WO2012124395A1 - Composition for ultraviolet absorbing material and ultraviolet absorbing material using same - Google Patents

Abstract

The present invention, seeking to resolve problems associated with the prior art, provides a composition for an ultraviolet absorbing material, as well as an ultraviolet absorbing material produced using the same, whereby superior light resistance can be maintained over a long duration of time and ultraviolet rays in the range of 380-400 nm, which conventionally have been difficult to block, can be adequately blocked even while a high degree of transmittance for visible light is maintained, and whereby coloration is reduced. More specifically, the present invention provides a composition for an ultraviolet absorbing material, the composition comprising at least one type of metal complex represented by formula (1) and at least one type of silane coupling agent having one or more functional groups selected from the group consisting of a thiol group, an amino group, a ureido group, and an isocyanate group. The present invention further provides an ultraviolet absorbing material produced using the composition.

Description

Composition for ultraviolet absorbing member and ultraviolet absorbing member using the same

The present invention includes at least one metal complex represented by the formula (1) and at least one functional group selected from the group consisting of a thiol group, an amino group, a ureido group, and an isocyanate group. The present invention relates to an ultraviolet absorbing member composition containing a silane coupling agent, and an ultraviolet absorbing member produced using the composition.

In recent years, members having a function of sufficiently transmitting visible light and simultaneously selectively blocking only ultraviolet light have been used in various fields. For example, in a window glass of an automobile, a window glass of a building, etc., an ultraviolet shielding glass is widely used for shielding ultraviolet rays that cause sunburn and deterioration of interior materials.

Also, in applications such as transparent resin plates used in carports, show windows, showcases, transparent shades for lighting, and various transparent containers, acrylic resins, polycarbonate resins, polyester resins, etc. that have been provided with an ultraviolet shielding function A molded body of a transparent thermoplastic resin is used.

As described above, in order to impart an ultraviolet shielding function to glass, resin, or the like, a method using inorganic metal oxide fine particles or an organic ultraviolet absorber as an ultraviolet absorber is generally used (Patent Documents 1 to 6). 4).

Although inorganic oxide fine particles are excellent in light resistance, the absorption wavelength is governed by the band gap inherent to the material, so it is difficult to optimize the absorption wavelength. Further, the absorption spectrum is broad in many cases, and there is a limit in selectively blocking only a desired wavelength region. Furthermore, since it cannot be dissolved in a solvent or the like, it is usually used in a fine particle dispersed state. However, in order to ensure transparency in the visible light region, it is necessary to reduce the particle diameter to the nano order, which requires a great deal of labor and cost. Cost.

On the other hand, the organic ultraviolet absorber can change the absorption wavelength to some extent by changing the molecular structure, and can be used by being dissolved in a solvent, so that transparency in the visible light region can be secured relatively easily. . However, in most cases, the light resistance is insufficient, and the reliability is insufficient in terms of the sustainability of the ultraviolet absorbing ability. In addition, since the extinction coefficient is small, it is difficult to obtain a sufficient absorption capacity by coating, and there are limitations on applicable applications.

In addition, for both inorganic oxide fine particles and organic ultraviolet absorbers, few materials are known that selectively absorb ultraviolet rays in the wavelength region of 380 to 400 nm and have a large extinction coefficient.

Here, ultraviolet rays with a wavelength of 380 to 400 nm are classified as ultraviolet rays having a relatively long wavelength called UV-A, and are the most abundant as ultraviolet rays of sunlight reaching the ground surface. Due to the depth, long exposure is known to cause pigmentation and wrinkles. Along with higher functionality in various fields, a material that can sufficiently shield ultraviolet rays of 380 to 400 nm in the vicinity of the boundary with the visible light region and sufficiently transmits visible light of 400 to 780 nm is desired.

JP 2006-052116 A JP 2010-1111729 A JP 2010-189215 A JP 2008-274246 A

The present invention is intended to solve the problems associated with the prior art as described above, and it has been difficult to shield while maintaining excellent light resistance for a long period of time and maintaining a high visible light transmittance. An object of the present invention is to provide a composition for an ultraviolet absorbing member that can sufficiently shield the ultraviolet rays in the range of 380 to 400 nm and has reduced coloring, and an ultraviolet absorbing member produced using the composition.

