CN117651750A

CN117651750A - Ultraviolet absorber, method for producing same, composition, molded article, and coating film

Info

Publication number: CN117651750A
Application number: CN202280048114.6A
Authority: CN
Inventors: 千叶优美香; 辰巳僚一; 槇大辅
Original assignee: Toyo Ink SC Holdings Co Ltd; Toyocolor Co Ltd
Current assignee: Toyocolor Co Ltd; Artience Co Ltd
Priority date: 2021-07-14
Filing date: 2022-07-11
Publication date: 2024-03-05
Also published as: JP7164783B1; WO2023286725A1; KR20240033216A; JP2023014019A

Abstract

An ultraviolet absorber comprising at least one ultraviolet absorbing dye selected from the group consisting of compounds represented by the following general formulae (1) to (3), and a metal component containing at least one metal atom selected from the group consisting of Na, mg, al, K, ca and Fe, wherein the content of the metal component in the ultraviolet absorber is 0.1ppm to 50000ppm relative to the ultraviolet absorber.

Description

Ultraviolet absorber, method for producing same, composition, molded article, and coating film

Technical Field

The present invention relates to an ultraviolet absorber, a method for producing the same, a composition, a molded article, and a coating film.

Background

Conventionally, ultraviolet absorbers have been blended with resins to impart ultraviolet absorbability to molded articles and coating films. It is pointed out that: among ultraviolet rays of light in a wavelength range (100 nm to 400 nm) shorter than the visible range in sunlight, not only ultraviolet rays having a wavelength of less than 400nm but also light in a short wavelength region of visible light having a wavelength of about 400nm to 420nm in recent years cause damage to organic matter and human body. Accordingly, in particular applications, there is a need for an ultraviolet absorber that absorbs light in the short wavelength range of visible light.

For example, in packaging materials for pharmaceutical agents, cosmetics, and the like, organic substances in the contents are degraded by the action of ultraviolet rays contained in sunlight and the like. Further, since specific components such as vitamins deteriorate under light in the short wavelength region of visible light of about 400nm to 420nm, an ultraviolet absorber capable of absorbing light in the longer wavelength region is demanded.

In addition, in a display device, an ultraviolet absorber is generally added to an optical film such as a polarizing plate protective film, to prevent discoloration of the optical film. In addition, in order to prevent the near infrared ray absorber included in the antireflection film from being degraded by ultraviolet rays, an ultraviolet ray absorber is added to the antireflection film. In addition, various organic substances such as fluorescent materials and phosphorescent materials are used in light emitting elements of organic Electroluminescence (EL) displays, and ultraviolet absorbers are added to surface films, substrates, adhesives, coating films on surfaces of polarizing plates, and the like of the displays in order to prevent deterioration of the organic substances due to ultraviolet rays.

In addition, for various applications such as optical lenses, solar cells, window films, etc., there is also a demand for an ultraviolet absorber that absorbs ultraviolet rays and light in a short wavelength region of visible light of about 400nm to 420nm for the purpose of protecting organic matters in materials. In addition, in recent years, in molded articles and coating films for such applications, further improvement in high ultraviolet ray shielding properties, heat resistance and light resistance has been demanded, and it has been demanded that coloring and deterioration due to heating or exposure to ultraviolet rays over a long period of time are less likely to occur, and that excellent visible transparency and ultraviolet ray shielding properties are maintained.

For example, patent documents 1 and 2 disclose benzotriazole ultraviolet absorbers that absorb light in a short wavelength region of visible light of about 400nm to 420 nm.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2018-177696

Patent document 2: japanese patent laid-open publication No. 2016-514756

Disclosure of Invention

Problems to be solved by the invention

However, the conventional ultraviolet absorber absorbs light in the short wavelength region of visible light of about 400nm to 420nm, but has problems such as low heat resistance and light resistance and low ultraviolet absorptivity due to heating or long-term exposure to ultraviolet light. Further, if the amount of the ultraviolet absorber added is increased to obtain sufficient ultraviolet shielding properties, there is a problem that the transparency of the coating film and the molded article is lowered.

An object of an embodiment of the present invention is to provide an ultraviolet absorber that has excellent ultraviolet absorbability that absorbs not only ultraviolet rays of less than 400nm but also light in a short wavelength region of visible light of about 400nm to 420nm, and that has heat resistance, light resistance, and transparency.

Technical means for solving the problems

Embodiments of the present invention are as follows.

1 > an ultraviolet absorber comprising at least one ultraviolet absorbing dye selected from the group consisting of compounds represented by the following general formulae (1) to (3), and a metal component containing at least one metal atom selected from the group consisting of Na, mg, al, K, ca and Fe, wherein the content of the metal component in the ultraviolet absorber is 0.1ppm to 50000ppm relative to the ultraviolet absorber.

[ chemical 1]

(in the general formulae (1) to (3), R _1b ～R _1g 、R _2a ～R _2g And R is _3a ～R _3g Independently represent a group selected from the group consisting of a hydrogen atom, a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a sulfo group, and R ₇ 、Ar ₁ And any one of the groups represented by the following general formulae (4-1) to (4-3).

R ₇ Represents any one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkenyloxy group having 1 to 20 carbon atoms, and may have a substituent of a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a carboxyl group, or a sulfo group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms and alkenyloxy having 1 to 20 carbon atoms may be bonded to each other through one or more groups selected from the group consisting of-O-, -CO-, -COO-, -OCO-, -CONH-, or-NHCO-.

Ar ₁ Represents any one selected from the group consisting of an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a biphenyl group, and may have a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number1 to 20 alkenyloxy groups, aryloxy groups having 6 to 20 carbon atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, nitrile groups, nitro groups, carboxyl groups, or substituents of sulfo groups.

In the general formulae (2) to (3), R ₄ 、R ₅ 、R ₆ Are respectively and independently selected from hydroxyl, R ₇ Ar, ar ₁ Any one of the group consisting of.

[ chemical 2]

General formula (4-1)

＊——X ₁ ——R ₈

In the general formula (4-1), X ₁ Represents a compound selected from the group consisting of-CO-, -COO-, -OCO-, -CONH-, and-NHCO-, is selected from the group consisting of, R is R ₈ Represents a group selected from the group consisting of hydrogen atoms, hydroxyl groups, R ₇ Ar, ar ₁ Any one of the group consisting of. Wherein, in the general formula (4-1), the bonding site with naphthalene ring of the general formula (1) to the general formula (3) is represented.

[ chemical 3]

General formula (4-2)

＊——X ₂ ——R ₉ ——X ₃ ——R ₁₀

In the general formula (4-2), X ₂ 、X ₃ Each independently represents a member selected from the group consisting of-CO-; -COO-, -OCO-, any one of the group consisting of-CONH-, and-NHCO-, R is R ₉ R represents an arylene group having 6 to 20 carbon atoms ₁₀ R represents ₇ Or Ar ₁ . Wherein, in the general formula (4-2), the bonding site with naphthalene ring of the general formula (1) to the general formula (3) is represented.

[ chemical 4]

General formula (4-3)

In the general formula (4-3), X ₄ 、X ₅ Each independently represents a member selected from the group consisting of-CO-; -COO-, -OCO-, any one of the group consisting of-CONH-, and-NHCO-, R is R ₁₁ Represents a linear or branched alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, R ₁₂ R represents ₇ Or Ar ₁ N is 1 to 20. Wherein, in the general formula (4-3), the bonding part with the naphthalene ring in the general formula (1) to the general formula (3)

<2> the ultraviolet absorber according to <1>, wherein the ultraviolet absorbing pigment comprises one or more compounds selected from the group consisting of compounds represented by the following formulas.

[ chemical 5]

< 3 > the ultraviolet absorber according to <1> or <2>, wherein the metal component contains Al.

A composition comprising the ultraviolet absorber according to any one of <1> to < 3 > and at least one second ultraviolet absorber selected from the group consisting of triazine ring-containing compounds, benzotriazole ring-containing compounds, and benzophenone ring-containing compounds, which are compounds other than the compounds represented by the general formulae (1) to (3).

A composition comprising the ultraviolet absorber according to any one of <1> to < 3 > and a color material for blocking light having a wavelength in the visible wavelength range of 450nm to 650 nm.

< 6 > the composition according to < 5 > wherein the color material comprises two or more chromatic colorants.

A composition comprising the ultraviolet absorber according to any one of < 1 > to < 3 > and at least one near infrared absorber selected from the group consisting of phthalocyanine compounds, naphthalocyanine compounds, squarylium compounds, cyanine compounds, and diketopyrrolopyrroles, wherein the near infrared absorber has a maximum absorption in a wavelength region of 600nm to 1500 nm.

< 8 > a composition comprising the ultraviolet absorber according to any one of < 1 > to < 3 > and a resin.

< 9 > the composition according to < 8 > wherein the resin comprises a thermoplastic resin.

A composition comprising the ultraviolet absorber according to any one of < 1 > to < 3 >, a photopolymerizable compound, and a photopolymerization initiator.

A molded article of < 11 > which is molded from the composition of any one of < 4 > to < 10 >.

A coating film of < 12 > which is formed from the composition according to any one of < 4 > to < 10 >.

A method for producing an ultraviolet absorber according to any one of < 1 > to < 3 > comprising the steps of adding a poor solvent containing water to a reaction solution for synthesizing an ultraviolet absorbing dye, separating the solution, and removing a metal component; a step of washing the ultraviolet absorbing pigment with alcohol or water or a mixture thereof after the separation and filtration; a step of reslurrying (reslurry) the ultraviolet-absorbing dye in alcohol, water, or a mixture thereof, and washing the resultant; and a step of reslurrying the ultraviolet-absorbing dye with an acid solution and cleaning the ultraviolet-absorbing dye, thereby adjusting the content of the metal component contained in the ultraviolet-absorbing dye.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the above embodiment, an ultraviolet absorber having excellent ultraviolet absorbability for absorbing not only ultraviolet rays of less than 400nm but also light in a short wavelength region of visible light of about 400nm to 420nm, heat resistance, light resistance, and transparency, a composition, a molded body, and a coating film using the same can be provided.

Drawings

Fig. 1 shows an example of a diffraction pattern of powder X-ray diffraction of an ultraviolet absorber according to an embodiment of the present invention.

Detailed Description

[ ultraviolet absorber ]

The ultraviolet absorber according to an embodiment of the present invention contains one or more ultraviolet absorbing pigments (hereinafter, also referred to as "ultraviolet absorbing pigments (a)") selected from the compounds represented by the following general formulae (1) to (3), and a metal component (hereinafter, also referred to as "metal component (B)") containing one or more metal atoms selected from the group consisting of Na, mg, al, K, ca and Fe, wherein the content of the metal component (B) is 0.1ppm to 50000ppm relative to the ultraviolet absorber.

[ chemical 6]

In the general formulae (1) to (3), R _1b ～R _1g 、R _2a ～R _2g And R is _3a ～R _3g Independently represent a group selected from the group consisting of a hydrogen atom, a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a sulfo group, and R ₇ 、Ar ₁ And any one of the groups represented by the following general formulae (4-1) to (4-3).

Ar ₁ Represents any one selected from the group consisting of an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a biphenyl group, and may have a substituent of a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a carboxyl group, or a sulfo group.

[ chemical 7]

General formula (4-1)

*——X ₁ ——R ₈

[ chemical 8]

General formula (4-2)

*——X ₂ ——R ₉ ——X ₃ ——R ₁₀

[ chemical 9]

General formula (4-3)

In the general formula (4-3), X ₄ 、X ₅ Each independently represents a member selected from the group consisting of-CO-; -COO-, -OCO-, any one of the group consisting of-CONH-, and-NHCO-, R is R ₁₁ Represents a linear or branched alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, R ₁₂ R represents ₇ Or Ar ₁ N is 1 to 20. Wherein, in the general formula (4-3), the bonding site with naphthalene ring of the general formula (1) to the general formula (3) is represented.

The ultraviolet absorber according to the embodiment of the present invention can absorb light in the short wavelength region of visible light of about 400nm to 420nm in addition to the ultraviolet region of less than 400nm by the action of the ultraviolet absorbing dye (a) having a naphthalene ring bonded to a triazine ring. The ultraviolet absorber has unexpected remarkable effects of ensuring light resistance, heat resistance, and ultraviolet absorptivity superior to the conventional ones by containing a metal component (B) containing at least one metal atom selected from the group consisting of Na, mg, al, K, ca and Fe in an appropriate amount. Further, since the high ultraviolet absorptivity enables wavelength absorption even with a small amount of the ultraviolet absorbing dye (a), the addition amount of the ultraviolet absorbing dye (a) can be suppressed, and the effects of suppressing the decrease in transparency of the molded article and the coating film and improving the transparency can be obtained.

The mechanism for obtaining such an effect is presumed as follows. That is, since the ultraviolet absorbing dye (a) included in the ultraviolet absorber according to the embodiment of the present invention includes a triazine ring site having a non-covalent electron pair in a molecular structure, a complex is formed between the ultraviolet absorbing dye (a) and a metal atom, and metal ions are easily incorporated into a dye skeleton. As a result, it is presumed that the crystallinity of the ultraviolet-absorbing pigment is improved, deterioration due to heating and light irradiation is less likely to occur, and heat resistance and light resistance are improved. On the other hand, if the ultraviolet-absorbing pigment is excessively incorporated into the metal ion, the ultraviolet-absorbing pigment component is reduced, and therefore, it is considered that the ultraviolet absorbability is reduced, and the total amount of the metal component (B) containing a metal atom with respect to the ultraviolet absorber is set to 0.1ppm to 50000ppm (more preferably 0.1ppm to 10000ppm, or 0.1ppm to 1000 ppm), so that the incorporation amount of the metal ion into the pigment skeleton can be made appropriate, and therefore, excellent ultraviolet absorbability can be maintained.

Ultraviolet absorbing pigment (A) >, and method for producing the same

The ultraviolet absorbing pigment (a) may be selected from one or more compounds represented by the general formulae (1) to (3), or may be individually combined. The compounds represented by the general formulae (1) to (3) absorb light in the short wavelength region of visible light of about 400nm to 420nm in addition to the ultraviolet region of less than 400 nm.

Among the general formulae (1) to (3), the compounds of the general formula (1) can absorb the longest wavelength, and are most preferable from the viewpoint of absorbing light of longer wavelength, and for example, compounds represented by the following formula are exemplified.

[ chemical 10]

In general formula (3), the maximum absorption wavelength is the shortest wavelength in general formulae (1) to (3), but is most preferably near colorless, and examples thereof include compounds represented by the following formulas.

[ chemical 11]

In addition, the general formula (2) is preferable in terms of obtaining a balance between absorbing light of a longer wavelength and being nearly colorless, and examples thereof include compounds represented by the following formulas.

[ chemical 12]

It is preferable to select or combine any of the general formulae (1) to (3) according to the wavelength region to be absorbed.

The ultraviolet absorber contains an ultraviolet absorbing pigment (A), and further contains a metal component (B) in an amount of 0.1 to 50000ppm based on 100 parts by mass of the ultraviolet absorber. By containing the metal component (B) in an appropriate amount, the decrease in transparency of the molded article and the coating film due to the addition of the ultraviolet-absorbing pigment (a) can be suppressed, and the transparency can be improved.

Method for producing ultraviolet absorbing pigment (A)

The method for synthesizing the compounds represented by the general formulae (1) to (3) contained in the ultraviolet-absorbing dye (a) can be synthesized using a known synthesis method of a compound having a triazine structure. Examples of the synthesis method of the general formula (1) include a method in which naphthol and cyanuric chloride are subjected to an addition reaction using aluminum trichloride. Examples of the synthesis method of the general formula (2) include a method in which naphthol and 2, 4-dichloro-6-phenyl-1, 3, 5-triazine are subjected to an addition reaction using aluminum trichloride. Examples of the synthesis method of the general formula (3) include a method in which naphthol and 2-chloro-4, 6-diphenyl-1, 3, 5-triazine are subjected to an addition reaction using aluminum trichloride. Further, for example, a method of subjecting methyl 2-hydroxy-1-naphthoate and benzamidine hydrochloride to a condensation cyclization reaction using sodium methoxide may be mentioned, but these synthesis methods are described as representative production methods, and are not limited thereto.

< Metal component (B) >)

The metal component (B) included in the ultraviolet absorber contains one or more metal atoms selected from the group consisting of Na, mg, al, K, ca and Fe. Among the metal atoms, al is often used as an acid catalyst used in the synthesis method, and thus the content of the metal component (B) can be controlled by controlling the amount of Al by a purification method after synthesis. In addition, according to the synthesis method of the ultraviolet absorbing pigment (a), the metal atoms are not contained at all in some cases, and therefore, the content of the metal component (B) can be controlled by adding the metal atoms separately after the synthesis of the ultraviolet absorbing pigment (a). Various methods are known for measuring metal atoms. The content of the metal component (B) can be easily determined by, for example, diluting a solution obtained by adding nitric acid to an ultraviolet absorber and decomposing the solution with microwaves to an appropriate concentration and using inductively coupled plasma luminescence analysis (inductively coupled plasma (inductively coupled plasma, ICP)). The content of the metal component (B) is preferably 0.1ppm to 50000ppm, more preferably 0.1ppm to 10000ppm, still more preferably 0.1ppm to 1000ppm, and further preferably 1ppm to 48200ppm based on the ultraviolet absorber. The content of the metal component (B) is a total value of Na, mg, al, K, ca and the content of each ion of Fe.

Method for purifying ultraviolet-absorbing pigment (A)

The method for purifying the ultraviolet absorbing pigment (a) after synthesis for adjusting the content of the metal component (B) includes: a method of adding a poor solvent such as methanol containing water to a synthesis reaction solution of the ultraviolet absorbing pigment (A) to separate the solution and removing the metal component; a method of spraying an alcohol such as methanol or water or a mixture thereof onto the wet cake (the compound concentrated in the metal component removal step) after the separation and filtration to clean the wet cake; a method of reslurrying and cleaning the wet cake in alcohol such as methanol or water or a mixed solution thereof; and spraying an acid solution such as diluted hydrochloric acid with a concentration of about 1% to 5% on the wet cake, and performing reslurry and cleaning.

The ultraviolet absorber is preferably: in the cukα ray-based X-ray diffraction pattern of the compound represented by the general formula (1), diffraction peaks are present at least at bragg angles 2θ (±0.3°) of 7.6 ° and 13.2 °, and the ratio (XRD ratio) of these diffraction peaks is 1:1.3 to 1:0.7 having diffraction peaks at least at bragg angles 2θ (±0.3°) of 8.0 ° and 14.5 ° in an X-ray diffraction pattern based on cukα rays of the compound represented by the general formula (2), and a ratio (XRD ratio) of these diffraction peaks is 1:1.3 to 1:0.7 having diffraction peaks at least at bragg angles 2θ (±0.3°) of 8.1 ° and 16.3 ° in an X-ray diffraction pattern based on cukα rays of the compound represented by the general formula (3), the ratio (XRD ratio) of these diffraction peaks being 1:1 to 1:0.3.

