2, 4-di-t-pentylphenyl, 2, 5-di-t-octylphenyl, biphenyl, 2,4, 5-trimethylphenyl, and the like, and examples of the alkylaryl group having 7 to 18 carbon atoms include benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, and the like.

As R in the above general formula (A)^A1、R^A4、R^A7And R^A10Examples of the straight-chain or branched alkenyl group having 3 to 8 carbon atoms include straight-chain and branched propenyl, butenyl, pentenyl, hexenyl, heptenyl and octenyl, and the position of the unsaturated bond is not limited.

As R in the above general formula (A)^A4、R^A7And R^A10Examples of the straight-chain or branched alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, octyl, and tert-octyl. Among them, methyl is preferable because of its excellent ultraviolet absorption ability.

The triazine compound represented by the general formula (a) preferably contains one or more triazine compounds represented by any one of the following compound nos. 1A to 5A.

[ chemical formula 4]

The triazine compound represented by the general formula (a) preferably contains one, or 2 or more triazine compounds represented by any one of the following compound nos. 6A to 8A.

[ chemical formula 5]

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

[ chemical formula 6]

In the above-mentioned general formula (B),

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

In the above general formula (B), R^B4、R^B5、R^B7～R^B9、R^B10～R^B12、R^B23、R^B24、R^B26～R^B28、R^B29～R^B31Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

In the above general formula (B), R^B4、R^B5、R^B7～R^B9、R^B10～R^B12、R^B23、R^B24、R^B26～R^B28、R^B29～R^B31Examples of the straight-chain or branched alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, 2-propyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, decyl, dodecyl and octadecyl.

In the above general formula (B), R^B4、R^B5、R^B7～R^B9、R^B10～R^B12、R^B23、R^B24、R^B26～R^B28、R^B29～R^B31Examples of the straight-chain or branched alkenyl group having 2 to 8 carbon atoms include vinyl, 1-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-ethyl-1-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl and the like.

In the above general formula (B), R^B4、R^B5、R^B7～R^B9、R^B10～R^B12、R^B23、R^B24、R^B26～R^B28、R^B29～R^B31Examples of the straight-chain or branched alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, tert-pentyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, isoheptyloxy, tert-heptyloxy, 1-octyloxy, isooctyloxy, and tert-octyloxy.

In the above general formula (B), R^B4、R^B5、R^B7～R^B9、R^B10～R^B12、R^B23、R^B24、R^B26～R^B28、R^B29～R^B31Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, indenyl, 2-methylphenyl, 3-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-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, 4-butylphenyl, 2, 5-di-tert-butylphenyl, 2, 6-di-tert-butylphenyl, 2, 4-di-tert-pentylphenyl, 2, 5-di-tert-octylphenyl, 2, 4-dicumylphenyl, 4-cyclohexylphenyl, (1,1' -biphenyl) -4-yl, 2,4, 5-trimethylphenyl, ferrocenyl and the like.

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

[ chemical formula 7]

In the above-mentioned Compound No.1B to Compound No.4B, R^A1、R^A2、R^B1、R^B2、R^C1、R^C2、R^D1And R^D2The alkyl groups may be the same or different and each represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 4 carbon atoms.

The method for synthesizing the triazine-based compound is not particularly limited, and any synthesis method commonly used for synthesizing a compound having a triazine structure may be used. For example, a method of causing an addition reaction of a phenol derivative or a resorcinol derivative with cyanuric chloride using aluminum trichloride is mentioned. The substituent group on the benzene ring bonded to the triazine ring by a single bond may be introduced after the triazine structure is formed, or may be introduced into the phenol compound or the resorcinol derivative before the triazine structure is formed.

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

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

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

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

The particulate ultraviolet absorber of the present embodiment is in the form of particles (japanese text: particulate). The granular ultraviolet absorber may be used in the form of granules as it is, or may be used after being processed into granules (ペレット), briquettes, tablets, and the like.

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

The amount of the screen residue on each screen of the particulate ultraviolet absorber of the present embodiment can be calculated by the following measurement procedure.

The given amount (g) of the granular ultraviolet absorber was sieved using a sieve having a mesh opening of 4.0mm, a sieve having a mesh opening of 2.8mm, a sieve having a mesh opening of 2.0mm and a sieve having a mesh opening of 1.0mm in this order, the residual weight (g) of the granular ultraviolet absorber remaining on each sieve was determined, and the weight ratio (wt%) of the residual weight to the given amount was calculated as the amount of the sieve remaining component.