The present invention relates to a composition for an ultraviolet absorbing member as shown below and an ultraviolet absorbing member using the same.
Item 1. Formula (1):

Wherein Y ¹ , Y ² , Y ³ and Y ⁴ are each independently NH, NR ⁵ , an oxygen atom or a sulfur atom,
R ⁵ of NR ⁵ belonging to Y ¹ , Y ² , Y ³ or Y ⁴ is an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms which may have a substituent. ^{Incidentally,} Y ^1, Y 2, when ^{Y 3} and at least two of ^{Y 4} is represented by NR ^5, the ^{R 5} of NR ⁵ represent a substituent independent of each other, respectively.
Z ¹ and Z ² are each independently a nitrogen atom, CH or CR ⁶ ;
R ⁶ of CR ⁶ assigned to Z ¹ or Z ² is an optionally substituted alkyl group having 1 to 8 carbon atoms or optionally substituted aryl having 6 to 15 carbon atoms. And a heteroaryl group having 4 to 12 carbon atoms which may have a substituent, a heteroaralkyl group having 5 to 12 carbon atoms or an aralkyl group having 7 to 15 carbon atoms which may have a substituent. . Incidentally, a substituent case, ^{R 6} of CR ⁶ is that each independently of one another ^{that Z 1} and ^{Z 2} are both represented by CR ^6.
Each of R ¹ , R ² , R ³ and R ⁴ is absent or, if present, represents two carbon atoms shared with a 5-membered ring of the six carbon atoms of one benzene ring. 1 to 4 of the 4 hydrogen atoms bonded to the removed 4 carbon atoms can be substituted, and all of the substituents substituted with 4 hydrogen atoms of the benzene ring are independent of each other. An optionally substituted alkyl group having 1 to 8 carbon atoms, hydroxyl group, carboxyl group, alkoxy group having 1 to 4 carbon atoms, halogeno group, and optionally having 1 to 8 carbon atoms An alkylaminosulfonyl group, a morpholinosulfonyl group which may have a substituent, a piperidinosulfonyl group which may have a substituent, a pyrrolidinosulfonyl group which may have a substituent, a substituent You may have A morpholinosulfonyl group, or may have a substituent group piperazino sulfonyl group,
M represents a metal atom. )
At least one metal complex represented by:
A composition for an ultraviolet absorbing member, comprising at least one silane coupling agent having at least one functional group selected from the group consisting of a thiol group, an amino group, a ureido group, and an isocyanate group.

Item 2. Item 2. The composition for an ultraviolet absorbing member according to Item 1, wherein the metal atom M in the formula (1) is a cobalt atom, a nickel atom, or a copper atom.
Item 3. 3. An ultraviolet absorbing member produced using the ultraviolet absorbing member composition according to item 1 or 2.
Item 4. Item 4. The ultraviolet absorbing member according to item 3, wherein the composition for ultraviolet absorbing member is coated on an organic or inorganic base material.

The present invention includes at least one functional group selected from the group consisting of a metal complex represented by the formula (1) as an ultraviolet absorber and a thiol group, amino group, ureido group, and isocyanate group. The composition for ultraviolet absorption members characterized by containing the silane coupling agent of this.

The metal complex represented by the formula (1) exhibits very good solubility and / or dispersibility with respect to the silane coupling agent.
Further, by dissolving or dispersing the metal complex represented by the formula (1) in the silane coupling agent, the weak absorption in the visible light region specific to the metal complex represented by the formula (1) is shifted in wavelength or As a result, the visible light transmittance of the finally obtained ultraviolet absorbing member can be improved.

Further, the present invention provides an ultraviolet absorbing member produced by blending into a resin substrate and / or applying a coating film on a glass substrate or resin substrate using the composition for ultraviolet absorbing member. provide.

The metal complex represented by the formula (1) efficiently absorbs ultraviolet light in the range of 380 to 400 nm, which has been difficult to shield, and exhibits much better light resistance than a general organic ultraviolet absorber. . Further, a sufficient amount of ultraviolet absorbing ability can be imparted with a small amount of addition, and transparency in the visible light region is very excellent.

Further, the metal complex represented by the formula (1) is stabilized in a polysiloxane network formed using the silane coupling agent as a precursor, and exhibits excellent light resistance.

According to the present invention, excellent light resistance can be maintained for a long period of time, and visible light transmittance can be maintained at a high level, and UV light in the range of 380 to 400 nm, which has been difficult to shield conventionally, can be sufficiently shielded. And the composition for ultraviolet absorbers which reduced coloring and the ultraviolet absorber produced using this can be provided.