For example, in the case of the compound represented by the general formula (1), the ratio of diffraction peaks having bragg angles 2θ (±0.3°) of 7.6 °, 13.2 ° is 1: when the content is 0.6 or less, the crystallinity is strong, particles grow greatly, and transparency of a molded article, a coating film or the like may be lowered. In addition, at the ratio of 1: when 1.4 or more, the crystallinity is low and the particles are fine, but there is a concern that the transparency of the molded article, coating film or the like is lowered due to the strong cohesive force. By using the ultraviolet absorber having the above-mentioned X-ray diffraction pattern, the balance between crystallinity and cohesive force can be suitably obtained, and the transparency of the molded article and the coating film can be further improved. The method for measuring the powder X-ray diffraction spectrum and the method for calculating the diffraction peak intensity ratio will be described later.

The ultraviolet light absorbers of embodiments of the present invention may be dissolved or present as particles in the composition. The average primary particle diameter of the particles is preferably about 5nm to 100. Mu.m, more preferably about 10nm to 10. Mu.m, and still more preferably about 20nm to 500 nm. The ultraviolet absorber can suppress the decrease in transparency by particles having a suitable average primary particle diameter. The average primary particle diameter can be obtained by arithmetically averaging the length diameters of about 20 primary particles in a magnified image of 1,000 to 10,000 times using a transmission electron microscope.

Method for producing ultraviolet absorber

The ultraviolet absorber can be produced, for example, by synthesizing a compound contained in the ultraviolet absorbing pigment (a) and then adjusting the content of the metal component (B) of the ultraviolet absorbing pigment (a), for example, the content of the metal component (B) can be reduced by < the purification method of the ultraviolet absorbing pigment (a) > or the content can be increased by adding a metal atom separately after synthesizing the ultraviolet absorbing pigment (a).

For example, a material required for synthesizing a compound contained in the ultraviolet-absorbing pigment (a) is placed in an Erlenmeyer flask, and the mixture is stirred to obtain a reaction solution, and a poor solvent such as methanol containing water is added to the reaction solution in small amounts successively to separate the solution and remove the metal component, and then alcohol, water, or a mixture thereof is sprayed on the wet cake (the compound concentrated in the metal component removal step) after the separation and filtration to wash the wet cake, whereby an ultraviolet absorber having a reduced content of the metal component (B) can be produced.

[ composition ]

The composition according to the embodiment of the present invention may contain a second ultraviolet absorber (hereinafter, also referred to as "ultraviolet absorber (C)") which is at least one selected from the group consisting of triazine ring-containing compounds, benzotriazole ring-containing compounds, and benzophenone ring-containing compounds which are compounds other than the compounds represented by the general formulae (1) to (3). The ultraviolet absorbing dye (a) and the compound contained in the ultraviolet absorber (C) are combined to shield a short wavelength region of visible light having a wavelength of about 400nm to 420nm in a wide range of ultraviolet rays, more easily and effectively than the ultraviolet absorbing dye (a) which is one or more selected from the group consisting of the compounds represented by the general formulae (1) to (3) and is shielded in the entire ultraviolet ray region. In addition, since the compounds contained in the ultraviolet absorbing pigment (a) and the ultraviolet absorbing agent (C) protect each other, more excellent light resistance and heat resistance can be obtained.

[ ultraviolet absorber (C) ]

In the ultraviolet absorber (C), the benzotriazole ring-containing compound is a compound which absorbs light having a wavelength of 360nm or less, and examples thereof include: 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl-3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate in combination with 2-ethylhexyl-3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate, 2- [ 2-hydroxy-3, 5-bis (. Alpha.,. Alpha. -dimethylbenzyl) phenyl ] -2H-benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethylacetate in combination with 95% of phenylpropionic acid, 3- (2H-benzotriazol-2-yl) - (1, 4-dimethyl-ethyl) -7-hydroxy-side chain linear C9-alkyl esters, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1, 3-tetramethylbutyl) phenol, 2- (2 ' -hydroxy-3 ',5' -di-t-pentylphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-5-t-octylphenyl) benzotriazole, 2-ethylhexyl-3- [ 3-t-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate, 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl-phenol, 2- (2H-benzotriazol-2-yl) -3-t-butylphenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -1, 3-t-butylphenol, 2- (2H-benzotriazol-2-yl) -3-methylphenol, 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl-phenol, 2' -methylenebis [6- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol ], and the like.

Commercially available products that can be used as the ultraviolet absorber (C) include: "Dixian (TINUVIN) P", "Dixian (TINUVIN) PS", "Dixian (TINUVIN) 109", "Dixian (TINUVIN) 234", "Dixian (TINUVIN) 326", "Dixian (TINUVIN) 328", "Dixian (TINUVIN) 329", "Dixian (TINUVIN) 360", "Dixian (TINUVIN) 384-2", "Dixian (TINUVIN) 900", "Dixian (TINUVIN) 928", "Dixian (TINUVIN) 99-2", "Dixian (TINUVIN) 1130", ai Dike "Adeka (Adeka) Inc." Addita wave (Adeka b) LA-29", otsuka chemical manufacturing" Lu Na (RUNA ") 93, etc. manufactured by BASF Japan.

In the ultraviolet absorber (C), the triazine ring-containing compound other than the compounds represented by the general formulae (1) to (3) is a compound that absorbs light having a wavelength of 360nm or less, and examples thereof include: 2- [4, 6-bis (2, 4-xylyl) -1,3, 5-triazin-2-yl ] -5-octyloxyphenol, 2- [4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl ] -5- [3- (dodecyloxy) -2-hydroxypropoxy ] phenol, the reaction product of 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine with (2-ethylhexyl-glycidic acid ester, 2, 4-bis (2-hydroxy-4-butoxyphenyl) -6- (2, 4-dibutoxyphenyl) -1,3, 5-triazine, 2- [4- [ (2-hydroxy-3- (2 '-ethyl) hexyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [ (2-hydroxy-4-butoxyphenyl) -6- (2, 4-dibutoxyphenyl) -1,3, 5-triazine, 2-hydroxy-3- (2' -ethyl) hexyl ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -2-hydroxy-3, 5-triazin-yl 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-hexyloxyphenol (III-5) bis-ethylhexoxyphenol, methoxyphenyltriazine, and the like.

Examples of the commercial products of the triazine ring-containing compounds other than the compounds represented by the general formulae (1) to (3) include: "Ke Mi Suobu (KEMISORB) 102 manufactured by Chemipro Kasei corporation," Di Nun (TINUVIN) 400 manufactured by Basf Japan, di Nun (TINUVIN) 405"," Di Nun Bin (TINUVIN) 460"," Di Nun Bin (TINUVIN) 477-DW "," Di Nun Bin (TINUVIN) 479"," Di Nun (TINUVIN) 1577", adeka stock limited" Aidi Coltstab (Adekstab) LA-46"," Aidi Coltstab (Adekstab) LA-F70", siro Sun Chemical corporation" Sisub Soy Cloth (CYORB) UV-1164", etc.

In the ultraviolet absorber (C), the benzophenone ring-containing compound is generally a compound that absorbs light having a wavelength of 360nm or less, and examples thereof include: 2, 4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 2-hydroxy-4-n-octoxybenzophenone, 2-di-hydroxy-4-methoxybenzophenone, hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, 2 '-dihydroxy-4, 4' -dimethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 1, 4-bis (4-benzoyl-3-hydroxyphenoxy) butane, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2', 4' -tetrahydroxybenzophenone, and the like.

Commercial products of benzophenone ring-containing compounds can be listed as follows: kai Mi Buluo, "Kai Mi Suobu (KEMISORB) 10", "Kai Mi Suobu (KEMISORB) 11", "Kai Mi Suobu (KEMISORB) 11S", "Kai Mi Suobu (KEMISORB) 12", "Kai Mi Suobu (KEMISORB) 111", sipulo formation (Shipro Kasei) made "Sicable cloth (SEESORB) 101", "Sicable cloth (SEESORB) 107", ai Dike (ADEKA) made "Adekatab) 1413", etc.

The content of the ultraviolet absorber (C) in the nonvolatile matter of the composition is preferably 0.005 to 50% by mass, more preferably 0.01 to 40% by mass. The content of the ultraviolet absorber may be designed according to the target spectral cut-off.

The content of the ultraviolet absorber containing the ultraviolet absorbing pigment (a) in the nonvolatile component of the composition is preferably 0.005 to 50% by mass, more preferably 0.01 to 40% by mass. The content of the ultraviolet absorber may be designed according to the target spectral cut-off.

[ color Material (D) ]

The composition of the embodiment of the present invention may contain a color material (hereinafter, also referred to as "color material (D)") that shields 80% or more of the wavelength range from light with respect to the visible wavelength range having a wavelength of 450nm to 650 nm. The color material (D) preferably contains two or more kinds of colored colorants. Since the ultraviolet absorber according to the embodiment of the present invention strongly absorbs wavelengths of 420nm or less, the ultraviolet absorber can cut off wavelengths of 700nm or less and use light in the near infrared region by combining with a colored colorant absorbing a specific wavelength range of 450nm to 650nm, and thus can be used as a bandpass material in which light splitting is appropriately adjusted according to the purpose, for example. In addition, since the ultraviolet absorber protects the color material (D) from ultraviolet rays, the light resistance and heat resistance of the entire composition can be improved.

Examples of the color material (D) include: blue pigment, yellow pigment, violet pigment, red pigment, etc.

Organic pigments may also be used, for example: and azo pigments such as diketopyrrolopyrrole pigments, azo, bisazo and polyazo, aminoanthraquinone, diaminoanthraquinone, anthrapyrimidine, xanthone, anthroquinone, indanthrone, pyranthrone and anthrone, quinacridone pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, reduction pigments and metal complex pigments.

Further, as the organic coloring matter, a dye may be used, and examples thereof include: anthraquinone dyes, monoazo dyes, disazo dyes, oxazine dyes, aminoketone dyes, xanthene dyes, quinoline dyes, triphenylmethane dyes, and the like. In the case of using a dye, a method of incorporating a polar group of an anionic dye or a cationic dye into a resin to impart solubility in an organic solvent is effective.

(blue pigment)

Examples of blue pigments include: c.i. pigment blue 1, 1: 2. 9, 14, 15: 1. 15: 2. 15: 3. 15: 4. 15: 6. 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56: 1. 60, 61: 1. 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. "C.I." means the dye Index (color Index) (C.I.; society of dyeing engineers (The Society of Dyers and Colourists) issue).

Examples of blue dyes include: c.i. acid blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41: 1. 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 62: 1. 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 84, 85, 86, 88, 89, 90: 1. 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127: 1. 128, 129, 135, 137, 138, 143, 145, 147, 150, 155, 159, 169, 174, 175, 176, 183, 198, 203, 204, 205, 206, 208, 213, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280, and the like.

Examples of the method include: c.i. direct blue 1, 2, 3, 4, 6, 7, 8: 1. 9, 10, 12, 14, 15, 16, 19, 20, 21: 1. 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98: 1. 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129, 130: 1. 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158: 1. 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 213, 215, 225, 226, 229, 230, 231, 242, 243, 244, 253, 254, 260, 263, etc.

(yellow pigment)

Examples of the yellow pigment include: c.i. pigment yellow 1, 1: 1. 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35: 1. 36, 36: 1. 37, 37: 1. 40, 41, 42, 43, 48, 53, 55, 61, 62: 1. 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127: 1. 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191). 1. 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, etc.

Examples of yellow dyes include: c.i. acid yellow 2, 3, 4, 5, 6, 7, 8, 9: 1. 10, 11: 1. 12, 13, 14, 15, 16, 17: 1. 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40: 1. 41, 42: 1. 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199, etc.

Examples of the method include: c.i. direct yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44: 1. 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134, etc.

(purple pigment)

Examples of violet pigments include: c.i. pigment violet 1, 1: 1. 2, 2: 2. 3, 3: 1. 3: 3. 5, 5: 1. 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc.

Examples of violet dyes include: c.i. acid violet 1, 2, 3, 4, 5: 1. 6, 7: 1. 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, etc.

Examples of the method include: c.i. direct violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97, etc.

(Red pigment)

Examples of the red pigment include: c.i. pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48: 1. 48: 2. 48: 3. 48: 4. 49, 49: 1. 49: 2. 50: 1. 52: 1. 52: 2. 53, 53: 1. 53: 2. 53: 3. 57, 57: 1. 57: 2. 58: 4. 60, 63: 1. 63: 2. 64, 64: 1. 68, 69, 81: 1. 81: 2. 81: 3. 81: 4. 83, 88, 90: 1. 101, 101: 1. 104, 108: 1. 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, etc.

Examples of orange pigments that function similarly to red pigments include: orange pigments such as c.i. pigment orange 36, 38, 43, 51, 55, 59, 61, and the like.

Examples of red dyes include: c.i. acid red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25: 1. 26, 26: 1. 26: 2. 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76: 1. 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131, 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 249, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388, etc.

Examples of the method include: c.i. direct red 1, 2: 1. 4, 5, 6, 7, 8, 10: 1. 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26: 1. 28, 29, 31, 33: 1. 34, 35, 36, 37, 39, 42, 43: 1. 44, 46, 49, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67: 1. 68, 72: 1. 73, 74, 75, 77, 78, 79, 81: 1. 85, 86, 88, 89, 90, 97, 100, 101: 1. 107, 108, 110, 114, 116, 117, 120, 121, 122: 1. 124, 125, 127: 1. 127: 2. 128, 129, 130, 132, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238, etc.

The dye in the color material (D) has good spectroscopic characteristics and excellent color development, but has problems in light resistance and heat resistance. Therefore, in order to improve these problems, it is preferable that a basic dye is used as a salt-forming compound that is salified using an organic acid and perchloric acid. The organic acid is preferably an organic sulfonic acid or an organic carboxylic acid. Among them, naphthalene sulfonic acid such as tall Bie Ya acid and perchloric acid are preferable in terms of tolerance.

In addition, it is preferable to use the compound as a salt-forming compound for salifying a resin having an anionic group, and also preferable to use the compound as a salt-forming compound for salifying a resin having a betaine structure and an organic acid.

In addition, in terms of heat resistance, light resistance, and solvent resistance, an anionic dye including an acid dye or a direct dye is preferably used as a salt-forming compound using a compound having a cationic group or a resin having a cationic group as a counter ion. In addition, in the synthesis of the salt-forming compound, a resin having a cationic group is preferably used, and more preferably, the resin having a cationic group in a side chain is used together with an organic acid to form a salt.

In addition, when an anionic dye is used as a sulfonamide compound by sulfonamide, it is preferable in terms of tolerance.

In the coating application, the color material (D) is preferably a blue pigment, blue: 3 or pigment, blue, 15: 6. yellow pigment, yellow pigment 139, violet pigment 23. In addition, in molding applications, it is preferable to use pigment, blue.15: 3 or pigment, blue, 15: 6. yellow pigment, 147, and red pigment, solvent, red pigment, 52.

The content of the color material (D) in the nonvolatile component of the composition is preferably 0.005 to 50% by mass, more preferably 0.005 to 20% by mass, and still more preferably 0.5 to 50% by mass. The content of the ultraviolet absorber may be designed according to the target spectral cut-off.

The composition of the embodiment of the present invention may optionally contain a pigment derivative.

The dye derivative is a compound having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. Examples of the pigment derivative include: compounds having acidic substituents such as sulfo, carboxyl and phosphate groups, amine salts of these, compounds having basic substituents such as sulfonamide groups or tertiary amino groups at the terminal, and compounds having neutral substituents such as phenyl or phthalimidoalkyl groups.

Examples of the organic coloring matter include: diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, viol-cyclic ketone-based pigments, perylene-based pigments, thiazine indigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, indole-based pigments such as benzisoindole, isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, naphthol-based pigments, vat-based pigments, metal complex-based pigments, azo-based pigments such as azo, disazo and polyazo-based pigments, and the like.

The pigment derivatives may be used singly or in combination of two or more.

[ near-infrared ray absorbent (E) ]

The composition of the embodiment of the present invention may contain one or more near infrared ray absorbers (hereinafter also referred to as "near infrared ray absorbers (E)") selected from the group consisting of cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, iminium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, and Ketone onium compounds, and the near infrared ray absorbers (E) have a great absorption in a wavelength region of 600nm to 1500 nm. Accordingly, the light splitting can be appropriately adjusted according to the purpose, and the ultraviolet absorber according to the embodiment of the present invention suppresses deterioration of the near infrared absorber (E), and thus the durability is improved.

The near infrared ray absorber (E) is a compound having a maximum absorption at a wavelength of 600nm to 1500 nm. Further, the maximum absorption is preferably 800nm to 1000nm.

Examples of the cyanine compound include compounds described in International publication No. 2006/006573, international publication No. 2010/073857, japanese patent application laid-open No. 2013-241598, japanese patent application laid-open No. 2016-113501, japanese patent application laid-open No. 2016-113504, and the like; examples of the phthalocyanine compound include compounds described in JP-A-4-23868, JP-A-06-192584, JP-A-2000-63691, international publication No. 2014/208514, etc.; examples of the naphthalocyanine compound include compounds described in JP-A-11-152414, JP-A-2000-86919, JP-A-2009-29955, international publication No. 2018/186490, etc.; examples of the indigo compound include those described in Japanese patent application laid-open No. 2013-230412; examples of the ammonium compound include compounds described in Japanese patent application laid-open No. 2005-336150, japanese patent application laid-open No. 2007-197492, japanese patent application laid-open No. 2008-88426, and the like; as the anthraquinone compound, there may be mentioned those described in Japanese patent application laid-open No. 62-903, japanese patent application laid-open No. 1-172458, etc.; examples of the pyrrolopyrrole compound include compounds described in Japanese patent application laid-open No. 2009-263614, japanese patent application laid-open No. 2010-90313 and Japanese patent application laid-open No. 2011-068731; examples of squarylium compounds include compounds described in Japanese patent application laid-open No. 2011-132361, japanese patent application laid-open No. 2016-142891, international publication No. 2017/135359, international publication No. 2018/225837, japanese patent application laid-open No. 2019-001987, international publication No. 2020/054718, and the like; examples of the Ketone onium compound include those described in International publication No. 2019/021767.

(squarylium compound)

The squarylium compound is preferably a compound represented by the following general formula (4).