The inventors found that the particle size distribution can be stably measured even for a powder having a somewhat broad particle size distribution and containing relatively large particles by using a sieving condition using a plurality of sieves having appropriate mesh openings.

In the present embodiment, the amount of the residual components on the sieve having a sieve opening of 4.0mm is, for example, 0.3 to 1.5 wt%, preferably 0.4 to 1.4 wt%, and more preferably 0.4 to 1.3 wt%.

The amount of the residual components on the screen having a screen opening of 2.8mm is, for example, 5.0 to 25.0 wt%, preferably 5.5 to 24.5 wt%, and more preferably 6.0 to 24.0 wt%.

The amount of the residual components on the screen having a screen opening of 2.0mm 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, and more preferably 26.0 wt% or more and 33.0 wt% or less.

The amount of the residual components on the screen having a screen opening of 1.0mm 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, and more preferably 37.0 wt% or more and 53.0 wt% or less.

When the amount of the screen residue in each screen is set within the above numerical range, the powder-like property, fluidity and melt-kneading property can be improved because the particle size distribution is appropriate within the range of 1mm or more. Therefore, a particulate ultraviolet absorber having excellent powder characteristics can be realized.

In the granular ultraviolet absorber of the present embodiment, the amount of the non-passing component when passing through a sieve having a mesh size of 5.0mm may be 0% by weight. By excluding coarse particles in this way, a particulate ultraviolet absorber having excellent powder characteristics and ultraviolet absorption characteristics can be realized. In addition, melt kneading properties can be improved.

In the granular ultraviolet absorber of the present embodiment, the amount of the passing component passing through a sieve having a mesh opening of 1.0mm 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, and more preferably 3.0 wt% or more and 14.0 wt% or less. By setting the content to the above upper limit or less, the dustiness and the fluidity can be improved.

In the granular ultraviolet absorber of the present embodiment, the total amount of the screen residue components of the screen having a screen opening of 4.0mm, the screen having a screen opening of 2.8mm, the screen having a screen opening of 2.0mm and the screen having a screen opening of 1.0mm is 100% by weight or less. The total of the amounts of the screen residue components and the amount of the passing components in the sieves having mesh openings of 4.0mm, 2.8mm, 2.0mm and 1.0mm can be 100% by weight.

In the present embodiment, the amount of the screen residue in each screen can be controlled by appropriately selecting, for example, the type and shape of the triazine compound, the method for producing the triazine compound, and the like. Among them, as an element for making the amount of the screen residue in each screen to be in a desired numerical range, for example, processing conditions such as melt solidification, pulverization, classification, and the like of the triazine compound are suitably employed.

Further, the present inventors have further studied and found that the powder characteristics of the triazine compound and the particulate ultraviolet absorber using the compound can be appropriately controlled by using an X-ray diffraction analysis chart as a guide. As a result of further studies based on the above findings, it has been found that the powder characteristics of the triazine compound and the particulate ultraviolet absorber using the same can be improved by setting the diffraction angle 2 θ at which the maximum intensity peak is present in the powder X-ray diffraction analysis chart within a predetermined numerical range.

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

The triazine compound of the present embodiment may have a maximum intensity peak in a powder X-ray diffraction analysis chart in a range where the diffraction angle 2 θ is 5.00 ° or more and 6.50 ° or less, preferably 5.20 ° or more and 6.00 ° or less, and more preferably 5.40 ° or more and 5.80 ° or less. This improves the charging properties and the compression pelletizability, and therefore, a triazine compound and a granular ultraviolet absorber having excellent powder characteristics can be realized.

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

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

In the powder X-ray diffraction analysis chart of the triazine compound, when the relative intensity of the maximum intensity peak is 100, no diffraction peak having a relative intensity of, for example, 30 or more and 60 or less, preferably 25 or more and 60 or less, more preferably 22 or more and 60 or less, is present in the range having a diffraction angle 2 θ of 3.0 ° or more and 45.0 ° or less. That is, by relatively increasing the peak intensity of the strongest peak, a particulate ultraviolet absorber having excellent powder characteristics and ultraviolet absorption characteristics can be realized.

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

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

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

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

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

Specific examples of the synthetic resin include the following resins.

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

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

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

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

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

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

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

The amount of the particulate ultraviolet absorber incorporated in the resin composition is, for example, preferably 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and still more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the synthetic resin. When the content is not less than the lower limit, a sufficient effect of the particulate ultraviolet absorber can be obtained. When the amount is not more than the above upper limit, desired resin physical properties can be achieved while enhancing the effect of adding the particulate ultraviolet absorber.