Hereinafter, the present invention will be described in detail.
The present invention relates to formula (1):

(In the formula, Y ¹ , Y ² , Y ³ and Y ⁴ are each independently NH, NR ⁵ , an oxygen atom or a sulfur atom, and belong to Y ¹ , Y ² , Y ³ or Y ^4. R ^{5 in} NR ⁵ is an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms, which may have a substituent, of Y ¹ , Y ² , Y ³ and Y ⁴ when at least two are represented by NR ^5, the ^{R 5} of NR ⁵ represent a substituent independent of each other, respectively. Further, ^{Z 1} and ^{Z 2} are each, independently of one another, a nitrogen atom, CH or CR ⁶ , R ⁶ of CR ⁶ belonging to Z ¹ or Z ² is an optionally substituted alkyl group having 1 to 8 carbon atoms, optionally having a substituent group having 6 to 15 carbon atoms. An aryl group or an optionally substituted hetero atom having 4 to 12 carbon atoms Lumpur group, a heteroaralkyl group or an aralkyl group having 7 to 15 carbon atoms to 12 carbon atoms 5 may have a substituent. In the case where Z ¹ and Z ² are both represented by CR ⁶ , R ⁶ of CR ⁶ each represents an independent substituent, and each of R ¹ , R ² , R ³ and R ⁴ is absent or, if present, 1 to 4 of 4 hydrogen atoms bonded to 4 carbon atoms except 2 carbon atoms shared with a 5-membered ring of carbon atoms can be substituted, and 4 benzene rings All of the substituents substituted with hydrogen atoms are independently of each other an optionally substituted alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 4 carbon atoms, Even if it has a halogeno group or a substituent An alkylaminosulfonyl group having 1 to 8 carbon atoms, a morpholinosulfonyl group which may have a substituent, a piperidinosulfonyl group which may have a substituent, and a pyrrole which may have a substituent A dinosulfonyl group, an optionally substituted thiomorpholinosulfonyl group or an optionally substituted piperazinosulfonyl group, and M represents a metal atom.)
At least one metal complex represented by:
Composition for ultraviolet absorbing member comprising at least one kind of silane coupling agent having at least one functional group selected from the group consisting of thiol group, amino group, ureido group and isocyanate group, and ultraviolet ray using the same An absorbent member is provided.

Further, Y ¹ , Y ² , Y ³ and Y ⁴ , Z ¹ and Z ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and M in Formula (1) are exemplified below.

In the formula, R ⁵ of the NR ⁵ attributed to Y ¹ , Y ² , Y ³ or Y ⁴ is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, alkyl groups such as sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl, n-heptyl group, n-octyl group, phenyl And aryl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-chlorophenyl group, 4-bromophenyl group, 3,4-dichlorophenyl group and naphthyl group.
^{Incidentally, Y 1, Y 2, Y} 3, when ^Y least two of the ^four is represented by NR ^5, the ^{R 5} of NR ⁵ represent a substituent independent of each other, respectively.

Here, Y ¹ , Y ² , Y ³ and Y ⁴ in Formula (1) are particularly preferably sulfur atoms from the viewpoint of simplicity of the synthesis method.

In the formula, R ⁶ of CR ⁶ attributed to Z ¹ or Z ² is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert group -Alkyl groups such as -butyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, n-octyl, phenyl, 2-methylphenyl Group, 3-methylphenyl group, 4-methylphenyl group, 3-chlorophenyl group, 4-bromophenyl group, 3,4-dichlorophenyl group, aryl group such as naphthyl group, 2-furyl group, 2-thienyl group, Such as 5-chloro-2-thienyl, 2-pyrrolyl, 2-oxazolyl, 5-methyl-2-oxazolyl, 2-thiazolyl, etc. A heteroaryl group such as a roaryl group, a 4-pyridylmethyl group, a 4-quinolylmethyl group, a 2-thienylmethyl group,