[ chemical 13]

General formula (4)

In the general formula (4), R ¹ ～R ⁴ Independently represent a halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aralkyl group, -OR ¹⁰ 、-COR ¹¹ 、-COOR ¹² 、-OCOR ¹³ 、-NR ¹⁴ R ¹⁵ 、-NHCOR ¹⁶ 、-CONR ¹⁷ R ¹⁸ 、-NHCONR ¹⁹ R ²⁰ 、-NHCOOR ²¹ 、-SR ²² 、-SO ₂ R ²³ 、-SO ₂ OR ²⁴ 、-NHSO ₂ R ²⁵ 、-SO ₂ NR ²⁶ R ²⁷ 、-B(OR ²⁸ ) ₂ -NHBR ²⁹ R ³⁰ Any one of the group consisting of. R is R ¹⁰ ～R ³⁰ Each independently represents any one selected from the group consisting of a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group. In addition, in-COOR ¹² R of (2) ¹² In the case of hydrogen (i.e., carboxyl group), the hydrogen atom may be dissociated (i.e., carbonate group) or may be in the form of a salt. In addition, in-SO ₂ OR ²⁴ R of (2) ²⁴ In the case of a hydrogen atom (i.e., a sulfo group), the hydrogen atom may be dissociated (i.e., a sulfonate group) or may be in the form of a salt. In addition, R ¹ And R is R ² 、R ³ And R is R ⁴ Or may be bonded to each other to form a ring.

Examples of the "substituent" include: halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aralkyl group, -OR ¹⁰⁰ 、-COR ¹⁰¹ 、-COOR ¹⁰² 、-OCOR ¹⁰³ 、-NR ¹⁰⁴ R ¹⁰⁵ 、-NHCOR ¹⁰⁶ 、-CONR ¹⁰⁷ R ¹⁰⁸ 、-NHCONR ¹⁰⁹ R ¹¹⁰ 、-NHCOOR ¹¹¹ 、-SR ¹¹² 、-SO ₂ R ¹¹³ 、-SO ₂ OR ¹¹⁴ 、-NHSO ₂ R ¹¹⁵ or-SO ₂ NR ¹¹⁶ R ¹¹⁷ Etc.

R ¹⁰⁰ ～R ¹¹⁷ Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. In addition, in-COOR ¹⁰² R of (2) ¹⁰² In the case of hydrogen (i.e., carboxyl group), the hydrogen atom may be dissociated (i.e., carbonate group) or may be in the form of a salt. In addition, in-SO ₂ OR ¹¹⁴ R of (2) ¹¹⁴ In the case of hydrogen atoms (i.e. sulfo)Radical), the hydrogen atom may be dissociated (i.e., sulfonate group), or may be in the form of a salt.

Examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom, iodine atom.

The carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 12, particularly preferably 1 to 8. The alkyl group may be any of linear, branched, and cyclic.

The carbon number of the alkenyl group is preferably 2 to 20, more preferably 2 to 12, particularly preferably 2 to 8. Alkenyl groups may be any of straight chain, branched, and cyclic.

The number of carbon atoms of the alkynyl group is preferably 2 to 20, more preferably 2 to 12, particularly preferably 2 to 8. Alkynyl groups may be any of straight-chain, branched, or cyclic.

The carbon number of the aryl group is preferably 6 to 25, more preferably 6 to 15, and particularly preferably 6 to 10.

The alkyl portion of the aralkyl group is the same as the alkyl group. The aryl moiety of the aralkyl group is the same as the aryl group. The carbon number of the aralkyl group is preferably 7 to 40, more preferably 7 to 30, particularly preferably 7 to 25.

The heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having a condensation number of 2 to 8, and particularly preferably a single ring or a condensed ring having a condensation number of 2 to 4. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. Heteroaryl is preferably a 5-membered ring or a 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and particularly preferably 3 to 12.

Alkyl, alkenyl, alkynyl, aryl, heteroaryl, and aralkyl groups may have a substituent or may be unsubstituted. The substituent may be the "substituent".

From the viewpoints of light resistance and heat resistance, the squarylium compound is more preferably a compound represented by the following general formula (5).

[ chemical 14]

General formula (5)

In the general formula (5), R ⁵ ～R ⁸ Independently represent a halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aralkyl group, -OR ⁵⁰ 、-COR ⁵¹ 、-COOR ⁵² 、-OCOR ⁵³ 、-NR ⁵⁴ R ⁵⁵ 、-NHCOR ⁵⁶ 、-CONR ⁵⁷ R ⁵⁸ 、-NHCONR ⁵⁹ R ⁶⁰ 、-NHCOOR ⁶¹ 、-SR ⁶² 、-SO ₂ R ⁶³ 、-SO ₂ OR ⁶⁴ 、-NHSO ₂ R ⁶⁵ 、-SO ₂ NR ⁶⁶ R ⁶⁷ 、-B(OR ⁶⁸ ) ₂ -NHBR ⁶⁹ R ⁷⁰ Any one of the group consisting of. R is R ⁵⁰ ～R ⁷⁰ Each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. In addition, in-COOR ⁵² R of (2) ⁵² In the case of hydrogen (i.e., carboxyl group), the hydrogen atom may be dissociated (i.e., carbonate group) or may be in the form of a salt. In addition, in-SO ₂ OR ⁶⁴ R of (2) ⁶⁴ In the case of a hydrogen atom (i.e., a sulfo group), the hydrogen atom may be dissociated (i.e., a sulfonate group) or may be in the form of a salt. In addition, R ⁵ And R is R ⁶ 、R ⁷ And R is R ⁸ Or may be bonded to each other to form a ring.

"substituent" is the same meaning as the "substituent".

Specific examples of squarylium compounds are shown below. The embodiments of the present invention are not limited to these.

[ 15]

[ 16]

(pyrrolopyrrole Compounds)

The pyrrolopyrrole compound is preferably a compound represented by the following general formula (6).

[ chemical 17]

General formula (6)

In the general formula (6), R ^1x R is R ^1y Each independently represents alkyl, aryl or heteroaryl, R ² R is R ³ Each independently represents a hydrogen atom or a substituent, R ² R is R ³ Can be bonded to each other to form a ring, R ⁴ Represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4x R ^4y Or a metal atom, R ⁴ Can be selected from R ^1x 、R ^1y R is R ³ At least one of the groups consisting of covalent bonding or coordination bonding, R ^4x 、R ^4y Each independently represents a substituent. General formula (6) is described in Japanese patent application laid-open No. 2009-263614, japanese patent application laid-open No. 2011-68731, and International publication No. 2015/166873.

R ^1x R is R ^1y Each independently is preferably aryl or heteroaryl, more preferably aryl. In addition, R ^1x R is R ^1y The alkyl, aryl and heteroaryl groups represented may have a substituent or may be unsubstituted. Examples of the substituent include: alkoxy, hydroxy, halogen atom, cyano, nitro, -OCOR ¹¹ 、-SOR ¹² 、-SO ₂ R ¹³ Etc. R is R ¹¹ ～R ¹³ Each independently represents a hydrocarbyl group or a heteroaryl group. Examples of the substituent include the substituents described in paragraphs 0020 to 0022 of japanese patent application laid-open No. 2009-263614. Among them, preferred substituents are alkoxy, hydroxy, halogen atom, cyano, nitro, -OCOR ¹¹ 、-SOR ¹² 、-SO ₂ R ¹³ . As R ^1x R is R ^1y The radicals represented are preferably alkoxy radicals having branched alkyl radicals, or have-OCOR ¹¹ Aryl groups having the indicated groups as substituents. The branched alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms.

R ² R is R ³ At least one of them is preferably an electron withdrawing group, more preferably R ² Represents an electron withdrawing group, R ³ Represents heteroaryl. Heteroaryl is preferably a 5-membered ring or a 6-membered ring. The heteroaryl group is preferably a single ring or a condensed ring, more preferably a single ring or a condensed ring having a condensation number of 2 to 8, and still more preferably a single ring or a condensed ring having a condensation number of 2 to 4. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. Examples of the hetero atom include: nitrogen atom, oxygen atom, sulfur atom. Heteroaryl groups preferably have more than one nitrogen atom. Two R in the general formula (6) ² May be the same as or different from each other. In addition, two R in the general formula (6) ³ May be the same as or different from each other.

R ⁴ Preferably hydrogen, alkyl, aryl, heteroaryl, or-BR ^4x R ^4y The radicals represented are more preferably hydrogen atoms, alkyl groups, aryl groups, or-BR ^4x R ^4y The radicals represented are particularly preferably-BR ^4x R ^4y The radicals represented. As R ^4x R ^4y The substituent represented is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and particularly preferably an aryl group. These groups may further have a substituent. Two R in the general formula (6) ⁴ May be the same or different from each other.

Specific examples of the pyrrolopyrrole compound are shown below. In the following structural formula, me represents methyl, and Ph represents phenyl. Examples of the pyrrolopyrrole compound include compounds described in paragraphs 0016 to 0058 of japanese patent application laid-open publication No. 2009-263614, paragraphs 0037 to 0052 of japanese patent application laid-open publication No. 2011-68731, paragraphs 0014 to 0027 of japanese patent application laid-open publication No. 2014-130343, and paragraphs 0010 to 0033 of international publication No. 2015/166873. The embodiments of the present invention are not limited to these.

[ chemical 18]

(naphthalocyanine Compound)

The naphthalocyanine compound is preferably a compound represented by the following general formula (7).

[ chemical 19]

General formula (7)

In the general formula (7), R ¹ ～R ²⁴ Each independently represents a hydrogen atom, a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, or a sulfamoyl group which may have a substituent.

Z is a polymer site containing a single unit represented by the general formula (8) or a phosphorus compound site represented by the general formula (9), and is a bond with Al.

[ chemical 20]

General formula (8)

In the general formula (8), X represents-CONH-R ²⁵ -、-COO-R ²⁶ -、-CONH-R ²⁷ -O-, or-COO-R ²⁸ -O-，R ²⁵ ～R ²⁸ Represents that the carbon atom and the carbon atom can pass through-O-, -CO-, -COO-; -OCO-, -CONH-, or-NHCO-linked alkylene or arylene. R is R ³¹ Represents a hydrogen atom or a methyl group.

[ chemical 21]

General formula (9)

In the general formula (9), R ²⁹ R is R ³⁰ Each independently represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent, R ²⁹ And R is R ³⁰ Or may be bonded to each other to form a ring.

Specific examples of the naphthalocyanine compound are shown below. The present invention is not limited to these.

[ chemical 22]

The content of the near infrared ray absorber (E) in the nonvolatile matter of the composition is preferably 0.005 to 50% by mass, more preferably 0.01 to 40% by mass. The content of the ultraviolet absorber may be designed according to the target spectral cut-off.

[ resin ]

The compositions of embodiments of the present invention may contain a resin. Examples of the resin include: thermoplastic resins, photocurable resins, thermosetting resins, and the like.

A composition containing the ultraviolet absorber and the thermoplastic resin according to the embodiment of the present invention will be described. The composition is useful, for example, for molded body applications. Examples of the thermoplastic resin include: polyolefin resins, polycarbonate resins, polyacrylic resins, polyester resins, polyamide resins, polyetherimide resins, cycloolefin resins, and the like.

(polyolefin resin)

Examples of the polyolefin resin include: polyethylene, polypropylene, polybutene-1, and poly-4-methylpentene, and copolymers thereof, and the like.

Examples of the polyethylene include low density polyethylene and high density polyethylene.

Examples of the polypropylene include crystalline polypropylene and amorphous polypropylene.

Examples of the copolymer used include: random copolymers of ethylene-propylene, block or graft copolymers, copolymers of alpha-olefins with ethylene or propylene, ethylene-vinyl acetate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-acrylic acid copolymers, and the like.

Among these, crystalline polypropylene or amorphous polypropylene, and random, block or graft copolymers of ethylene-propylene are preferable, and propylene-ethylene block copolymers are more preferable. In addition, polypropylene resin is preferable in view of the low cost and the small specific gravity, and the weight of the molded product can be reduced.

The number average molecular weight of the polyolefin resin was about 30,000 ～ 500,000.

The Melt Flow Rate (MFR) of the polyolefin resin is preferably 1 (g/10 min) to 100 (g/10 min). The MFR was determined according to Japanese Industrial Standard (Japanese Industrial Standard, JIS) K-7210.

(polycarbonate resin)

The polycarbonate resin is synthesized by reacting a carbonate precursor such as carbonyl chloride or carbonic acid diester with an aromatic dihydroxy compound. In the case of using a synthesis reaction of phosgene, for example, an interfacial method is preferable. In addition, in the case of using a synthesis reaction of a carbonic acid diester, a transesterification method in which a molten reaction is used is preferable.

Examples of the aromatic dihydroxy compound include: 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2-bis (4-hydroxy-3-methylphenyl) propane bis (hydroxyaryl) alkanes such as 1, 1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2-bis (4-hydroxy-3-bromophenyl) propane, 2-bis (4-hydroxy-3, 5-dibromophenyl) propane, and 2, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane; bis (hydroxyaryl) cycloalkanes such as 1, 1-bis (4-hydroxyphenyl) cyclopentane and 1, 1-bis (4-hydroxyphenyl) cyclohexane; dihydroxydiaryl ethers such as 4,4' -dihydroxydiphenyl ether and 4,4' -dihydroxy-3, 3' -dimethyldiphenyl ether; dihydroxydiaryl sulfides such as 4,4' -dihydroxydiphenyl sulfide and 4,4' -dihydroxy-3, 3' -dimethyldiphenyl sulfide; dihydroxydiaryl sulfoxides such as 4,4' -dihydroxydiphenyl sulfoxide and 4,4' -dihydroxy-3, 3' -dimethyldiphenyl sulfoxide; dihydroxydiaryl sulfones such as 4,4' -dihydroxydiphenyl sulfone and 4,4' -dihydroxy-3, 3' -dimethyldiphenyl sulfone. In addition, piperazine, dipiperidinylhydroquinone, resorcinol, and 4,4' -dihydroxydiphenyl may be used in combination.

Examples of carbonate precursors include: diaryl carbonates such as carbonyl chloride, diphenyl carbonate and xylene carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

The aromatic dihydroxy compound and the carbonate precursor may be used singly or in combination of two or more.

The viscosity average molecular weight of the polycarbonate resin is preferably 15,000 ～ 30,000, more preferably 16,000 ～ 27,000. In the present specification, the viscosity average molecular weight is a value obtained by converting the solution viscosity measured at 25 ℃ using methylene chloride as a solvent.

Examples of commercial products of the polycarbonate resin include: you Pilong (Iuppilon) H-4000 (manufactured by Mitsubishi engineering plastics Co., ltd., viscosity average molecular weight of 16,000), you Pilong (manufactured by Mitsubishi engineering plastics Co., ltd., viscosity average molecular weight of 23,000), you Pilong (manufactured by Mitsubishi engineering plastics Co., ltd., viscosity average molecular weight of 27,000) E-2000, and the like.

(polyacrylic resin)

The polyacrylic resin is a compound obtained by polymerizing a monomer such as methyl methacrylate and/or ethyl methacrylate, and other monomers optionally used, by a known method. Examples of the polyacrylic resin include: ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, and the like. In addition to the above-mentioned monomers, for example, monomers such as butadiene, α -methylstyrene, maleic anhydride and the like may be added to polymerize, and the heat resistance, fluidity and impact resistance may be adjusted depending on the amount and molecular weight of the monomers.

(polyester resin)

The polyester resin is a resin having an ester bond in the main chain of the molecule, and examples thereof include: polycondensates synthesized from dicarboxylic acids (including derivatives thereof) and diols (diols or diphenols); polycondensates synthesized from dicarboxylic acids (including derivatives thereof) and cyclic ether compounds; ring-opening polymers of cyclic ether compounds, and the like. The polyester resins can be exemplified by: homopolymers formed from polymers of dicarboxylic acids and diols, copolymers using various raw materials, polymer blends obtained by mixing these, and the like. The derivative of the dicarboxylic acid is an acid anhydride, an ester, or the like. The dicarboxylic acid includes aliphatic and aromatic dicarboxylic acids, and aromatic dicarboxylic acids are more preferable from the viewpoint of improving heat resistance.

Examples of the aromatic dicarboxylic acid include: terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, isophthalic acid, terephthaloyl acid, diphenyldiacetic acid, diphenyl-p, p ' -dicarboxylic acid, diphenyl-4, 4' -diacetic acid, diphenylmethane-p, p ' -dicarboxylic acid, diphenylethane-m, m ' -dicarboxylic acid, diphenyldicarboxylic acid, diphenylbutane-p, p ' -dicarboxylic acid, benzophenone-4, 4' -dicarboxylic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-1, 5-dicarboxylic acid, naphthalene-2, 6-dicarboxylic acid, naphthalene-2, 7-dicarboxylic acid, p-carboxyphenoxyacetic acid, p-carboxyphenoxybutyl acid, 1, 2-diphenoxypropane-p, p ' -dicarboxylic acid, 1, 5-diphenoxypentane-p, p ' -dicarboxylic acid, 1, 6-diphenoxyhexane-p, p ' -dicarboxylic acid, p- (p-carboxyphenoxy) benzoic acid, 1, 2-bis (2-methoxyphenoxy) -ethane-p, 1, 3-bis (2-methoxyphenoxy) -propane, p-bis (2-methoxyphenoxy) -p, 2-diphenoxy pentane, and the like.

Examples of aliphatic dicarboxylic acids include: oxalic acid, succinic acid, adipic acid, suberic acid (core acid), azelaic acid, sebacic acid, dodecanedicarboxylic acid, undecanedicarboxylic acid, maleic acid, fumaric acid, and the like.

Examples of the diol include: ethylene glycol, trimethylene glycol, butane-1, 3-diol, butane-1, 4-diol, 2-dimethylpropane-1, 4-diol, cis-2-butene-1, 4-diol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, cyclohexanedimethanol, and the like. Among these, ethylene glycol, butane-1, 4-diol, and cyclohexanedimethanol are also preferable.

Examples of dihydric phenols include: hydroquinone, resorcinol, bisphenol a, and the like.

Examples of the cyclic ether compound include ethylene oxide and propylene oxide.

The dicarboxylic acid and the diol may be used singly or in combination of two or more.

(Polyamide resin)

The polyamide resin is a crystalline resin, and can be synthesized by, for example, subjecting a carboxylic acid component and a compound (Am) having two or more amino groups to a dehydration condensation reaction.

Examples of the carboxylic acid component include: adipic acid, sebacic acid, isophthalic acid, terephthalic acid, and the like. In addition, a compound having three or more carboxyl groups can be used as the carboxylic acid component.

For example, a known compound (Am) having two or more amino groups can be used, and examples thereof include: aliphatic polyamines such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, etc.; aliphatic polyamines containing alicyclic polyamines such as isophorone diamine and dicyclohexylmethane-4, 4' -diamine; aromatic polyamines such as phenylenediamine and xylylenediamine; diamino alcohols such as 1, 3-diamino-2-propanol, 1, 4-diamino-2-butanol, 1-amino-3- (aminomethyl) -3, 5-trimethylcyclohexane-1-ol, 4- (2-aminoethyl) -4,7, 10-triazadecan-2-ol, and 3- (2-hydroxypropyl) -o-xylene- α, α' -diamine.

Examples of the commercial products of the polyamide resin include 6 nylon (manufactured by Toli Co., ltd.), 66 nylon (manufactured by Toli Co., ltd.), and 610 nylon (manufactured by Toli Co., ltd.).