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

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

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

Examples of the phenolic antioxidant include 2, 6-di-t-butyl-p-cresol, 2, 6-diphenyl-4-octadecyloxyphenol, distearyl (3, 5-di-t-butyl-4-hydroxybenzyl) phosphonate, 1, 6-hexamethylenebis [ (3, 5-di-t-butyl-4-hydroxyphenyl) propionamide ], 4' -thiobis (6-t-butyl-m-cresol), 2' -methylenebis (4-methyl-6-t-butylphenol), 2' -methylenebis (4-ethyl-6-t-butylphenol), 4' -butylidenebis (6-t-butyl-m-cresol), 2' -ethylenebis (4, 6-di-tert-butylphenol), 2' -ethylenebis (4-sec-butyl-6-tert-butylphenol), 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3, 5-tris (2, 6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -2,4, 6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 2-tert-butylidenebis (4-methyl-4-hydroxy-5-t-butylbenzyl) isocyanurate, Stearyl (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid methyl ester ] methane, thiodiethylene glycol bis [ (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 1, 6-hexamethylenebis [ (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], bis [3, 3-bis (4-hydroxy-3-tert-butylphenyl) butanoic acid ] ethylene glycol ester, bis [ 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl ] terephthalate, 1,3, 5-tris [ (3, 5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl isocyanurate, 3, 9-bis [1, 1-dimethyl-2- { (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy } ethyl ] -2,4,8, 10-tetraoxaspiro [5,5] undecane, triethylene glycol bis [ (3-t-butyl-4-hydroxy-5-methylphenyl) propionate ], and the like.

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

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

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

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

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

Examples of the near-infrared absorber include polymethine dyes (cyanine dyes), indocyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, naphthol metal complex dyes, squarylium dyes, trisazo dyes, dithiol metal complex salt dyes, pyrylium dyes, thiopyrylium dyes, indoaniline dyes, azoanthraquinone dyes, naphthoquinone dyes, anthraquinone dyes, bis (dithioene) dyes, triphenylmethane dyes, aluminum (aluminum) dyes, and diimmonium dyes. Further, an inorganic near-infrared absorber can be used, and examples thereof include carbon black, tin oxide doped with antimony oxide or indium oxide, and oxides, carbides, or borides of metals belonging to groups 4A, 5A, or 6A of the periodic table.

Examples of the nucleating agent include metal salts of benzoic acids such as aluminum p-tert-butylbenzoate and sodium benzoate, metal salts of aromatic phosphates such as sodium bis (2, 4-di-tert-butylphenyl) phosphate, sodium methylenebis (2, 4-di-tert-butylphenyl) phosphate, and aluminum bis [ methylenebis (2, 4-di-tert-butylphenyl) phosphate ] hydroxy, metal salts of aromatic phosphates, dibenzylidene sorbitols such as alkali metal compounds, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, and bis (dimethylbenzylidene sorbitol), metal salts of amino acids, metal salts of rosin, N '-tris [ 2-methylcyclohexyl ] -1,2, 3-propanetricarboxylic acid amide, N' -tricyclohexyl-1, amide compounds such as3, 5-benzenetricarboxylic acid amide, N' -dicyclohexylnaphthalimide, and 1,3, 5-tris (dimethylisopropylamido) benzene.

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

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

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

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

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

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

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

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

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

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

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

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

Examples of the phosphate flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris (dichloropropyl) phosphate, triphenyl phosphate, tricresyl phosphate, tolyldiphenyl phosphate, trixylyl phosphate, octyldiphenyl phosphate, ditolyl diphenyl phosphate, triisopropylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tert-butylphenyl diphenyl phosphate, bis (tert-butylphenyl) phenyl phosphate, tris (tert-butylphenyl) phosphate, isopropylphenyl diphenyl phosphate, bis (isopropylphenyl) diphenyl phosphate, and tri (isopropylphenyl) phosphate.

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

Examples of the other inorganic flame retardant aid include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide and talc, and surface-treated products thereof, and various commercially available products such as TIPAQUE R-680 (titanium oxide: manufactured by Shikugaku Kogyo Co., Ltd.) and KYOWAMAG 150 (magnesium oxide: manufactured by Kyowa Kagaku Co., Ltd.) can be used.