(polyetherimide resin)

The polyetherimide resin is an amorphous resin having a glass transition temperature exceeding 180 ℃, has good transparency, and has high strength, high heat resistance, high elastic modulus, and wide chemical resistance. Therefore, it is widely used for various applications such as automobiles, telecommunications, aerospace, electric/electronic, transportation and health care.

One of the processes for producing the polyetherimide resin is by bisphenol A disodium salt (BPA. Na) ₂ ) The polymerization of alkali metal salts of dihydroxy aromatic compounds with bis (halophthalimide) is carried out. The molecular weight of the obtained polyetherimide resin can be controlled by two methods. The first method is to use a molar excess of bis (halophthalimide) for the alkali metal salt of the dihydroxy aromatic compound. The second method is to prepare bis (halophthalic anhydride) in the presence of monofunctional compounds such as phthalic anhydride, which form the capping agent. Phthalic anhydride reacts with a portion of the organic diamine to form a monohalo-bis (phthalimide). The monohalo-bis (phthalimide) functions as a capping agent in the polymerization step by reacting with the benzene oxide end groups in the growing polymer chain.

Examples of the commercially available polyetherimide resin include Wutai Mu (ULTEM) (manufactured by Sade basic industries Co., ltd.).

(cycloolefin resin)

The cycloolefin resin is an amorphous resin having an alicyclic structure in the main chain and/or the side chain. Examples of the alicyclic structure include: norbornene polymers, monocyclic cyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. Among these, norbornene polymers are also preferable in terms of excellent moldability and transparency. Examples of norbornene polymers include: bicyclo [2.2.1 ]Hept-2-ene (commonly known as norbornene), tricyclo [4.3.0.1 ] ^2,5 ]Dec-3, 7-diene (commonly known as dicyclopentadiene), 7, 8-benzotricyclo [4.3.0.1 ] ^2,5 ]Dec-3-ene (common name: methano-tetrahydrofluorene), tetracyclo [4.4.0.1 ] ^2,5 .1 ^7,10 ]Dodec-3-ene (common name: tetracyclododecene), and the like.

Examples of the commercially available cycloolefin resin include Topas (manufactured by Bao Litsea plastics) and Apel (manufactured by Mitsui chemical Co., ltd.).

(polyvinyl acetal resin)

The polyvinyl acetal resin is preferably a polyvinyl acetal obtained by acetalizing a polyvinyl alcohol with an aldehyde. The polyvinyl acetal resin is more preferably a polyvinyl butyral resin. The polyvinyl butyral resin can be synthesized, for example, by reacting polyvinyl alcohol with butyraldehyde under acidic conditions.

The thermoplastic resin may be used singly or in combination of two or more.

The content of the ultraviolet absorber is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 1 part by mass, relative to 100 parts by mass of the thermoplastic resin.

The composition containing the ultraviolet absorber and the thermoplastic resin is preferably produced, for example, as a master batch in which the ultraviolet absorber is blended at a high concentration. When a master batch is produced and then melt-kneaded with a diluent resin (thermoplastic resin) to produce a molded article, the ultraviolet absorber can be easily uniformly dispersed in the molded article as compared with a molded article produced without the master batch, and aggregation of the ultraviolet absorber can be suppressed. Thereby improving the transparency of the molded article.

The master batch can be produced, for example, by melt-kneading an ultraviolet absorber and a thermoplastic resin, and granulating the mixture using a granulator. In order to prevent the ultraviolet absorber from agglomerating, it is preferable to prepare a master batch by previously preparing a dispersion obtained by melt-kneading the ultraviolet absorber and wax, and then melt-kneading the dispersion with a thermoplastic resin. Here, the dispersion is preferably prepared, for example, using a blending mixer or a three-roll mill.

When the composition is produced as a master batch, the amount of the ultraviolet absorber to be blended is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the thermoplastic resin. The mass ratio of the master batch (X) to the diluting resin (Y) is preferably X/y=1/5 to 1/100. When the amount is within the above range, the molded article can easily obtain good optical characteristics.

The composition according to the embodiment of the present invention can be prepared into a liquid masterbatch, and then melt kneaded together with a diluent resin (thermoplastic resin) to prepare a molded article.

The liquid master batch is obtained by dissolving or dispersing an ultraviolet absorber in a liquid resin.

The liquid resin has a viscosity of 8,000 mPas or less at 25 ℃. The viscosity is preferably 10 to 5,000 mPas, more preferably 100 to 3,000 mPas. When the amount is within the above range, the ultraviolet absorber can be easily dispersed in the liquid master batch. The viscosity in the present specification is in accordance with JIS K7117-1:1999 and measured at 25 ℃ using a type B viscometer.

The content of the liquid resin in 100 parts by mass of the liquid master batch is preferably 50% by mass or more, more preferably 60% by mass to 95% by mass, and still more preferably 70% by mass to 90% by mass. In this range, for example, the melt viscosity can be suppressed during melt kneading, and thus the ultraviolet absorber can be easily dispersed. When the liquid masterbatch is used, a molded article having high transparency can be obtained.

The number average molecular weight (Mn) of the liquid resin is preferably 100 to 3000, more preferably 200 to 2000, still more preferably 500 to 1500, and particularly preferably 1000 to 1500. When Mn is 100 or more, the molded article can easily have both moldability and transparency. Further, when Mn is 3000 or less, dispersibility and antistatic properties are improved.

Examples of the liquid resin include: epoxy resins such as epoxidized soybean oil and epoxidized flax oil, aliphatic polyester resins, polyalkylene glycol resins, polyether ester resins, or acetyl tributyl citrate, etc., and when a high molding temperature of polyethylene terephthalate (polyethylene terephthalate, PET), polycarbonate, etc. is required for the main resin, aliphatic polyester resins, polyalkylene glycol resins, polyether ester resins, or acetyl tributyl citrate is preferable in terms of high heat resistance and excellent antistatic properties.

(aliphatic polyester resin)

The aliphatic polyester resin is a resin obtained by reacting an aliphatic polycarboxylic acid with a polyhydric alcohol.

The aliphatic polycarboxylic acid is an aliphatic carboxylic acid having two or more carboxyl groups. Examples of the aliphatic polycarboxylic acid include: succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, tricarballylic acid, 1,3, 6-hexanetricarboxylic acid, 1,3, 5-hexanetricarboxylic acid, and the like.

The polyol is an alcohol having two or more hydroxyl groups. Examples of the polyol include: and polyalkylene glycols such as aliphatic diols including ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 2-dimethyl-1, 3-propanediol, 2-diethyl-1, 3-propanediol, 2-n-butyl-2-ethyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-ethyl-1, 3-hexanediol, 2-methyl-1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 12-octadecanediol, and diethylene glycol and dipropylene glycol.

The aliphatic polycarboxylic acid and the polyhydric alcohol may be used singly or in combination of two or more.

The freezing point of the aliphatic polyester resin is preferably-5℃or lower, more preferably-50℃to-10 ℃.

Examples of commercial products of aliphatic polyester resins include: ai Dike Session (Adeka sizer) PN-170 (manufactured by Ai Dike (ADEKA) Co., ltd., viscosity 800 mPa.s at 25 ℃ C., freezing point-15 ℃ C., adipic acid polyester), ai Dike Session (Adeka sizer) P-200 (manufactured by Ai Dike (ADEKA) Co., ltd., viscosity 2,600 mPa.s at 25 ℃ C., freezing point-20 ℃ C., adipic acid polyester), ai Dike Session (Adeka sizer) PN-250 (manufactured by Ai Dike (ADEKA) Co., ltd., viscosity 4,500 mPa.s at 25 ℃ C., freezing point-20 ℃ C., adipic acid polyester), etc.

(polyether resin)

The polyether resin is a resin having a repeating unit of an alkylene oxide group. The carbon number of the alkylene oxide group is preferably 1 to 6. The polyether resin preferably has a viscosity of 10,000 mPas or less at 25 ℃. The viscosity is suitable for use in a liquid masterbatch. The alkylene oxide group preferably has 2 to 4 carbon atoms. This improves the compatibility and suppresses the water absorption.

Examples of the polyether resin include: polyethylene glycol having 2 carbon atoms in the repeating unit, polytrimethylene glycol and polypropylene glycol having 3 carbon atoms in the repeating unit, polytetramethylene glycol and polytetramethylene glycol having 4 carbon atoms in the repeating unit, and the like.

(polyetherester resin)

The polyether ester resin is an ester compound of an aliphatic polycarboxylic acid resin and an alkylene glycol resin.

Examples of commercial products of polyetherester resins include: ai Dike Securium (Adeka sizer) RS-107 (manufactured by Adeka sizer Co., ltd., viscosity at 25 ℃ C. 20 mPa.s, freezing point-47 ℃ C., adipate-based resin), ai Dike Securium (Adeka sizer) RS-700 (manufactured by Adeka sizer Co., ltd., viscosity at 25 ℃ C., 30 mPa.s, freezing point-53 ℃ C., polyether-based resin) and the like.

The solidification point of the polyether ester resin is preferably-5℃or lower, more preferably-50℃to-10 ℃.

The composition of the present specification can be used to prepare a plasticizer dispersion, and then melt-kneaded together with a diluent resin (thermoplastic resin) to prepare a molded article.

The content of the ultraviolet absorber in the plasticizer dispersion is preferably 0.1 to 30 mass%.

The plasticizer dispersion is prepared by dissolving or dispersing an ultraviolet absorber in a plasticizer.

Examples of plasticizers include: phthalate esters, adipate esters, trimellitate esters, polyesters, phosphate esters, citrate esters, epoxidized vegetable oils, sebacate esters, and the like. Of these, triethylene glycol-di-2-ethylhexanoate and triethylene glycol-di-n-heptanoate are also preferable, and triethylene glycol-di-2-ethylhexanoate is more preferable.

The plasticizer may be used singly or in combination of two or more kinds.

In the plasticizer dispersion, the content of the plasticizer is preferably 60 to 99.9 mass%.

(resin-type dispersant)

The liquid master batch and the plasticizer dispersion in the present invention may contain a resin-type dispersing agent. Thus, the ultraviolet absorber is more uniformly dispersed in the liquid master batch and the plasticizer dispersion, and the molded article can have higher transparency. In addition, by including the resin-type dispersing agent, the storage stability of the liquid master batch and the plasticizer dispersion is improved.

The resin type dispersing agent is a resin containing an adsorption site having a property of adsorbing to the ultraviolet absorber and the color material and a relaxation site having compatibility with components other than the ultraviolet absorber and the color material. The resin-type dispersant may be exemplified by: basic dispersants, acidic dispersants, neutral dispersants, amphoteric dispersants, and the like. Examples of the main skeleton of the resin-type dispersant include: polyurethane skeleton, polyolefin skeleton, poly (meth) acryl skeleton, polyester skeleton, polyamide skeleton, polycarbonate skeleton, polyether skeleton, polysiloxane skeleton, polyvinyl skeleton, polyimide skeleton, polyurea skeleton, and the like, and further may be a composite resin of these skeletons. The molecular structure of the resin-type dispersant is not limited, and examples thereof include a random structure, a block structure, a chain structure, a comb structure, and a star structure.

In addition, in the case where the resin-type dispersant has an acidic group or a basic group, a part or all of the resin-type dispersant may be neutralized.

Examples of the acidic group include: sulfo, phenol, phosphate or carboxyl groups. Among these, carboxyl groups are also preferable.

Examples of the basic group include: primary amino, secondary amino, tertiary amino, and quaternary ammonium salt sites. Among these, tertiary amino groups and quaternary ammonium salt sites are preferable.

Among the above dispersants, a resin-type dispersant having a basic functional group and a polymer dispersant having a basic functional group are preferable, and a graft copolymer having a nitrogen atom, an acrylic block copolymer having a tertiary amino group, a quaternary ammonium salt group, a nitrogen atom containing functional group containing a nitrogen-containing heterocycle or the like in a side chain, a urethane-type resin-type dispersant, a urethane-type polymer dispersant, and the like are more preferable, because the viscosity of the dispersion is reduced by a small amount of the dispersant.

The resin type dispersant may be used singly or in combination of two or more.

The content of the resin type dispersing agent is preferably about 5 to 200 mass%, more preferably about 10 to 100 mass%, based on 100 parts by mass of the ultraviolet absorber.

Examples of commercial products of the resin-type dispersing agent include: disepbik (Disepbyk) -101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, and BYK-Chemie Japan (BYK Japan) 2155 or Anbody Tara-U (Anti-Terra-U) 203, 204, or Pick (BYK) -P104, P104S, 220S, 6919, or Lycra (Lactimon), lycra (Lactimon) -WS or Bykumen, etc., sonupase (SOLSPERRE) -3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., and alfuka (EFKA) -46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and al Ji Sipa (ajisespb) PA111, 822, 824, 821, etc., manufactured by Fine chemical PB Fine-tech (ajinomotpb) company.

In the case where the resin-type dispersing agent is dissolved in an organic solvent, it is preferable to add a liquid resin, decompress and heat the resin, and distill off the solvent for use. In this case, the liquid master batch containing the same does not contain an organic solvent, and therefore is easy to use in terms of steps.

Method for producing liquid masterbatch

The liquid master batch can be produced by mixing an ultraviolet absorber with a liquid resin. In addition, it is preferable to use a resin-type dispersing agent at the time of production. For the mixing, for example, a kneader, a twin roll mill, a three roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, a ring bead mill, or an attritor may be used.

Process for producing plasticizer dispersion

The plasticizer dispersion may be prepared by mixing an ultraviolet absorber with a plasticizer. In addition, it is preferable to use a resin-type dispersing agent at the time of production. The apparatus described in the above "method for producing a liquid masterbatch" can be used for mixing.

The composition of the present specification may contain, in addition to the thermoplastic resin and the ultraviolet absorber, an antioxidant, a light stabilizer, a dispersant, a wax, and the like as optional components.

The composition containing the ultraviolet absorber and the thermoplastic resin can be used as a coating material, for example.

The thermoplastic resin is preferably a resin having a glass transition temperature of 30℃or higher. Examples of the thermoplastic resin include nitrocellulose and polyester.

The coating material may contain a resin-type dispersant having a carboxyl group as the resin-type dispersant. The molecular structure of the resin-type dispersant having a carboxyl group may be comb-type, linear, or the like.

(comb-type resin-type dispersant)

Examples of the comb-shaped resin-type dispersing agent having a carboxyl group include the following (S1) and (S2).

[ resin-type dispersant (S1) ]

The resin-type dispersant (S1) can be produced by known methods such as international publication No. 2008/007776, japanese patent application laid-open publication No. 2008-029901, and japanese patent application laid-open publication No. 2009-155406.

For example, a resin-type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tetracarboxylic dianhydride; and a resin-type dispersant which is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tetracarboxylic dianhydride.

[ resin-type dispersant (S2) ]

The resin type dispersant (S2) can be produced by known methods such as international publication No. 2008/007776, japanese patent application laid-open publication No. 2009-155406, japanese patent application laid-open publication No. 2010-185934, and japanese patent application laid-open publication No. 2011-157416.

For example, there can be mentioned a resin-type dispersant having a side chain obtained by polymerizing an ethylenically unsaturated monomer having a thermally crosslinking group such as a hydroxyl group, a tertiary butyl group or an oxetane skeleton, a blocked isocyanate group, or the like, and the other in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tetracarboxylic dianhydride; and a resin-type dispersant obtained by reacting an ethylenically unsaturated monomer having an isocyanate group with a hydroxyl group of the side chain.

(Linear resin-type dispersant)

The linear resin-type dispersant can be produced by a known method, and can be synthesized by a known method such as that shown in JP 2009-251481A, JP 2007-23195A, and JP 8-143651A. As an example of a method for producing a linear dispersant, a dispersant having a carboxyl group can be produced by adding a tricarboxylic anhydride to a hydroxyl group using a vinyl polymer having one hydroxyl group at one end as a raw material.

(other resinous dispersing agent)

As the other resin-type dispersant, as long as it contains an affinity site having a property of adsorbing to an ultraviolet absorber and a color material and a site having compatibility with an ultraviolet absorber or a color material carrier and has an action of adsorbing to an added ultraviolet absorber and color material and stabilizing dispersion to a colorant carrier, a dispersant which is repeated as described above may be used, and specifically, a polycarboxylic acid ester such as a polyurethane or a polyacrylate, an unsaturated polyamide, a polycarboxylic acid, a (partial) amine salt, an ammonium salt of a polycarboxylic acid, an alkylamine salt of a polycarboxylic acid, a long-chain polyaminoamide phosphate, a polycarboxylic acid ester containing a hydroxyl group, an amide formed by a reaction of these, a poly (lower alkylene imine) and a polyester having a free carboxyl group, and an oily dispersant such as a (meth) acrylic acid-styrene copolymer, a (meth) acrylic acid ester copolymer, a styrene-maleic acid copolymer, a polyvinyl alcohol, a water-soluble resin such as a polyvinyl pyrrolidone, a water-soluble polymer compound, a polyester, a modified polyacrylate, an ethylene oxide/propylene oxide compound, an addition compound, or a mixture of these may be used alone or as a mixture of two of these.

The polymer dispersant having a basic functional group includes: a nitrogen atom-containing graft copolymer, a nitrogen atom-containing acrylic block copolymer having a tertiary amino group, a quaternary ammonium salt group, a functional group containing a nitrogen-containing heterocycle or the like in a side chain, a urethane-based polymer dispersant, and the like.

Commercial products of the resin type dispersant are the same as those described above.

Next, a composition containing the ultraviolet absorber and the photocurable resin according to the embodiment of the present invention will be described. The composition can be used for coating film applications such as hard coat layers, top coat layers, and intermediate layers of various laminates. In this case, the composition preferably contains an ultraviolet absorber, a photopolymerizable compound, and a photopolymerization initiator. The ultraviolet absorber in the composition more preferably contains a photohardenable site. In addition, the composition may contain a resin. The composition may contain an additive known as a photocurable composition and an organic solvent as needed.

The photopolymerizable compound includes monomers and oligomers. Examples of the photopolymerizable compound include: methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, beta-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, phenoxy tetraethylene glycol (meth) acrylate, phenoxy hexaethylene glycol (meth) acrylate, trimethylolpropane propylene oxide (propylene oxide, PO) modified tri (meth) acrylate, trimethylolpropane ethylene oxide (ethylene oxide, EO) modified tri (meth) acrylate, isocyanuric acid EO modified di (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1, 6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) glycidyl ether di (meth) acrylate, various acrylates and methacrylates such as tricyclodecyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.

Examples of the photopolymerization initiator include: acetophenone ring-containing compounds, benzoin ring-containing compounds, benzophenone ring-containing compounds, thioxanthone ring-containing compounds, triazine ring-containing compounds, oxime ester-containing compounds, phosphine-containing compounds, quinone-containing compounds, boric acid ester-containing compounds, carbazole ring-containing compounds, imidazole ring-containing compounds, titanocene-containing compounds, and the like. Among these, oxime ester compounds are preferable in terms of high sensitivity.

Next, a composition containing the ultraviolet absorber and the thermosetting resin according to the embodiment of the present invention will be described. The composition is useful, for example, in coating, adhesive applications. In this case, the composition preferably contains an ultraviolet absorber and a thermosetting resin, and more preferably contains a curing agent. In other words, the composition preferably contains an ultraviolet absorber, a thermosetting resin (adhesive resin), and a curing agent.

The adhesive resin has a glass transition temperature of-50 to-20 ℃. Examples of the type of the adhesive resin include: acrylic resins, polyesters, urethane resins, and the like. The adhesive resin preferably has a functional group capable of reacting with the curing agent. Examples of the functional group include a carboxyl group and a hydroxyl group.

Examples of the hardening agent include: isocyanate hardeners, epoxy hardeners, aziridine hardeners, metal chelate hardeners, and the like.

Formed body

The molded article according to the embodiment of the present invention can be produced by melt-kneading and molding a composition containing an ultraviolet absorber, a resin, and the like. When the composition is a master batch, it is preferable to melt-knead the master batch with a diluent resin to prepare a molded article. In the embodiment of the present invention, the molded article is obtained by pouring a resin into a mold. The molded article includes an article obtained without using a mold, such as a plastic film, and a molded article. The diluent resin is preferably a thermoplastic resin as already described.

In the melt kneading, for example, a single-shaft kneading extruder, a twin-shaft kneading extruder, a tandem twin-shaft kneading extruder, or the like is preferably used. The melt kneading temperature varies depending on the type of thermoplastic resin, and is usually about 150℃to 320 ℃.

Examples of the molding method include: extrusion molding, injection molding, blow molding, and the like. Examples of extrusion molding include: compression molding, tube extrusion molding, lamination molding, T-die molding, inflation molding, melt spinning, and the like.

The molding temperature depends on the softening point of the diluted resin and is usually 160 to 320 ℃.

The molded article according to the embodiment of the present invention is useful for, for example, pharmaceutical packaging materials, food packaging materials, displays, glass intermediate films, optical lenses, solar cells, window films, and spectacle lenses.

The pharmaceutical packaging material and the food packaging material are preferably obtained by using, for example, a polyester resin, a cycloolefin resin, or the like as the thermoplastic resin. The molded article has improved flexibility and visibility, and can suppress deterioration of the content.

The molded article usable for displays, glass intermediate films, optical lenses, and solar cells may be any molded article comprising a thermoplastic resin, and is preferably a film comprising a resin having a property of being transparent to a desired wavelength. The resin constituting such a molded article includes: polyetherimide-based resins, polyethersulfone-based resins, polyethylene terephthalate-based resins, polyimide-based resins, polysulfone-based resins, polyarylate-based resins, polyamide-based resins, polycarbonate-based resins, olefin polymer-based resins having an alicyclic structure (alicyclic olefin polymer-based resins), cellulose ester-based resins, and the like.

Coating film

The coating film according to the embodiment of the present invention can be produced by applying a coating material including a composition containing an ultraviolet absorber and a resin, an organic solvent, or the like to a substrate or the like and drying the coating material. Examples thereof include a hard coat layer, a top coat layer, a coating film layer such as an intermediate layer of various laminates, an adhesive layer, and the like.

In applications such as materials for displays, materials for sensors, optical control materials, various industrial coating materials, automobile parts, home electric appliances, building materials for houses, and cosmetics (cosmetics), etc., a film for shielding ultraviolet rays is formed by applying a film to a substrate or the like, and deterioration of organic materials and the like can be suppressed.

The adhesive layer may be formed by, for example, applying the adhesive layer to a release sheet and drying the same, and then bonding a substrate to the adhesive layer to produce an adhesive sheet.

The pressure-sensitive adhesive sheet of the present specification is preferably used by being bonded to each substrate in applications such as displays (for example, televisions, personal computers, smartphones, and the like), automobile parts, members for sensors, home appliances, building materials for houses, and the like, and glass interlayer applications. The adhesive sheet can absorb light in the short wavelength region of ultraviolet rays and visible light contained in backlight and sunlight, suppress adverse effects on eyes and human bodies, and suppress degradation of display elements of a display by including the ultraviolet absorber according to the embodiment of the present invention. In addition, sheets, films and tapes are synonymous.

< use and Effect >

The ultraviolet absorber, the composition, the molded article, and the coating film according to the embodiments of the present invention can reduce damage to organic matter and human body caused by ultraviolet rays having a wavelength of less than 400nm and light in a short wavelength region of visible light of about 400nm to 420 nm.

In display applications, for example, the film can be used for optical films and the like which can be used for televisions, personal computers, smartphones and the like. The laminate using the molded body or the coating film according to the embodiment of the present invention can suppress adverse effects on eyes by absorbing light in the short wavelength region of ultraviolet light and visible light contained in the backlight of the display, and can suppress degradation of the display element of the display by absorbing light in the short wavelength region of ultraviolet light and visible light contained in sunlight.

The glass interlayer film is used for example in laminated glass for automobiles, buildings, and the like. A laminated glass using a molded article comprising the composition can suppress adverse effects on eyes and human bodies by absorbing light in a short wavelength region of ultraviolet rays and visible light contained in sunlight.

The present invention is applicable to lenses, for example, lenses usable for spectacles, optical sensors, and the like. Lenses using molded articles comprising the composition can suppress adverse effects on eyes and human bodies by absorbing light in a short wavelength region of ultraviolet rays and visible light contained in sunlight, for example, in spectacle applications, and can improve the sensitivity of sensors by blocking light of unnecessary wavelengths that may become noise in optical sensor applications.

In packaging materials for pharmaceutical agents, cosmetics, and the like, specific components such as vitamins contained in the packaging materials are degraded even under light in the short wavelength region of visible light of about 400nm to 420nm, and thus degradation can be further reduced as compared with conventional ultraviolet absorbers.

Generally, since ultraviolet light and light in a short wavelength region of visible light of about 400nm to 420nm deteriorate resins, when the ultraviolet absorber according to the embodiment of the present invention is used, deterioration of resins can be reduced in the entire use of the resins, and thus the life of molded articles and coating films can be prolonged, and as a result, waste can be reduced.

In the present specification, a numerical range indicated by "to" is used to indicate a range including numerical values described before and after "to" as a minimum value and a maximum value, respectively. In the numerical ranges described in stages in the present specification, the upper limit value or the lower limit value of the numerical range in a certain stage may be arbitrarily combined with the upper limit value or the lower limit value of the numerical range in another stage.

The present invention is associated with the subject matter of japanese patent application No. 2021-116306 filed at 7/14 of 2021, the entire disclosure of which is incorporated herein by reference.

Examples

The present invention will be described in more detail below. The present invention is not limited to the examples. The "parts by mass" is referred to as "parts" and the "%" is referred to as "%".

Method for producing ultraviolet-absorbing pigment (A-1)

(ultraviolet light absorbing pigment A-1)

A300 mL Erlenmeyer flask was charged with 160 parts of nitrobenzene, 8 parts of cyanuric chloride, and 17.4 parts of aluminum chloride, and stirred and suspended. Then, 21.9 parts of 2-naphthol was added in small amounts while cooling with ice water. After that, the mixture was stirred overnight while gradually returning to room temperature, to obtain a reaction solution (A' -1). On the other hand, 38.1 parts of water, 10.0 parts of 35% hydrochloric acid and 45.0 parts of methanol were charged into a 500mL beaker, and the reaction solution (A' -1) was gradually and little-dropped. After stirring for 30 minutes, filtration separation was performed, thereby obtaining a wet cake (a-1) containing the ultraviolet absorbing pigment (a-1).

[ chemical 23]

Ultraviolet ray absorbing pigment (A-1)

< method for producing ultraviolet absorber 1 to ultraviolet absorber 4 >

[ ultraviolet absorber 1]

45g of methanol was sprayed on the wet cake (a-1) and washed, followed by filtration and separation to obtain a wet cake (a-2). The obtained wet cake (a-2) was dried at 80℃overnight to obtain an ultraviolet absorber 1 comprising an ultraviolet absorbing pigment (A-1).

(method for identifying Compound)

Nuclear magnetic resonance (nuclear magnetic resonance, NMR) is used for the identification of the ultraviolet absorbing pigment (a) represented by the general formulae (1) to (3) according to the embodiment of the present invention.

< measurement conditions >

The device comprises: bruce Azos (BRUKER AVANCE) 400

Resonant frequency: 400 MHz% ¹ H-NMR)

A solvent: dimethyl sulfoxide-d ₈

Use of tetramethylsilane as a catalyst ¹ The internal standard of H-NMR, the chemical shift value is represented by delta value (ppm), and the coupling constant is represented by Hertz. S is abbreviated as single, d is abbreviated as double, and m is abbreviated as multiple. The content of the obtained NMR spectrum is as follows.

δ＝12.05(s，3H)，8.70(d，J＝8.4Hz，3H)，8.07(d，J＝8.8Hz，3H)，7.93(d，J＝8.0Hz，3H)，7.46-7.50(m，3H)，7.38-7.42(m，3H)，7.34(d，J＝9.2Hz，3H)

As described above, the ultraviolet absorbing pigment (A-1) was subjected to NMR measurement, and as a result, the structure was supported. The other ultraviolet-absorbing pigments were also identified by NMR in the same manner as described above, but the data were omitted.

(method for measuring Metal component)

ICP emission analysis is used in the measurement of the metal component (B) of the ultraviolet absorber according to the embodiment of the present invention.

< measurement conditions >

Approximately 0.2g of the ultraviolet absorber 1 was precisely weighed, and subjected to a decomposition treatment (2 mL of nitric acid for precise analysis was added as a decomposition reagent) by a microwave sample pretreatment apparatus (MLS-1200 MEGA manufactured by Milston (Milestone General)). Then, ultrapure water was added to the obtained decomposed solution, and 25mL of the filtered filtrate was subjected to constant volume using a volumetric flask. The solution was measured by ICP emission analysis (manufactured by Varian Co., ltd., 720-ES ICP emission spectrometer (Optical emission spectrometer)), and the metal ions were quantified. The content of the metal component (B) shown in this example is a total value of the contents of Na, mg, al, K, ca and Fe ions.

Metal analysis was performed on the ultraviolet absorber 1, and as a result, na:1432ppm, mg:836ppm, al:42750ppm, K:147ppm, ca:2428ppm, fe:548 ppm. The total value of the metal components (B) was 48141ppm.

As described above, in the present specification, the ultraviolet absorber 1 is taken as an example, and the metal atoms are measured by ICP emission analysis. Other ultraviolet absorbers were also measured in the same manner as described above. The measurement results are shown in Table 1.

(method for measuring powder X-ray diffraction of ultraviolet absorber)

A powder X-ray diffraction apparatus is used for measuring the X-ray diffraction pattern of the ultraviolet absorber.

Powder X-ray diffraction measurement is carried out at a diffraction angle (2. Theta.) in the range of 3 DEG to 35 DEG in accordance with Japanese Industrial Standard JIS K0131 (X-ray diffraction analysis rule).

The measurement conditions are as follows.

X-ray diffraction device: RINT2100 manufactured by Rigaku Co., ltd

Sampling width: 0.02 degree

Scanning speed: 2.0 DEG/min

Divergence slit: 1 degree

Divergent longitudinal limiting slit: 10mm of

Scattering slit: 2 degree

Light receiving slit: 0.3mm

Tube ball: cu (Cu)

Tube voltage: 40kV (kilovolt)

Tube current: 40mA

Fig. 1 shows an example of a diffraction pattern of powder X-ray diffraction of an ultraviolet absorber. In fig. 1, the X-axis is the bragg angle (2θ) and the Y-axis is the intensity (count) of the diffraction peak. The method for calculating the intensity ratio of the diffraction peak will be described below.

Background removal of the diffraction pattern in fig. 1 is performed by a usual method. As an example, a straight line tangent to the vicinity of 6 ° of the lower-angle side skirt of 7.6 ° of the bragg angle (2θ) and the vicinity of 8.5 ° of the higher-angle side skirt is drawn, and the value on the straight line is removed as a background. Similarly, a straight line tangent to the vicinity of 12 ° of the lower-angle side skirt and the vicinity of 14 ° of the higher-angle side skirt of the bragg angle (2θ) 13.2 ° is drawn, and the value on the straight line is removed as a background. The intensity ratio of diffraction peaks was calculated as iα/iβ, assuming that the peak intensity at bragg angle (2θ) of 7.6 ° was iα, the peak intensity at 13.2 ° was iβ.

[ ultraviolet absorber 2]

The wet cake (a-2) was put back into 100g of methanol, reslurried at room temperature for 30 minutes, and filtered to obtain a wet cake (a-3). The obtained wet cake (a-3) was dried at 80℃overnight to obtain an ultraviolet absorber 2 containing an ultraviolet absorbing pigment (A-1).

[ ultraviolet absorber 3]

After obtaining the wet cake (a-3), 45g of water was sprayed for washing, and filtration was carried out to obtain a wet cake (a-4). The obtained wet cake (a-4) was dried at 80℃overnight to obtain an ultraviolet absorber 3 containing an ultraviolet absorbing pigment (A-1).

[ ultraviolet absorber 4]

The wet cake (a-4) was put back into 150g of water, reslurried at room temperature for 30 minutes, and filtered to separate to obtain a wet cake (a-5). The obtained wet cake (a-5) was dried at 80℃overnight to obtain an ultraviolet absorber 4 containing an ultraviolet absorbing pigment (A-1).

Method for producing ultraviolet-absorbing pigment (A-2)

(ultraviolet light absorbing pigment A-2)

A300 mL Erlenmeyer flask was charged with 160 parts of chlorobenzene, 8 parts of 2, 4-dichloro-6-phenyl-1, 3, 5-triazine, 11.8 parts of aluminum chloride, and stirred and suspended. Next, 12.8 parts of 2-naphthol was added in small portions while cooling with ice water. After that, the mixture was stirred overnight while gradually returning to room temperature, to obtain a reaction solution (A' -2). On the other hand, 38.1 parts of water, 10.0 parts of 35% hydrochloric acid and 45.0 parts of methanol were charged into a 500mL beaker, and the reaction solution (A' -2) was gradually and little-dropped. After stirring for 30 minutes, filtration separation was performed, thereby obtaining a wet cake (a-6) containing the ultraviolet absorbing pigment (a-2).

[ chemical 24]

Ultraviolet ray absorbing pigment (A-2)

Ultraviolet absorber 5-method for producing ultraviolet absorber 8

[ ultraviolet absorber 5-ultraviolet absorber 8]

The wet cake (a-7) to wet cake (a-10) were obtained by the same method as the ultraviolet light absorbers 1 to 4, to thereby obtain the ultraviolet light absorbers 5 to 8 containing the ultraviolet light absorbing pigment (A-2).

Method for producing ultraviolet-absorbing pigment (A-3)

(ultraviolet light absorbing pigment A-3)

A300 mL Erlenmeyer flask was charged with 160 parts of toluene, 8 parts of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, and 8.0 parts of aluminum chloride, and stirred and suspended. Next, 6.5 parts of 2-naphthol was added in small portions while cooling with ice water. After that, the mixture was stirred overnight while gradually returning to room temperature. On the other hand, the reaction solution was added dropwise in small amounts successively by charging 38.1 parts of water, 10.0 parts of 35% hydrochloric acid and 45.0 parts of methanol into a 500mL beaker. After stirring for 30 minutes, filtration separation was performed, thereby obtaining a wet cake (a-11) containing the ultraviolet absorbing pigment (A-3).

[ chemical 25]

Ultraviolet ray absorbing pigment (A-3)

Ultraviolet absorber 9-ultraviolet absorber 12 production method

[ ultraviolet absorber 9 to ultraviolet absorber 12]

The wet cake (a-12) to wet cake (a-15) were obtained by the same method as the ultraviolet light absorbers 1 to 4, thereby obtaining the ultraviolet light absorbers 9 to 12 containing the ultraviolet light absorbing pigment (A-3).

Method for producing ultraviolet absorber 13

[ ultraviolet absorber 13]

A300 mL Erlenmeyer flask was charged with 160 parts of xylene, 8 parts of cyanuric chloride, and 17.4 parts of aluminum chloride, and stirred and suspended. Next, 21.9 parts of 2-naphthol was added in small amounts. Thereafter, the mixture was stirred at 80℃for 6 hours to obtain a reaction solution (A' -3). On the other hand, 38.1 parts of water, 10.0 parts of 35% hydrochloric acid and 45.0 parts of methanol were charged into a 500mL beaker, and the reaction solution (A' -3) was gradually and little-dropped. After stirring for 30 minutes, filtration separation was performed, thereby obtaining a wet cake (a-16) containing the ultraviolet absorbing pigment (A-1). The obtained wet cake (a-16) was dried at 80℃overnight to obtain a dried product.

To 1000 parts of methanesulfonic acid, 40.0 parts of the dried product was gradually added while stirring, and the mixture was stirred for 4 hours to dissolve the dried product. Then, the solution was gradually added dropwise to 8000 parts of 25℃water with stirring for 30 minutes, filtered, washed with water, and dried at 80℃to obtain an ultraviolet absorber 13 containing an ultraviolet absorbing pigment (A-1).

Method for producing ultraviolet absorber 14

[ ultraviolet absorber 14]

300 parts of an ultraviolet absorber 13, 1500 parts of sodium chloride and 400 parts of diethylene glycol were charged into a 3L double arm kneader to form a dough (dough), and the dough was kneaded at a material temperature of 60℃for 6 hours. The obtained dough (kneaded mass) was taken out, reslurried in water in an amount about 10 times the weight of the dough, stirred at 25℃for 1.5 hours, and then filtered. Further, the resultant was reslurried, filtered and washed with water to obtain a paste pigment, and dried in a heating oven at 80℃for 48 hours to obtain an ultraviolet absorber 14 containing an ultraviolet absorbing pigment (A-1).

Method for producing ultraviolet absorber 15

[ ultraviolet absorber 15]

A300 mL Erlenmeyer flask was charged with 160 parts of methyl benzoate, 8 parts of 2, 4-dichloro-6-phenyl-1, 3, 5-triazine, and 11.8 parts of aluminum chloride, and stirred and suspended. Next, 12.8 parts of 2-naphthol was added in small portions while cooling with ice water. After that, the mixture was stirred overnight while gradually returning to room temperature. On the other hand, the reaction solution was added dropwise in small amounts successively by charging 38.1 parts of water, 10.0 parts of 35% hydrochloric acid and 45.0 parts of methanol into a 500mL beaker. After stirring for 30 minutes, filtration separation was performed, thereby obtaining a wet cake (a-17) containing the ultraviolet absorbing pigment (A-2). The obtained wet cake (a-17) was dried at 80℃overnight to obtain a dried product.

To 1000 parts of methanesulfonic acid, 40.0 parts of the dried product was gradually added while stirring, and the mixture was stirred for 4 hours to dissolve the dried product. Then, the solution was gradually added dropwise to 8000 parts of 25℃water with stirring for 30 minutes, filtered, washed with water, and dried at 80℃to obtain an ultraviolet absorber 15 containing an ultraviolet absorbing pigment (A-2).