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

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

Examples of the blowing agent include decomposition type organic blowing agents such as azodicarbonamide, azobisisobutyronitrile, p '-oxybisbenzenesulfonylhydrazide, n' -dinitrosopentamethylenetetramine, p-toluenesulfonyl semicarbazide, and trihydrazinotriazine, and decomposition type inorganic blowing agents such as sodium hydrogencarbonate, ammonium carbonate, ammonium hydrogencarbonate, ammonium nitrite, azide, and sodium borohydride.

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

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

Examples of the epoxy-based stabilizer include compounds having an aliphatic, aromatic, alicyclic, araliphatic or heterocyclic structure and an epoxy group as a side chain. The epoxy group is preferably bonded as a glycidyl group to the residue of the molecule via an ether or ester bond, or it may be an N-glycidyl derivative of a heterocyclic amine, amide or imide. Specific examples thereof include epoxidized soybean oil, epoxidized linseed oil, and epoxidized monoester. Commercially available epoxy stabilizers include, for example, those available under the product names "ADK CIZER O-130P", "ADK CIZER O-180A", "ADK CIZER D-32", "ADK CIZER EP-13" and "ADK CIZER FEP-13" from ADEKA, Inc.

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

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

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

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

Examples of the aminosilane compound include γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, and γ - (2-aminoethyl) aminopropyltrimethoxysilane.

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

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

The fluorescent whitening agent is a compound that absorbs ultraviolet rays of sunlight or artificial light, converts the ultraviolet rays into violet to blue visible light, and then emits the visible light to promote the whiteness and bluish property of the molded article. Examples of the fluorescent whitening agent include benzoxazole compounds C.I. FluoresscentBrightner 184; coumarin-based compound c.i. fluorescent Brightner 52; diaminostyrene disulfonic acid compounds c.i Fluorescent Brightner 24, 85, 71, etc.

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

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

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

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

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

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

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

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

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

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

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

In the resin composition of the present embodiment, the particulate ultraviolet absorber of the present embodiment, the synthetic resin used as the binder resin, and other additive components as necessary are dissolved in a solvent to prepare a varnish resin (varnish-like resin composition that is liquid at room temperature). As the solvent, an organic solvent or an aqueous solvent can be used. The resin varnish may be used in the form of an emulsion in which a powdery ultraviolet absorber is dispersed, using an emulsifier, if necessary.

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

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

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

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

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

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

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

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

Examples

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

[ preparation of particulate ultraviolet absorber ]

(example 1)

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

In a 300ml four-necked flask, 10.00g of 2,4, 6-tris (2, 4-dihydroxy-3-methylphenyl) triazine, 22.68g of sodium hydroxide, 80.00g of dimethylformamide and 11.07g of 1-bromohexane were charged, the temperature was raised to 80 ℃ and the reaction was allowed to proceed for 9 hours. After neutralization with hydrochloric acid, washed with water and desolventized under reduced pressure, the residue was purified from toluene isopropanol ═ 1: 1 to obtain crystals. Then, the molten object (crystal) is dropped onto a metal plate and cooled to obtain a thin sheet (melt-solidification process). The obtained flakes were roughly pulverized and classified, thereby obtaining 11.89g (yield: 76%) of pale yellow particles having a melting point of 145 ℃.

The compound obtained (pale yellow granules) was subjected to¹H-NMR measurement. The pale yellow particles obtained were identified as the granular compound (granular ultraviolet absorber) represented by the following formula No.1 according to the following analysis results.

[ chemical formula 8]

(examples 2 to 5)

In the same manner as in example 1, different batches of granular compound No.1 (granular ultraviolet absorber) were obtained.

Comparative example 1

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

Comparative example 2

In example 1, the compound having a coarse particle diameter obtained at the time of classification was collected to obtain a particulate ultraviolet absorber.

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

[ Table 1]

(particle size distribution)

The 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 the substance remaining on each sieve. The details are as follows.

First, about 200g (total amount) of the obtained granular ultraviolet absorber was placed in the uppermost sieve, and vibrated for 3 minutes using a vibratory sieving apparatus (AS 300, manufactured by RETSCH corporation) having a sieve under the conditions of the sieve having the below-described sieve opening and vibration amplitude (sieving operation). The weight (g) of the granular ultraviolet absorber remaining on each sieve was measured, and the weight ratio (wt%) of the ultraviolet absorber to the total amount introduced was calculated as the amount of the sieve remaining component.