Method for producing ultraviolet absorber 16

[ ultraviolet absorber 16]

A300 mL Erlenmeyer flask was charged with 128 parts of xylene, 32 parts of methyl benzoate, 8 parts of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, and 8.0 parts of aluminum chloride, and stirred and suspended. Next, 6.5 parts of 2-naphthol was added in small portions while cooling with ice water. After that, the mixture was stirred overnight while gradually returning to room temperature. On the other hand, the reaction solution was added dropwise in small amounts successively by charging 38.1 parts of water, 10.0 parts of 35% hydrochloric acid and 45.0 parts of methanol into a 500mL beaker. After stirring for 30 minutes, filtration separation was performed, thereby obtaining a wet cake (a-18) containing the ultraviolet absorbing pigment (A-3). The obtained wet cake (a-18) was dried at 80℃overnight to obtain a dried product.

To 1000 parts of methanesulfonic acid, 40.0 parts of the dried product was gradually added while stirring, and the mixture was stirred for 4 hours to dissolve the dried product. Then, the solution was gradually added dropwise to 8000 parts of 25℃water with stirring for 30 minutes, filtered, washed with water, and dried at 80℃to obtain an ultraviolet absorber 16 containing an ultraviolet absorbing pigment (A-3).

Method for producing ultraviolet absorber 17

[ ultraviolet absorber 17]

To 1000 parts of methanesulfonic acid, 40.0 parts of ultraviolet absorber 1 was gradually added while stirring, and the mixture was stirred for 4 hours to dissolve the ultraviolet absorber. Then, the solution was gradually added dropwise to 50000 parts of water at 0℃for 30 minutes while stirring, filtered, washed with water, and dried at 80℃to obtain an ultraviolet absorber 17 containing an ultraviolet absorbing pigment (A-1).

Method for producing ultraviolet absorber 18

[ ultraviolet absorber 18]

35.0 parts of ultraviolet absorber 3 and 350 parts of diethylene glycol were mixed, and heated and stirred at 120℃for 3 hours. The resultant was filtered and washed with warm water, and dried at 80℃to obtain an ultraviolet absorber 18 containing an ultraviolet absorbing pigment (A-1) represented by the general formula (1).

Method for producing ultraviolet absorber 19

[ ultraviolet absorber 19]

An ultraviolet absorber 19 containing an ultraviolet absorbing pigment (a-3) was obtained in the same manner as in the production of the ultraviolet absorber 17 except that the ultraviolet absorber 9 was used instead of the ultraviolet absorber 1.

Method for producing ultraviolet absorber 20

[ ultraviolet absorber 20]

An ultraviolet absorber 20 containing an ultraviolet absorbing pigment (a-3) was obtained in the same manner as in the production of the ultraviolet absorber 18 except that the ultraviolet absorber 11 was used instead of the ultraviolet absorber 3.

Method for producing ultraviolet absorber 21

(ultraviolet light absorbing pigment A-4)

A wet cake (a-19) containing the ultraviolet absorbing pigment (A-4) was obtained in the same manner as in the production of the ultraviolet absorbing pigment (A-1), except that 24.3 parts of 1, 3-dihydroxynaphthalene was added in place of 21.9 parts of 2-naphthol. 45g of methanol was sprayed on the wet cake (a-19) and washed, followed by filtration to obtain a wet cake (a-20). The wet cake (a-20) was then put back into 100g of methanol, reslurried at room temperature for 30 minutes, and separated by filtration. Then, 45g of water was sprayed and washed, and the wet cake (a-21) was obtained by filtration and separation. The obtained wet cake (a-21) was dried at 80℃overnight to obtain an ultraviolet absorber 21 comprising an ultraviolet absorbing pigment (A-4).

Method for producing ultraviolet absorber 22

(ultraviolet light absorbing pigment A-5)

An ultraviolet absorber 22 containing an ultraviolet absorbing pigment (A-5) was obtained by the same method as that for the production of the ultraviolet absorber 21 except that 33.9 parts of 6-bromo-2-naphthol was added instead of 24.3 parts of 1, 3-dihydroxynaphthalene.

[ chemical 26]

Method for producing ultraviolet absorber 23

(ultraviolet light absorbing pigment A-6)

A wet cake (a-22) containing the ultraviolet absorbing pigment (A-6) was obtained in the same manner as in the production of the ultraviolet absorbing pigment (A-3), except that 9.1 parts of methyl 6-hydroxy-2-naphthoate was added instead of 6.5 parts of 2-naphthol. 45g of methanol was sprayed on the wet cake (a-22) and washed, followed by filtration and separation to obtain a wet cake (a-23). The wet cake (a-23) was then put back into 100g of methanol, reslurried at room temperature for 30 minutes, and separated by filtration. Further, 45g of water was sprayed and washed, and then, the wet cake (a-24) was obtained by filtration and separation. The obtained wet cake (a-24) was dried at 80℃overnight to obtain an ultraviolet absorber 23 comprising an ultraviolet absorbing pigment (A-6).

Method for producing ultraviolet absorber 24

(ultraviolet light absorbing pigment A-7)

An ultraviolet absorber 24 containing an ultraviolet absorbing pigment (A-7) was obtained in the same manner as in the production of the ultraviolet absorber 23 except that 8.4 parts of 6-hydroxy-2-naphthoic acid was added instead of 9.1 parts of methyl 6-hydroxy-2-naphthoate.

[ chemical 27]

Method for producing ultraviolet absorber 25

(ultraviolet light absorbing pigment A-8)

An ultraviolet absorber 25 containing an ultraviolet absorbing pigment (a-8) was obtained in the same manner as in the production of the ultraviolet absorber 23 except that 11.0 parts of sodium 2-naphthol-6-sulfonate hydrate was added instead of 9.1 parts of methyl 6-hydroxy-2-naphthoate.

Method for producing ultraviolet absorber 26

(ultraviolet light absorbing pigment A-9)

In the ultraviolet light absorbing pigment (A-2) production, except that 8 parts of 2- (4-biphenyl) -4, 6-dichloro-1, 3, 5-triazine, 9.5 parts of 2-naphthol, 8.8 parts of aluminum chloride were added in place of 8 parts of 2, 4-dichloro-6-phenyl-1, 3, 5-triazine, 12.8 parts of 2-naphthol, and 11.8 parts of aluminum chloride, the same procedure was followed to obtain a wet cake (a-25) containing the ultraviolet light absorbing pigment (A-9). 45g of methanol was sprayed on the wet cake (a-25) and washed, followed by filtration to obtain a wet cake (a-26). The wet cake (a-26) was then put back into 100g of methanol, reslurried at room temperature for 30 minutes, and separated by filtration. Further, 45g of water was sprayed and washed, and then, the wet cake (a-27) was obtained by filtration and separation. The obtained wet cake (a-27) was dried at 80℃overnight to obtain an ultraviolet absorber 26 containing an ultraviolet absorbing pigment (A-9).

[ chemical 28]

Method for producing ultraviolet absorber 27

(ultraviolet light absorbing pigment A-10)

Into a 300mL Erlenmeyer flask, 8 parts of ultraviolet absorber 1 and 80 parts of N-methyl-2-pyrrolidone were placed, and the mixture was stirred and dissolved. Next, 5.4 parts of tripotassium phosphate was charged, stirred and suspended. Then, 5.8 parts of 1-iodobutane was charged, and the mixture was heated to 110℃with stirring, and stirred for 3 hours to obtain a reaction solution. On the other hand, 400 parts of water was charged into a 1L beaker, and the reaction solution was gradually and little-by-little added dropwise. After stirring overnight, the mixture was separated by filtration to give a wet cake (a-28). The wet cake (a-28) was reslurried in 400g of water, stirred for 3 hours, and then filtered to obtain a wet cake (a-29). The obtained wet cake (a-29) was dried at 80℃overnight, and the obtained dried product was pulverized with 80 meshes, thereby obtaining an ultraviolet absorber 27 containing an ultraviolet absorbing pigment (A-10).

Method for producing ultraviolet absorber 28

(ultraviolet light absorbing pigment A-11)

A500 mL Erlenmeyer flask was charged with 100 parts of N-methyl-2-pyrrolidone and 10 parts of ultraviolet absorber 24, and dissolved. Then, 6.7 parts of 2-ethylhexyl glycidyl ether and 0.3 parts of 3, 5-lutidine were charged, and the temperature was raised to 120℃and stirred for 6 hours to obtain a reaction solution. After the reaction solution was cooled to 50℃or lower, 40 parts of 35% hydrochloric acid and 200 parts of methanol were gradually and little-by-little added dropwise to the reaction solution. After stirring for 30 minutes, filtration separation was performed, and the obtained wet cake (a-30) was put back into 100 parts of methyl ethyl ketone and stirred at 40℃for 30 minutes. Then, 100 parts of methanol was added thereto, and the mixture was stirred for 30 minutes while being cooled in an ice bath, and then, the mixture was separated by filtration. The obtained wet cake (a-31) was put back into 100 parts of methanol, stirred for 30 minutes, and then separated by filtration. The obtained wet cake (a-32) was dried at 80℃overnight to obtain an ultraviolet absorber 28 containing an ultraviolet absorbing pigment (A-11).

[ chemical 29]

Method for producing ultraviolet absorber 29

(ultraviolet light absorbing pigment A-12)

A300 mL Erlenmeyer flask was charged with 100 parts of 98% sulfuric acid, 10 parts of ultraviolet absorber 9, and 9.9 parts of 2-chloro-2-methylpropane, and the mixture was stirred in an ice bath at 10℃or lower for 6 hours to obtain a reaction solution. Next, the reaction solution was gradually and little dropped into a mixed solution of 200 parts of ice and 400 parts of water. After stirring for 30 minutes, filtration separation was performed, the obtained wet cake (a-33) was put back into 450 parts of a mixed solution of methanol/water=10/1, reslurrying was performed at room temperature for 30 minutes, and filtration separation was performed. The wet cake (a-34) thus obtained was then put back into 100 parts of water at 50℃or higher, reslurried at room temperature for 30 minutes, and separated by filtration. The obtained wet cake (a-35) was dried at 80℃overnight to obtain an ultraviolet absorber 29 containing an ultraviolet absorbing pigment (A-12).

Method for producing ultraviolet absorber 30

(ultraviolet light absorbing pigment A-13)

A500 mL Erlenmeyer flask was charged with 100 parts of N-methyl-2-pyrrolidone, 10 parts of an ultraviolet absorber 24, 0.01 part of methyl hydroquinone, 6.8 parts of glycidyl methacrylate, and 0.3 part of N, N-dimethylbenzylamine, and the mixture was heated to 100℃and stirred for 4 hours, and then cooled to 40℃to obtain a reaction solution. Then, 100 parts of methanol, 50 parts of 35% hydrochloric acid, and 50 parts of water were added dropwise to the reaction solution in small amounts. After stirring for 30 minutes, filtration was performed, and the obtained wet cake (a-36) was put back into 100 parts of methanol, and after stirring for 30 minutes, filtration was performed. The wet cake (a-37) thus obtained was then put back into 100 parts of water, stirred for 30 minutes, and then separated by filtration. The obtained wet cake (a-38) was dried under reduced pressure at 60℃to obtain an ultraviolet absorber 30 containing an ultraviolet absorbing pigment (A-13).

[ chemical 30]

Method for producing comparative material 1

Comparative Material 1

The wet cake (a-1) was dried at 80℃overnight to obtain a comparative material 1 containing the ultraviolet absorbing pigment (A-1) represented by the general formula (1).

Method for producing comparative material 2

Comparative Material 2

Water was added to the reaction solution (A' -1) to conduct extraction and separation, and 5% sodium hydrogencarbonate water and saturated brine were added to the obtained organic layer to conduct separation. The obtained organic layer was concentrated under reduced pressure to obtain comparative material 2.

Method for producing comparative material 3

Comparative Material 3

The wet cake (a-6) was dried at 80℃overnight to obtain a comparative material 3 containing the ultraviolet absorbing pigment (A-2) represented by the general formula (1).

Method for producing comparative material 4

Comparative Material 4

Water was added to the reaction solution (A' -2) to conduct extraction and separation, and 5% sodium hydrogencarbonate water and saturated brine were added to the obtained organic layer to conduct separation. The obtained organic layer was concentrated under reduced pressure to obtain comparative material 4.

Method for producing comparative material 5

Comparative Material 5

The wet cake (a-11) was dried at 80℃overnight to obtain a comparative material 5 containing an ultraviolet absorbing pigment (A-3).

Method for producing comparative material 6

Comparative Material 6

Water was added to the reaction solution (A' -3) to conduct extraction and separation, and 5% sodium hydrogencarbonate water and saturated brine were added to the obtained organic layer to conduct separation. The obtained organic layer was concentrated under reduced pressure to obtain comparative material 6.

Method for producing comparative material 7

Comparative Material 7

35.0 parts of comparative material 1 and 350 parts of diethylene glycol were mixed and stirred at 120℃for 3 hours. The resultant was filtered and washed with warm water, and dried at 80℃to obtain a comparative material 7 containing the ultraviolet-absorbing pigment (A-1) represented by the general formula (1).

Method for producing comparative material 8

Comparative Material 8

To 1000 parts of methanesulfonic acid, 40.0 parts of comparative material 2 was gradually added while stirring, and the mixture was stirred for 4 hours to dissolve the same. Then, the solution was gradually added dropwise to 50000 parts of water at 0℃for 30 minutes while stirring, filtered, washed with water, and dried at 80℃to obtain comparative material 8 containing ultraviolet-absorbing pigment (A-1).

Method for producing comparative material 9

Comparative Material 9

A comparative material 9 containing an ultraviolet absorbing pigment (a-3) was obtained in the same manner as in the production of the comparative material 7 except that the comparative material 5 was used instead of the comparative material 1.

Method for producing comparative material 10

Comparative Material 10

A comparative material 10 containing an ultraviolet absorbing pigment (a-3) was obtained in the same manner as in the production of the comparative material 8 except that the comparative material 6 was used instead of the comparative material 2.

The amounts of metals and the X-ray diffraction peak ratios of the obtained ultraviolet absorbers 1 to 30 and the comparative materials 1 to 10 are shown in table 1.

TABLE 1

< solution Spectroscopy >)

Examples 1-1 to 1-30 and comparative examples 1-1 to 1-10

The ultraviolet to visible absorption spectra were measured for the ultraviolet absorbers 1 to 30 and the comparative materials 1 to 10. The results are shown in Table 2. The method for preparing a solution for measuring absorbance and the measurement conditions are as follows.

Solution preparation method

Example 1-1

1 part of ultraviolet absorber 1 and 1000 parts of tetrahydrofuran were mixed and completely dissolved. Then, 2 parts of the previous solution and 98 parts of tetrahydrofuran were uniformly mixed to prepare a solution having a concentration of 20 ppm.

The concentrations of the ultraviolet light absorbers 2 to 30 and the comparative materials 1 to 10 were also adjusted as shown in table 2.

< measurement Condition >

The device comprises: u-3500 (Hitachi manufacturing Co., ltd.)

Measurement wavelength: 300nm to 700nm

A solvent: tetrahydrofuran (THF)

Concentration: table 1 shows that

The evaluation criteria for the ultraviolet to visible absorption spectra are as follows. AA. A, B is a level that is practically unproblematic.

[ evaluation criterion ]

AA: the absorbance at 400nm is 0.8 or more

A: the absorbance at 400nm is 0.4 or more and less than 0.8

B: the absorbance at 400nm is 0.2 or more and less than 0.4

C: absorbance at 400nm is less than 0.2

TABLE 2

As shown in Table 2, it was found that when the metal content was 50000ppm or less, the absorbance at a wavelength of 400nm was high and the absorbability was good. In addition, when the metal component is 10000ppm or less, the absorbability is more excellent.

< shaped body >)

The ultraviolet absorber (C) used in the examples is shown below.

(C-1): di Nu Bin (TINUVIN) 326 (benzotriazole series manufactured by BASF Japan)

(C-2): di Nu Bin (TINUVIN) 400 (manufactured by BASF Japan, triazine series)

(C-3): aidi Coltstaw (Adekastab) 1413 (Ai Dike (manufactured by ADEKA) Co., ltd., benzophenone series)

The color material (D) used in the examples is shown below.

(D-1) c.i. pigment blue PB15:6

(D-2) C.I. solvent Red SR52

(D-3) C.I. pigment yellow PY147

The near infrared ray absorber (E) used in the examples is shown below.

[ 31]

The thermoplastic resins used in the examples are shown below.

(F-1) polyethylene (Sataiku (santec) LD M2270, MFR=7g/10 min, manufactured by Asahi chemical Co., ltd.)

(F-2) polyethylene (noobtai base (Novatec) UJ790, mfr=50 g/10min, manufactured by japan polyethylene corporation)

(F-3) Polypropylene (Novatec) PP FA3EB, mfr=10.5 g/10min, manufactured by Japanese Polypro company, japan Li Pulao

(F-4) Polypropylene (Prime Polypro Li Pulao) J226T, MFR=20g/10 min, prime Polymer Co

(G-1) Polyester (Polyester) MA-2101M (Polyester resin, you Niji available from Unitika Co., ltd., crystalline resin, melting point 264 ℃ C., MFR 45G/10min (280 ℃ C./2.16 kg))

(G-2) You Pilong (Iupplon) S-3000 (polycarbonate resin, manufactured by Mitsubishi engineering plastics Co., ltd., amorphous resin, glass transition temperature 145 ℃ C., MFR 15G/10min (300 ℃ C./1.2 kg))

(G-3) Topas 6013M-07 (cycloolefin resin, manufactured by Bao Li Plastic (Polymer) Co., ltd., amorphous resin, glass transition temperature 142 ℃ C., MFR 13G/10min (260 ℃ C./2.16 kg))

(G-4) xylonite (Apel) (cycloolefin resin, amorphous resin manufactured by Sanjing chemical Co., ltd., glass transition temperature 135 ℃ C., MFR 11G/10min or more (260 ℃ C./2.16 kg))

(G-5) Amiran CM3001-N (Polyamide resin, manufactured by Toli Co., ltd., crystalline resin, melting point 265 ℃ C., MFR 7G/10min or more (235 ℃ C./2.16 kg))

(G-6) Wutaimu (ULTEM) (polyetherimide resin, manufactured by Saint Foundation Industrial Co., ltd., amorphous resin, glass transition temperature 217 ℃ C., MFR 8G/10min or more; 337 ℃ C./6.6 kg)

The liquid resins used in the examples are shown below.

(H-1): you Niao celluloid (Unior) D-1200 (polyalkylene glycol resin, polypropylene glycol resin, number average molecular weight 1200, viscosity 200 mPa.s manufactured by Nitro oil Co., ltd.)

(H-2): PEG-400 (polyalkylene glycol resin, polypropylene glycol resin, number average molecular weight 400, viscosity 90 mPa.s, manufactured by Sanyo chemical industry Co., ltd.)

(H-3): you Niao celluloid (Unior) D-400 (polyalkylene glycol resin, polypropylene glycol resin, number average molecular weight 400, viscosity 100 mPa.s manufactured by Nitro oil Co., ltd.)

(H-4): ai Dike Seze (Adeka sizer) RS-107 (manufactured by Adeka Co., ltd., ether ester resin, adipic acid Ether ester resin, number average molecular weight 430, viscosity 20 mPa.s)

(H-5): ai Dike Seze (Adeka sizer) RS-700 (Ai Dike (ADEKA) manufactured by the Co., ltd., ether ester resin, number average molecular weight 550, viscosity 30 mPa. Multidot.s)

(H-6): ai Dike Seze (Adeka sizer) PN-250 (Ai Dike (ADEKA) manufactured by Co., ltd.), fatty acid polyester resin, adipic acid polyester resin, number average molecular weight 2100, viscosity 4,500 mPa.s

(H-7): ai Dike Seze (Adeka sizer) PN-350 (Ai Dike (ADEKA) manufactured by Co., ltd.), fatty acid polyester resin, adipic acid polyester resin, number average molecular weight 4500, viscosity 10,000 mPa.s

The plasticizers used in the examples are shown below.

(I-1) triethylene glycol-di-2-ethylhexanoate

(I-2) triethylene glycol-di-n-heptanoate

Resin dispersant (J) >

(production of resin-type dispersant solution (J-1))

To the resin type dispersant solution (J-1) of the non-volatile component/liquid resin (H-4) =1/1 of the pith (BYK) -LPN6919 manufactured by the japan pith chemical company having a non-volatile component of 60%, the liquid resin (H-4) equivalent to the pith (BYK) -LPN6919 was added, heated to 100 ℃ and distilled off under reduced pressure to remove the solvent.

[ Synthesis of ethylenically unsaturated monomer (b-5) ]

A reaction vessel including a stirrer and a thermometer was charged with 60 parts of ethyl methacrylate, 29 parts of 3- (dimethylamino) propylamine, and 120 parts of Tetrahydrofuran (THF), and stirred at room temperature for 5 hours. After completion of the reaction was confirmed by Fourier transform infrared spectroscopy (Fourier Transform Infrared, FT-IR), the solvent was distilled off by a rotary evaporator to obtain 73 parts of the following ethylenically unsaturated monomer (b-5) (yield 82%) as a pale yellow transparent liquid. Identification of the obtained Compounds by ¹ H-NMR was performed.

[ Synthesis of ethylenically unsaturated monomer (b-9) ]

6.6 parts of the ethylenically unsaturated monomer (b-5) obtained in the synthesis of the ethylenically unsaturated monomer (b-5) and 5 parts of ion-exchanged water were charged into a reaction vessel comprising a stirrer and a thermometer, and after stirring at room temperature, 8 parts of a 35% aqueous hydrochloric acid solution was added dropwise. The completion of the reaction was confirmed by the amine number measurement, and 20 parts of an aqueous solution of an ethylenically unsaturated monomer (b-9) was obtained as a pale yellow transparent liquid. Identification of the obtained Compounds by ¹ H-NMR was performed.

[ chemical 32]

(production of resin-type dispersant solution (J-2))

17.7 parts of methyl methacrylate, 53.2 parts of n-butyl methacrylate and 13.2 parts of tetramethyl ethylenediamine are charged into a reaction vessel equipped with a gas introduction pipe, a condenser, a stirring blade and a thermometer, and nitrogen substitution is performed in the system by stirring at 50℃for 1 hour while flowing nitrogen. Next, 2.6 parts of bromoisobutyric acid ethyl ester, 5.6 parts of cuprous chloride, and 100 parts of PGMAc were charged, and the temperature was raised to 110 ℃ under a nitrogen stream to start the polymerization of the first block. After 4 hours of polymerization, the polymerization solution was sampled and measured for nonvolatile components, and it was confirmed that the polymerization conversion was 98% or more in terms of nonvolatile components.

Next, 20 parts of PGMAc, 21.2 parts of an ethylenically unsaturated monomer (b-5) as a second block monomer, and 27 parts (nonvolatile matter 38%) of an aqueous solution of the ethylenically unsaturated monomer (b-9) were charged into the reaction vessel, and the reaction was continued while stirring under a nitrogen atmosphere at 110 ℃. After 2 hours, the polymerization solution was sampled and measured for nonvolatile components, and the polymerization conversion of the second block was confirmed to be 98% or more by conversion from the nonvolatile components, and the polymerization was stopped by cooling the reaction solution to room temperature.

PGMAc was added to the previously synthesized block copolymer solution so that the nonvolatile content became 40 mass%. Thus, a resin type dispersant solution having an amine value of 50mgKOH/g, a quaternary ammonium salt value of 20mgKOH/g, a weight average molecular weight (Mw) of 9,800 and a nonvolatile content of 40 mass% per unit nonvolatile content was obtained.

Further, a liquid resin (H-4) equivalent to the nonvolatile content of the resin-type dispersant solution was added, and the PGMAc and water were distilled off by heating to 100 ℃ and reducing the pressure, thereby obtaining a resin-type dispersant solution (J-2) in which the nonvolatile content of the resin-type dispersant solution/liquid resin (H-4) =1/1.

Example 2-1

< manufacturing of masterbatch >

2 parts of the ultraviolet absorber 1 and 98 parts of the polyolefin resin (F-1) were fed from the same feed port into a twin-screw extruder (manufactured by Nippon Steel Co., ltd.) having a screw diameter of 30mm, melt-kneaded at 240℃and then cut into pellets by a pelletizer to prepare a master batch (K-1).

Film formation

10 parts of the obtained master batch (K-1) were mixed with 90 parts of the polyolefin resin (F-1) as a diluent resin, and melt-mixed at 180℃using a T-die forming machine (manufactured by Toyo Seiki Seisaku-Miao Co., ltd.) to form a film (X-1) having a thickness of 250. Mu.m.

Examples 2-2 to 2-30 and comparative examples 2-1 to 2-10

In the same manner as in example 2-1, films (X-2) to (X-30) and films (XX-1) to (XX-10) were formed with a thickness of 250 μm using the materials described in Table 3.

[ ultraviolet absorbability ]

The transmittance of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by shimadzu corporation) and evaluated for whether the following conditions were satisfied. AA. A, B is a level that is practically unproblematic.

[ evaluation criterion ]

AA: the light transmittance of the wavelength of 400nm to 420nm is less than 1% in the whole area: very good

A: the light transmittance at a wavelength of 400nm to 420nm is 1% or more and less than 5% in the entire region: good quality

B: the light transmittance at a wavelength of 400nm to 420nm is 5% or more and less than 10% in the entire region: practical field

C: the light transmittance at a wavelength of 400nm to 420nm is 10% or more over the entire region: cannot be practically used

Transparency (transparency)

The transparency of the obtained film was evaluated visually. The evaluation criteria are as follows. A. B is a practically unproblematic level.

[ evaluation criterion ]

A: no turbidity was seen at all: good quality

B: several cloudiness were seen: practical field

C: turbidity was evident: cannot be practically used

[ light fastness ]

For the obtained film, a xenon weather resistance tester (xenon weather meter) was used at 60W/m ² Is exposed for 1000 hours at a wavelength of 300nm to 400 nm. A. B is a practically unproblematic level.

[ evaluation criterion ]

A: the absorbance decrease rate of the maximum absorption wavelength is less than 10%: good quality

B: the absorbance reduction rate of the maximum absorption wavelength is 10% or more and less than 30%: practical field

C: the absorbance reduction rate of the maximum absorption wavelength is 30% or more: cannot be practically used

TABLE 3

Examples 2 to 31

< manufacturing of masterbatch >

2 parts of the ultraviolet absorber 1 and 98 parts of the polyester resin (G-1) were fed from the same feed port into a twin-screw extruder (manufactured by Nippon Steel Co., ltd.) having a screw diameter of 30mm, melt-kneaded at 240℃and then cut into pellets by a pelletizer to produce a master batch (K-31).

Film formation

10 parts of the obtained master batch (K-31) was mixed with 95 parts of the polyester resin (G-1) as a diluent resin, and melt-mixed at 180℃using a T-die forming machine (manufactured by Toyo Seiki Seisaku-Miao Co., ltd.) to form a film (X-21) having a thickness of 250. Mu.m.

Examples 2-32 to 2-60 and comparative examples 2-11 to 2-20

As in examples 2-21, films (X-32) to (X-60) and films (XX-11) to (XX-20) were molded with a thickness of 250 μm using the materials described in Table 4-1.

Examples 2 to 61

< manufacturing of liquid masterbatch >

A liquid master batch (K-61) was produced by kneading 10 parts of the ultraviolet absorber 1 with 90 parts of the liquid resin (H-1) by a roll.

Film formation

The obtained liquid master batch (K-61) was mixed in an amount of 0.5 part with respect to 99.5 parts of the thermoplastic resin (G-1) as a diluent resin, and the mixture was melt-mixed at a temperature of 300℃by using a T-die molding machine (manufactured by Toyo Seiki Seisaku-Sho Co., ltd.) to form a film (X-61) having a thickness of 250. Mu.m.

Examples 2-62 to 2-90

As in examples 2-61, films (X-62) to (X-90) having a thickness of 250 μm were formed using the materials described in Table 4-2.

Examples 2 to 91

< manufacturing of liquid masterbatch >

A liquid master batch (K-91) was produced by dispersing 10 parts of an ultraviolet absorber 1, 20 parts of a resin-type dispersing agent (J-1), and 70 parts of a liquid resin (H-1) by a bead mill.

Film formation

0.5 part of the obtained liquid master batch (K-91) was mixed with 99.5 parts of the thermoplastic resin (G-1) as a diluent resin, and the mixture was melt-mixed at a temperature of 300℃using a T-die molding machine (manufactured by Toyo Seiki Seisaku-ku-ji Co., ltd.), to thereby form a film (X-91) having a thickness of 250. Mu.m.

Examples 2-92 to 2-120

As in examples 2 to 91, films (X-92) to (X-120) having a thickness of 250 μm were formed using the materials described in Table 4-2.

Examples 2 to 121

Production of plasticizer dispersion

A plasticizer dispersion (K-121) was produced by bead-dispersing 10 parts of ultraviolet absorber 1 and 90 parts of plasticizer (I-1).

Film formation

2 parts of the obtained plasticizer dispersion (K-121) were mixed with 98 parts of a thermoplastic resin (G-1) as a diluent resin, and melt-mixed at a temperature of 280℃using a T-die forming machine (manufactured by Toyo Seiki Seisaku-Miao Co., ltd.) to form a T-die film (X-121) having a thickness of 250. Mu.m.

Examples 2-122 to 2-150

As in examples 2 to 121, films (X-122) to (X-150) having a thickness of 250 μm were formed using the materials described in Table 4 to 3.

Examples 2 to 151

Production of plasticizer dispersion

A plasticizer dispersion (K-151) was produced by dispersing 10 parts of an ultraviolet absorber 1, 20 parts of a resin type dispersant (J-1), and 70 parts of a plasticizer (I-1) by a bead mill.

Film formation

The obtained plasticizer dispersion (K-151) was mixed in an amount of 0.5 parts with respect to 99.5 parts of the thermoplastic resin (G-1) as a diluent resin, and the mixture was melt-mixed at a temperature of 280℃by using a T-die forming machine (manufactured by Toyo Seiki Seisaku-Sho-K.K.), to thereby form a film (X-151) having a thickness of 250. Mu.m.

Examples 2 to 152 to 2 to 180

As in examples 2 to 151, films (X-152) to (X-180) having a thickness of 250 μm were formed using the materials described in Table 4 to 3.

[ Table 4-1]

[ Table 4-2]

/>

[ ultraviolet absorbability ]

[ evaluation criterion ]

Transparency (transparency)

[ evaluation criterion ]

A: no turbidity was seen at all: good quality

B: several cloudiness were seen: practical field

C: turbidity was evident: cannot be practically used

< haze value >)

The haze value of the obtained film was measured by a haze meter, and evaluated based on the following criteria. AAA, AA, A, B is a level that is practically unproblematic.

[ evaluation criterion ]

AAA: less than 0.2: extremely good

AA:0.2 or more and less than 0.5: very good

A:0.5 or more and less than 2: good quality

B:2 or more and less than 5: good quality

C:5 or more: cannot be practically used

[ light fastness ]

For the obtained film, a xenon weather resistance tester was used at 60W/m ² Is exposed for 1000 hours at a wavelength of 300nm to 400 nm. A. B is a practically unproblematic level.

[ evaluation criterion ]

[ tables 4 to 4]

[ tables 4 to 5]

As shown in tables 4 to 4 and 4 to 5, the molded articles according to the embodiments of the present invention have high ultraviolet absorptivity per unit weight and high light resistance in the visible light short wavelength region of 400nm to 420 nm. In addition, it is found that the film has high transparency and low haze because the film is practically used by adding a small amount.

Example 3-1

< manufacturing of masterbatch >

2 parts of the ultraviolet absorber 1 and 98 parts of the thermoplastic resin (G-1) were fed from the same feed port into a twin-screw extruder (manufactured by Nippon Steel Co., ltd.) having a screw diameter of 30mm, melt-kneaded at 300℃and then cut into pellets by a pelletizer to produce a master batch (K-31).

Film formation

10 parts of the obtained master batch (K-31) was mixed with 90 parts of the thermoplastic resin (G-1) as a diluent resin, and melt-mixed at a temperature of 300℃using a T-die forming machine (manufactured by Toyo Seiki Seisaku-Miao). Then, the mixture was left at 300℃for 20 minutes. Thereafter, a film (Y-1) having a thickness of 250 μm was formed.

Examples 3-2 to 3-150 and comparative examples 3-1 to 3-10

As in example 3-1, films (Y-2) to (Y-150) and (YY-1) to (YY-10) were formed to have a thickness of 250 μm using the materials described in tables 4-1 to 4-3.

[ ultraviolet absorbability ]

[ evaluation criterion ]

[ Heat resistance ]

The obtained films (Y-1) to (Y-150) were compared with the films (X-31) to (X-180) and the films (XX-11) to (XX-20) obtained in examples (2-31) to (2-180) and comparative examples (2-11) to (2-20) for their differences in ultraviolet absorptivity, and evaluated. The evaluation criteria are as follows. A. B is a practically unproblematic level.

[ evaluation criterion ]

A: the difference in light transmittance at wavelengths of 400nm to 420nm is less than 1%: good quality

B: the difference in light transmittance at wavelengths of 400nm to 420nm is 1% or more and less than 5%: practical field

C: the difference in light transmittance at wavelengths of 400nm to 420nm is 5% or more: cannot be practically used

The raw materials and the blending ratios of examples 3-1 to 3-150 and comparative examples 3-1 to 3-10 are the same as those of examples 2-31 to 2-180 and comparative examples 2-11 to 2-20, respectively, and therefore, only the results are shown in Table 5-1 and Table 5-2.

[ Table 5-1]

[ Table 5-2]

As shown in tables 5-1 and 5-2, the molded articles using the ultraviolet absorber according to the embodiment of the present invention have a small rate of change in ultraviolet absorbability due to the residence time during melt mixing at the time of film molding. Therefore, it was confirmed that the heat resistance was good.

Example 4-1

< manufacture of ultraviolet region absorbing masterbatch >

1 part of ultraviolet absorber 3, 1 part of ultraviolet absorber C-1, and 98 parts of polyester resin (G-1) were fed from the same feed port into a twin-screw extruder (manufactured by Nippon Steel Co., ltd.) having a screw diameter of 30mm, melt-kneaded at 240℃and then cut into pellets using a pelletizer to produce a master batch (K-121).

Film formation

10 parts of the obtained master batch (K-121) was mixed with 90 parts of the polyester resin (G-1) as a diluent resin, and melt-mixed at 180℃using a T-die forming machine (manufactured by Toyo Seiki Seisaku-Miao Co., ltd.) to form a film (Z-1) having a thickness of 250. Mu.m.

Examples 4-2 to 4-3

As in example 4-1, films (Z-2) to (Z-3) having a thickness of 250 μm were formed using the materials shown in Table 6-1.

[ spectroscopic Property ]

The transmittance of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by shimadzu corporation) and evaluated for whether the following conditions were satisfied. A. B is a practically unproblematic level.

[ evaluation criterion ]

A: the light transmittance of the wavelength of 400nm to 420nm is less than 1% in the whole area: very good

B: the light transmittance at a wavelength of 400nm to 420nm is 1% or more and less than 5% in the entire region: good quality

C: the light transmittance at wavelengths of 400nm to 420nm is 5% or more over the entire region: cannot be practically used

[ light fastness ]

[ evaluation criterion ]

[ Heat resistance ]

The heat resistance was evaluated by the same method as in example 3. The evaluation criteria are as follows. A. B is a practically unproblematic level.

[ evaluation criterion ]

Transparency (transparency)

[ evaluation criterion ]

A: no turbidity was seen at all: good quality

B: several cloudiness were seen: practical field

C: turbidity was evident: cannot be practically used

Examples 4 to 4

< manufacture of ultraviolet-visible region absorbing masterbatch >

1 part of an ultraviolet absorber 3, 1 part of a color material D-1, 1 part of a color material D-2, 1 part of a color material D-3, and 96 parts of a polyester resin (G-1) were fed from the same feed port into a twin-screw extruder (manufactured by Nippon Steel Co., ltd.) having a screw diameter of 30mm, melt-kneaded at 240℃and then cut into pellets using a pelletizer to produce a master batch (K-124).

Film formation

10 parts of the obtained master batch (K-124) was mixed with 90 parts of the polyester resin (G-1) as a diluent resin, and melt-mixed at 180℃using a T-die forming machine (manufactured by Toyo Seiki Seisaku-Miao Co., ltd.) to form a film (Z-4) having a thickness of 250. Mu.m.

Examples 4-5 to 4-6

As in example 4-4, films (Z-5) to (Z-6) having a thickness of 250 μm were formed using the materials shown in Table 6-1.

[ spectroscopic Property ]

[ evaluation criterion ]

A: the light transmittance of the wavelength of 400 nm-650 nm is less than 1% in the whole area: good quality

B: the light transmittance at a wavelength of 400nm to 650nm is 1% or more and less than 5% in the entire region: practical field

C: the light transmittance at a wavelength of 400nm to 650nm is 5% or more over the entire region: cannot be practically used

The light resistance and heat resistance were evaluated in the same manner as in example 4-1.

Examples 4 to 7

< manufacture of UV-near infrared region masterbatch >

1 part of an ultraviolet absorber 3, 1 part of a near infrared absorbing pigment E-1, and 98 parts of a polyester resin (G-1) were fed from the same feed port into a twin-screw extruder (manufactured by Nippon Steel Co., ltd.) having a screw diameter of 30mm, melt-kneaded at 240℃and then cut into pellets by a pelletizer to produce a master batch (K-127).

Film formation

10 parts of the obtained master batch (K-127) was mixed with 90 parts of the polyester resin (G-1) as a diluent resin, and melt-mixed at 180℃using a T-die forming machine (manufactured by Toyo Seiki Seisaku-Miao Co., ltd.) to form a film (Z-7) having a thickness of 250. Mu.m.