Sieve opening: 4.0mm, 2.8mm, 2.0mm, 1.0mm (from top to bottom)

Amplitude: 1.00mm, 3 minutes

In table 1, the screen residual component amount indicates the weight ratio of the particulate ultraviolet absorber remaining on the screen by the screening operation. The amount of the pass component indicates the weight ratio of the particulate ultraviolet absorber passing through a sieve having a (pass) opening of 1.0 mm.

In addition, Table 1 shows the results of the amount (wt%) of the screen residue on the screen having a mesh opening of 5.0mm when the obtained granular ultraviolet absorber was sieved using a screen having a mesh opening of 5.0 mm.

(dusty)

Operability

0.2 part by mass of the obtained granular ultraviolet absorber was mixed with 100 parts by mass of a polycarbonate resin, and the mixture was mixed for 10 minutes by a Henschel mixer to obtain a mixture. The workability was evaluated according to the following evaluation criteria.

Very good: little fly ash was observed.

X: a large amount of fly ash was observed.

Working environment property

The obtained granular ultraviolet absorber was dropped onto a tray from 30cm above, and the amount of the ultraviolet absorber carried on the tray was measured. The working environment property was evaluated according to the following evaluation criteria.

O: the remaining amount in the tray is relatively large.

X: the remaining amount in the tray is small and most spills out of the tray.

(fluidity)

0.2 part by mass of the obtained granular ultraviolet absorber was mixed with 100 parts by mass of a polycarbonate resin, and the mixture was mixed for 10 minutes by a henschel mixer to obtain a mixture, and the obtained mixture was fed from a hopper of an extruder to the extruder. The fluidity in the hopper was evaluated according to the following evaluation criteria.

Very good: the fluidity of the mixture was good and no feeding failure occurred.

O: the mixture was relatively fluid and no feeding failure occurred within a range that was not problematic in practical use.

X: the fluidity of the mixture is reduced and poor feeding occurs.

(melt kneading Property)

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

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

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

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

The obtained particulate ultraviolet absorbers of example 1 and comparative example 1 were subjected to X-ray diffraction analysis. The evaluation results are shown in tables 2 to 4.

[ Table 2]

(X-ray diffraction)

The obtained granular ultraviolet absorber was subjected to powder X-ray diffraction measurement using Ultima IV (Ri gaku corporation) under the following measurement conditions.

(measurement conditions)

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

without removal of CuK α 2)

Tube voltage/tube current: 40kV/40mA

Accessories: multifunctional film sample holder

A monochromator: fixing

A filter: is free of

Divergent slit: 2/3 degree

Divergent vertical restriction slit: 10mm

Scattering slit: 1.17mm

Light receiving slit: 0.3mm

The scanning type is as follows: continuous scanning

Scanning speed: 4 °/min

Sampling width: 0.02 degree

Scanning axis 2 theta/omega

Scanning range: 3-90 °

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

[ Table 3]

TABLE 3

Fig. 2 shows the results of the powder X-ray diffraction analysis of the particulate ultraviolet absorber of comparative example 1. Table 4 shows diffraction angle 2 θ, d value, and relative intensity corresponding to each peak in fig. 2. In table 4, the threshold value of the peak intensity is set to 1/100.

[ Table 4]

TABLE 4

(feeding Property)

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

Quantitative Property

The amount discharged from the gravimetric feeder (feed amount) was measured every 10 minutes over time. When the variation in the feed amount was small, the evaluation was O, and when the variation in the feed amount was large, the evaluation was X.

Long term property

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

(compression granulation Property)

Using a roller compactor (manufactured by Mikrron corporation, model M-25), at the nip: 3.2mm and roll speed: the obtained granular ultraviolet absorber was granulated by compression at 14rpm to obtain plate-like granules having a thickness of 4 mm. The obtained plate-like granules were pulverized, coarse powder was removed by a 5-mesh vibrating screen, and fine powder was removed by a 24-mesh vibrating screen (size stabilization), to obtain plate-like granules remaining on the 24-mesh vibrating screen.

The appearance of the resulting granulated substance was observed, and the degree of disintegration of the granulated substance was evaluated based on the following criteria.

When no disintegration was observed in 10 granules out of 10, it was marked as "o", when partial disintegration was observed in 1 to 4 granules out of 10, it was marked as "Δ", and when partial or total disintegration was observed in 5 or more granules out of 10, it was marked as "x".