Examples 4-8 to 4-11

As in examples 4 to 7, films (Z-8) to (Z-11) having a thickness of 250 μm were formed using the materials shown in Table 6-1.

[ spectroscopic Property ]

[ evaluation criterion ]

A: the light transmittance of the light with the wavelength of 400nm to 420nm and the wavelength of 700nm to 800nm is less than 1% in the whole area: good quality

B: the light transmittance of the light having a wavelength of 400-420 nm and a wavelength of 700-800 nm is 1% or more and less than 5% in the whole region: practical field

C: the light transmittance of the light having a wavelength of 400nm to 420nm and a wavelength of 700nm to 800nm is 5% or more in the entire region: cannot be practically used

Examples 4 to 12

< manufacture of UV-near infrared absorbing masterbatch >

1 part of ultraviolet absorber 3, 1 part of ultraviolet absorber C-1, 1 part of near infrared absorbing pigment E-1, and 97 parts of polyester resin (G-1) were fed from the same feed port into a twin-screw extruder (manufactured by Nippon Steel Co., ltd.) having a screw diameter of 30mm, melt-kneaded at 240℃and then cut into pellets using a pelletizer to produce a master batch (K-132).

Film formation

10 parts of the obtained master batch (K-132) was mixed with 90 parts of the polyester resin (G-1) as a diluent resin, and melt-mixed at 180℃using a T-die forming machine (manufactured by Toyo Seiki Seisaku-Miao Co., ltd.) to form a film (Z-12) having a thickness of 250. Mu.m.

Examples 4-13 to 4-16

As in examples 4 to 12, films (Z-13) to (Z-16) having a thickness of 250 μm were formed using the materials described in Table 6-1.

[ spectroscopic Property ]

[ evaluation criterion ]

A: the light transmittance of the light with the wavelength of 300nm to 420nm and the wavelength of 700nm to 800nm is less than 1% in the whole area: good quality

B: the light transmittance of the light having a wavelength of 300nm to 420nm and a wavelength of 700nm to 800nm is 1% or more and less than 5% in the whole region: practical field

C: the light transmittance of the light having a wavelength of 300nm to 420nm and a wavelength of 700nm to 800nm is 5% or more in the entire region: cannot be practically used

The light resistance and heat resistance were evaluated in the same manner as in example 4-1. The results are shown in Table 6-2.

[ Table 6-1]

[ Table 6-2]

TABLE 6-2	Spectral characteristics	Light resistance	Heat resistance	Transparency of
					Example 4-1	A	A	A	A
Example 4-2	A	A	A	A
					Examples 4 to 3	A	A	A	A
Examples4-4	A	A	A	A
					Examples 4 to 5	A	A	A	A
Examples 4 to 6	A	A	A	A
					Examples 4 to 7	A	A	A	A
Examples 4 to 8	A	A	A	A
					Examples 4 to 9	A	A	A	A
Examples 4 to 10	A	A	A	A
					Examples 4 to 11	A	A	A	A
Examples 4 to 12	A	A	A	A
					Examples 4 to 13	A	A	A	A
Examples 4 to 14	A	A	A	A
					Examples 4 to 15	A	A	A	A
Examples 4 to 16	A	A	A	A

Coating material

Example 5-1

The following compositions were mixed with stirring to prepare a paint.

1.5 parts of ultraviolet absorber

9.5 parts of polyester (manufactured by Bayer process (Vylon) GK 250)

Methyl ethyl ketone 90.0 parts

Examples 5-2 to 5-20 and comparative examples 5-1 to 5-10

As shown in Table 7, the coatings of examples 5-2 to 5-30 and comparative examples 5-1 to 5-10 were obtained in the same manner as in example 5-1.

< formation of coating film >

The obtained paint was applied to a glass substrate having a thickness of 1000 μm using a bar coater so that the thickness of the paint became 10 μm by dry film thickness, and dried at 100℃for 2 minutes to form a coating film.

(evaluation of coating film)

The obtained coating film was evaluated by the following method.

[ ultraviolet absorbability ]

The transmittance of the obtained coating was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by shimadzu corporation) and evaluated for whether the following conditions were satisfied. AA. A, B is a level that is practically unproblematic.

[ evaluation criterion ]

[ light fastness ]

For the obtained coating, a xenon weather resistance tester was used at 60W/m ² Is exposed for 1000 hours at a wavelength of 300nm to 400 nm. A. B is a practically unproblematic level.

[ evaluation criterion ]

Transparency (transparency)

The transparency of the obtained coating was evaluated visually. The evaluation criteria are as follows. A. B is a practically unproblematic level.

[ evaluation criterion ]

A: no turbidity was visible at all. Good quality

B: several clouding was seen. Practical field

C: the turbidity was clearly seen. Cannot be practically used

TABLE 7

As shown in table 7, the coating film using the ultraviolet absorber according to the embodiment of the present invention has high ultraviolet absorptivity in the visible light short wavelength region of 400nm to 420nm and high light resistance. It is found that the addition of a small amount of the coating composition brings about a practical field, and therefore the transparency of the coated article is not impaired.

Photocurable composition

Example 6-1

The raw materials were stirred and mixed in accordance with the following compositions to prepare photocurable compositions.

1.0 part of ultraviolet absorber

Photopolymerizable compound (multifunctional acrylate "Kayarad (Kayarad) DPHA", manufactured by Japanese chemical Co., ltd.)

18.0 parts

Photopolymerization initiator (made of IGM resin (IGM ResinBV) 'Omnirad' 184

Propylene glycol monomethyl ether 80.0 parts

Examples 6-2 to 6-30 and comparative examples 6-1 to 6-10

As shown in Table 8, photo-curable compositions of examples 6-2 to 6-30 and comparative examples 6-1 to 6-10 were obtained in the same manner as in example 6-1.

(formation of coating film)

The photocurable composition was applied to a glass substrate having a thickness of 1mm using a bar coater so that the dry film thickness became 6. Mu.m. The obtained coating layer was dried at 100℃for 1 minute, and then irradiated with 400mJ/cm by a high-pressure mercury lamp ² And hardening the ultraviolet rays of (a) to form a coating.

(evaluation of coating film)

The obtained coating film was evaluated by the following method.

[ ultraviolet absorbability ]

[ evaluation criterion ]

[ light fastness ]

For the obtained coating, a xenon weather resistance tester was used at 60W/m ² Is exposed for 1000 hours at a wavelength of 300nm to 400 nm. A.B is a practically unproblematic level.

[ evaluation criterion ]

Transparency (transparency)

[ evaluation criterion ]

A: no turbidity was visible at all. Good quality

B: several clouding was seen. Practical field

C: the turbidity was clearly seen. Cannot be practically used

[ scratch resistance ]

The coated article was set on a vibration tester and vibrated 10 times under a load of 250g using steel wool. The coating material taken out was visually evaluated in the following five stages to determine the adhesion of flaws. The larger the number, the better the scratch resistance of the cured film.

[ evaluation criterion ]

5: no flaws at all.

4: a flaw was slightly attached.

3: although a flaw was attached, the substrate was not visible.

2: a flaw was attached, and a part of the cured film was peeled off.

1: the hardened film is peeled off, and the substrate is exposed.

TABLE 8

As shown in table 8, the coating film using the ultraviolet absorber according to the embodiment of the present invention has high ultraviolet absorptivity in the visible light short wavelength region of 400nm to 420nm and high light resistance. It is found that the addition of a small amount of the coating composition brings about a practical field, and therefore the transparency of the coated article is not impaired. In addition, it was found that the scratch resistance was excellent.

< adhesive >

(production example of adhesive resin (L-1))

Using a reaction apparatus comprising a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer and a dropping tube, 96.0 parts of n-butyl acrylate, 4.0 parts of 2-hydroxyethyl acrylate, 50% of the total amount, 0.2 parts of 2,2' -azobisisobutyronitrile as a polymerization initiator, 150 parts of ethyl acetate as a solvent were charged into a reaction vessel under a nitrogen atmosphere, and the remaining 50% of the total amount and a proper amount of ethyl acetate were charged into a dropping vessel. After the start of the reaction in the reaction vessel, the contents of the dropping tube and 0.01 part of ethyl acetate diluent of 2,2' -azobisisobutyronitrile were added dropwise under reflux. After the completion of the dropwise addition, the reaction was directly carried out for 5 hours while maintaining the reflux state. After the completion of the reaction, the mixture was cooled and an appropriate amount of ethyl acetate was added to obtain an adhesive resin (L-1) as an acrylic resin. The adhesive resin (L-1) thus obtained had a weight average molecular weight of 50 ten thousand, a nonvolatile content of 40%, and a viscosity of 3,200 mPa.s.

(production example of adhesive resin (L-2))

Using a reaction apparatus comprising a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube, 96.0 parts of n-butyl acrylate, 50% of the total amount of 4.0 parts of acrylic acid, 0.2 parts of 2,2' -azobisisobutyronitrile as a polymerization initiator, and 150 parts of ethyl acetate as a solvent were charged into a reaction vessel under a nitrogen atmosphere, and the remaining 50% of the total amount and a proper amount of ethyl acetate were charged into the dropping vessel. After the start of the reaction in the reaction vessel, the contents of the dropping tube and 0.01 part of ethyl acetate diluent of 2,2' -azobisisobutyronitrile were added dropwise under reflux. After the completion of the dropwise addition, the reaction was directly carried out for 5 hours while maintaining the reflux state. After the completion of the reaction, the mixture was cooled and an appropriate amount of ethyl acetate was added to obtain an adhesive resin (L-2) as an acrylic resin. The weight average molecular weight of the obtained adhesive resin (L-2) was 60 ten thousand, the nonvolatile content was 40%, and the viscosity was 4,000 mPa.s.

Example 7-1

As the adhesive resin, 1.0 part of an ultraviolet absorber 1 was mixed with 100 parts of a nonvolatile component of the adhesive resin (L-1), 0.1 part of KBM-403 (manufactured by Xinyue chemical industry Co., ltd.) as a silane coupling agent, and 0.4 part of trimethylolpropane adduct of toluene diisocyanate (abbreviated as TDI-TMP (tolylene diisocyanate-trimethylol propane), NCO value=13.2, nonvolatile component=75%) as a curing agent were added, and the mixture was sufficiently stirred to obtain an adhesive. Thereafter, the adhesive was applied to a release film of a polyethylene terephthalate substrate having a thickness of 38 μm so that the thickness thereof became 50 μm after drying, and dried for 2 minutes by a hot air oven at 100 ℃. Then, a 25 μm polyethylene terephthalate film was attached to the adhesive layer side, and aged at room temperature for 7 days in this state, thereby obtaining an adhesive sheet.

Examples 7-2 to 7-30 and comparative examples 7-1 to 7-10

As shown in Table 9, adhesive sheets of examples 7-2 to 7-30 and comparative examples 7-1 to 7-10 were obtained in the same manner as in example 7-1.

(evaluation of adhesive sheet)

[ adhesion ]

The obtained adhesive sheet was prepared in a size of 25mm wide and 150mm long. The adhesive layer exposed by peeling the release film from the adhesive sheet was attached to a glass plate at 23℃under a relative humidity of 50%, and was repeatedly pressed by a 2kg roller. After leaving for 24 hours, the adhesion was measured in a 180℃tear test in which the film was peeled off at a speed of 300mm/min in a 180℃direction using a tensile tester, and evaluated based on the following evaluation criteria (according to JIS Z0237: 2000). A is a practically unproblematic level.

[ evaluation criterion ]

A: the adhesive force is more than 10N, and the adhesive force is good.

C: the adhesion is less than 10N, which is not practical.

[ holding force ]

The obtained adhesive sheet was prepared in a size of 25mm wide and 150mm long. According to JIS Z0237:2000 the releasable sheet was peeled off from the adhesive sheet and polished, and an adhesive layer was attached to a portion of a polished stainless steel plate having a width of 30mm and a longitudinal length of 150mm and a width of 25mm and a transverse length of 25mm, and the sheet was repeatedly pressed and bonded once by a 2kg roller, and then a load of 1kg was applied to the sheet at 40℃for 7 ten thousand seconds, whereby the holding force was measured. For evaluation, the length of the downward offset of the upper end portion of the adhesive sheet attaching surface was measured. A is a practically unproblematic level.

[ evaluation criterion ]

A: the offset length of the adhesive sheet is less than 0.5mm. Good.

C: the offset length of the adhesive sheet is 0.5mm or more. And is impractical.

[ ultraviolet absorbability ]

The transmittance of the obtained adhesive sheet was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by shimadzu corporation), and whether or not the following conditions were satisfied was evaluated. AA. A, B is a level that is practically unproblematic.

[ evaluation criterion ]

[ light fastness ]

For the obtained adhesive sheet, a xenon weather-proof tester was used at 60W/m ² Is exposed for 1000 hours at an illuminance (300 nm to 400 nm). A. B is a practically unproblematic level.

[ evaluation criterion ]

Transparency (transparency)

The transparency of the obtained adhesive sheet was evaluated visually. The evaluation criteria are as follows. A. B is a practically unproblematic level.

[ evaluation criterion ]

A: no turbidity was visible at all. Good quality

B: several clouding was seen. Practical field

C: the turbidity was clearly seen. Cannot be practically used

TABLE 9

As shown in table 9, the coating film using the ultraviolet absorber according to the embodiment of the present invention has high ultraviolet absorptivity in the visible light short wavelength region of 400nm to 420nm and high light resistance. It is found that the addition of a small amount of the adhesive agent brings about a practical field, and therefore the transparency of the adhesive sheet is not impaired. In addition, it is known that the adhesive force and the holding force are good.

Claims

1. An ultraviolet absorber comprising: one or more ultraviolet absorbing pigments selected from the group consisting of compounds represented by the following general formulae (1) to (3); and a metal component containing at least one metal atom selected from the group consisting of Na, mg, al, K, ca and Fe, wherein the content of the metal component in the ultraviolet absorber is 0.1ppm to 50000ppm relative to the ultraviolet absorber,

[ chemical 1]

General formula (3)

(in the general formulae (1) to (3), R ₁ b～R _1g 、R ₂ a～R _2g And R is ₃ a～R _3g Independently represent a group selected from the group consisting of a hydrogen atom, a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a sulfo group, and R ₇ 、Ar ₁ And any one of the groups represented by the following general formulae (4-1) to (4-3);

R ₇ represents any one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkenyloxy group having 1 to 20 carbon atoms, and may have a substituent of a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a carboxyl group, or a sulfo group, alkyl group having 1 to 20 carbon atoms, alkenyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms and alkenyloxy having 1 to 20 carbon atoms may be bonded to each other through one or more groups selected from the group consisting of-O-, -CO-, -COO-, -OCO-, -CONH-, or-NHCO-;

Ar ₁ A substituent which is selected from the group consisting of an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a biphenyl group, and which may have a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitrile group, a nitro group, a carboxyl group, or a sulfo group;

in the general formulae (2) to (3), R ₄ 、R ₅ 、R ₆ Are respectively and independently selected from hydroxyl, R ₇ Ar, ar ₁ Any one of the group consisting of;

[ chemical 2]

General formula (4-1)

＊——X ₁ ——R ₈

In the general formula (4-1), X ₁ Represents a member selected from the group consisting of-CO-COO-, -OCO-, -CONH-, and-NHCO-, R ₈ Represents a group selected from the group consisting of hydrogen atoms, hydroxyl groups, R ₇ Ar, ar ₁ Any one of the group consisting of; wherein, in the general formula (4-1), the bonding part of the naphthalene ring in the general formula (1) to the general formula (3) is represented;

[ chemical 3]

General formula (4-2)

*——X ₂ ——R ₉ ——X ₃ ——R ₁₀

In the general formula (4-2), X ₂ 、X ₃ Each independently represents a member selected from the group consisting of-CO-; -COO-, -OCO-, any one of the group consisting of-CONH-, and-NHCO-, R is R ₉ R represents an arylene group having 6 to 20 carbon atoms ₁₀ R represents ₇ Or Ar ₁ The method comprises the steps of carrying out a first treatment on the surface of the Wherein, in the general formula (4-2), the bonding part with the naphthalene ring of the general formula (1) to the general formula (3);

[ chemical 4]

General formula (4-3)

In the general formula (4-3), X ₄ 、X ₅ Each independently represents a member selected from the group consisting of-CO-; -COO-, -OCO-, any one of the group consisting of-CONH-, and-NHCO-, R is R ₁₁ Represents a linear or branched alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, R ₁₂ R represents ₇ Or Ar ₁ N is 1-20; wherein, in the general formula (4-3), the bonding site with naphthalene ring of the general formula (1) to the general formula (3) is represented.

2. The ultraviolet absorber according to claim 1 wherein said ultraviolet absorbing pigment comprises one or more compounds selected from the group consisting of compounds represented by the following formulas,

[ chemical 5 ]]

3. The ultraviolet absorber according to claim 1 or 2, wherein the metal component comprises Al.

4. A composition comprising: a uv absorber as claimed in any one of claims 1 to 3; and at least one second ultraviolet absorber selected from the group consisting of triazine ring-containing compounds, benzotriazole ring-containing compounds, and benzophenone ring-containing compounds, which are compounds other than the compounds represented by the general formulae (1) to (3).

5. A composition comprising the ultraviolet absorber according to any one of claims 1 to 3, and a color material for blocking light having a wavelength in the visible wavelength range of 450nm to 650 nm.

6. The composition of claim 5, wherein the color material comprises two or more chromatic colorants.

7. A composition comprising: a uv absorber as claimed in any one of claims 1 to 3; and at least one near infrared ray absorber selected from the group consisting of phthalocyanine compounds, naphthalocyanine compounds, squarylium compounds, cyanine compounds, and diketopyrrolopyrroles,

the near infrared ray absorber has a great absorption in a wavelength region of 600nm to 1500 nm.

8. A composition comprising the ultraviolet absorber of any one of claims 1 to 3, and a resin.

9. The composition of claim 8, wherein the resin comprises a thermoplastic resin.

10. A composition comprising the ultraviolet absorber according to any one of claims 1 to 3, a photopolymerizable compound, and a photopolymerization initiator.

11. A shaped body formed from the composition of any one of claims 4 to 10.

12. A coating film formed from the composition of any one of claims 4 to 10.

13. The method for producing an ultraviolet absorber according to any one of claims 1 to 3, wherein the content of the metal component contained in the ultraviolet absorbing dye is adjusted by performing at least one step selected from the group consisting of:

Adding a poor solvent containing water to the ultraviolet-absorbing pigment synthesis reaction solution to separate the solution, and removing metal components; a step of washing the ultraviolet absorbing pigment with alcohol or water or a mixture thereof after the separation and filtration; a step of reslurrying the ultraviolet-absorbing pigment in alcohol, water, or a mixture thereof, and washing the resultant; and a step of reslurrying the ultraviolet-absorbing dye with an acid solution and cleaning the resultant.