[ preparation of resin composition ]

(production of film)

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

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

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

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

(production of Container)

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

(production of coating Material)

Ultraviolet absorbing layer

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

Preparation of the NIR-absorbing layer

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

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

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

The granular ultraviolet absorbers of examples 1 to 5 were excellent in dustiness and fluidity as compared with comparative example 1, and excellent in melt-kneading property as compared with comparative example 2, and thus, exhibited good powder characteristics. In addition, the compounds of examples 1 to 5 have excellent ultraviolet absorption characteristics, and thus can be suitably used as ultraviolet absorbers.

The present application claims priority based on japanese application laid-open No. 2018-067807 filed on 30/3/2018 and japanese application laid-open No. 2018-067830 filed on 30/3/2018, the entire disclosures of which are incorporated herein.

Claims (14)

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

the granular ultraviolet absorber satisfies the following particle size distribution calculated according to the following procedure for measuring the amount of the screen residue:

the amount of the screen residue on a screen having a screen opening of 4.0mm is 0.3 to 1.5% by weight,

the amount of the screen residue on the screen having a screen opening of 2.8mm is 5.0 to 25.0 wt%,

the amount of the screen residue on the screen having a screen opening of 2.0mm is 25.0 to 35.0 wt%,

the amount of the screen residue on a screen having a screen opening of 1.0mm is 35.0 to 55.0 wt%,

measuring the amount of the screen residue:

a predetermined amount of the granular ultraviolet absorber was sieved using a sieve having a mesh size of 4.0mm, a sieve having a mesh size of 2.8mm, a sieve having a mesh size of 2.0mm and a sieve having a mesh size of 1.0mm in this order, the residual weight of the granular ultraviolet absorber remaining on each sieve was measured, and the weight ratio of the residual weight to the predetermined amount was calculated as the amount of the sieve residue, wherein the unit of the weight of the granular ultraviolet absorber was gram and the unit of the amount of the sieve residue was weight%.

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

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

R¹represents a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a substituent represented by the following general formula (II),

R²and R³Each independently represents a hydrogen atom, a substituted or unsubstituted straight chain or a moietyA branched C1-20 alkyl group or-O-R, wherein R represents a substituted or unsubstituted straight-chain or branched C1-20 alkyl group, a C3-20 cycloalkyl group, a C6-20 aryl group, a C7-20 alkylaryl group, or a C7-20 arylalkyl group,

R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹and R¹²Each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted, linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkenyl group having 2 to 8 carbon atoms,

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

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

in the general formula (II) described above,

R²¹and R²²Each independently represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or-O-R, wherein R represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having a lower alkyl,Or an arylalkyl group having 7 to 20 carbon atoms,

R²³、R²⁴、R²⁵、R²⁶、R²⁷、R²⁸、R²⁹、R³⁰and R³¹Each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted, linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkenyl group having 2 to 8 carbon atoms,

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

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

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

L¹Is a straight-chain or branched alkylene group having 1 to 8 carbon atoms,

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

represents R bonded to the compound of formula (I)¹The site of the attached oxygen atom(s),

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

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

in the general formula (A) described above,

R^A1represents a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a linear or branched alkenyl group having 3 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms or an arylalkyl group having 7 to 18 carbon atoms,

R^A2and R^A3The same or different from each other, represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched alkoxy group having 1 to 12 carbon atoms,

R^A4、R^A7、R^A10the same or different from each other, represent a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkenyl group having 3 to 8 carbon atoms,

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

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

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

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

in the general formula (B) described above,

R^B4、R^B5、R^B7～R^B9、R^B10～R^B12、R^B23、R^B24、R^B26～R^B28、R^B29～R^B31independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and n represents an integer of 8 to 14, wherein, in 3 benzene rings connected to the triazine ring, para-positions of 2 benzene rings represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, and one of ortho-positions represents a hydrogen atom or a hydroxyl group.

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

in the compounds No.1B to No.4B, R is^A1、R^A2、R^B1、R^B2、R^C1、R^C2、R^D1And R^D2The alkyl groups are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 4 carbon atoms.

7. The granular ultraviolet absorber as claimed in any one of claims 1 to 6, wherein the amount of the non-passing components when the granular ultraviolet absorber passes through a sieve having a 5.0mm mesh size is 0% by weight.

8. The particulate ultraviolet absorber according to any one of claims 1 to 7, wherein when the step of measuring the amount of the screen residue component is performed, the amount of the screen residue component passing through a screen having a screen opening of 1.0mm is 1.0 wt% or more and 15.0 wt% or less.

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

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

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

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

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

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

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