4-acetamidobenzyl group, 3-aminobenzyl group, 4-aminobenzyl group, 3-methoxybenzyl group, 2-methoxyphenethyl group, 4- (n-pentyloxy) benzyl group, 2-allyloxyphenethyl group, 5- Allyl-2-hydroxy-3-methoxybenzyl group, 4-phenylbenzyl group, 2-bromobenzyl group, 3-phenethyl group, 4-bromobenzyl group, 2-chlorobenzyl group, 3-chlorobenzyl group, 4-chloro Benzyl group, 6-bromo-2-hydroxybenzyl group, 5-bromo-3-nitro-2-hydroxyphenethyl group, 4- (n-butyl) benzyl group, 3-bromo-5-methoxy-4-hydroxybenzyl group 4-benzyloxybenzyl group, 6-bromo-3-methoxy-2-hydroxybenzyl group, (1-bromo-2 Naphthyl) -n-propyl group, 2-benzyloxybenzyl group, 3,5-bistrifluoromethylphenethyl group, 4-tert-butylbenzyl group, 5-bromo-2-fluorobenzyl group, 3-bromo-4-methoxy Benzyl group, 5-bromo-2-methoxybenzyl group, 3-bromo-5-chloro-2-hydroxybenzyl group, 4-bromo-2-fluorobenzyl group, 2-bromo-4,5-dimethoxyphenethyl group, 3 , 4-ethylenedioxybenzyl group, 3-bromo-4-fluorophenethyl group, 6-bromo-3,4-methylenedioxybenzyl group, 3-bromo-4-hydroxybenzyl group, 2-bromo-5-fluoro Phenethyl group, 4-cyanobenzyl group, 4-trifluorobenzyl group, 4- (4-chlorophenoxy) phenethyl group, 4- (N, N-diethylamino) benzyl group, 3,4-diacetoxybenzyl group, 4- (N, N-diphenylamino) benzyl group, 4- [N- (4,4-dioxothiomorpholino)] benzyl group, 4- (N-pyrrolidino) benzyl group, 3- (2-hydroxyethoxy) benzyl group, 4- (2-hydroxyethoxy) phenethyl group, 4-hydroxy-3,5-dimethylbenzyl group, (6-hydroxy-2-naphthyl) ) Aralkyl groups such as -n-propyl group, 4-isopropylbenzyl group, 4-isobutylbenzyl group.

Among those exemplified as R ⁶ of CR ⁶ attributed to Z ¹ or Z ² , an aralkyl group is particularly preferable from the viewpoint of simplicity of the synthesis method and reactivity.
Incidentally, a substituent case, ^{R 6} of CR ⁶ is that each independently of one another ^{that Z 1} and ^{Z 2} are both represented by CR ^6.

Furthermore, Z ¹ and Z ² in Formula (1) are particularly preferably nitrogen atoms from the viewpoint of simplicity of the synthesis method.

In the formula, examples of the alkyl group having 1 to 8 carbon atoms which may have the above-mentioned substituents belonging to R ¹ , R ² , R ³ or R ⁴ include, for example, methyl group, ethyl group, 2 -Methoxyethyl group, n-propyl group, isopropyl group, 3-chloro-n-propyl group, n-butyl group, sec-butyl group, tert-butyl group, 4-hydroxy-n-butyl group, n-pentyl group , Isopentyl group, neopentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl, 6-phenyl-n-hexyl group, n-heptyl group, n-octyl group and the like.

In the formula, examples of the alkoxy group having 1 to 4 carbon atoms belonging to R ¹ , R ² , R ³ or R ⁴ include a methoxy group, an ethoxy group, and a tert-butoxy group.

In the formula, examples of the halogeno group belonging to R ¹ , R ² , R ³ or R ⁴ include a fluoro group, a chloro group, a bromo group, and an iodo group.

In the formula, the alkylaminosulfonyl group having 1 to 8 carbon atoms which may have the above-mentioned substituents belonging to R ¹ , R ² , R ³ or R ⁴ includes, for example, N-methylaminosulfonyl Group, N-ethylaminosulfonyl group, N-isopropylaminosulfonyl group, Nn-propylaminosulfonyl group, Nn-butylaminosulfonyl group, N, N-dimethylaminosulfonyl group, N, N-methylethylamino Sulfonyl group, N, N-diethylaminosulfonyl group, N, N-ethylisopropylaminosulfonyl group, N, N-diisopropylaminosulfonyl group, N, N-di-n-propylaminosulfonyl group, N, N-di-n -Butylaminosulfonyl group, N, N-diisobutylaminosulfonyl group and the like can be mentioned.

In the formula, examples of the morpholinosulfonyl group optionally having a substituent belonging to R ¹ , R ² , R ³ or R ⁴ include morpholinosulfonyl group, 2-methylmorpholinosulfonyl group, 3-methyl Morpholinosulfonyl group, 2-ethylmorpholinosulfonyl group, 3-n-propylmorpholinosulfonyl group, 3-n-butylmorpholinosulfonyl group, 2,3-dimethylmorpholinosulfonyl group, 2,6-dimethylmorpholinosulfonyl group, 3-phenyl Examples thereof include a morpholinosulfonyl group.

In the formula, examples of the piperidinosulfonyl group optionally having a substituent belonging to R ¹ , R ² , R ³ or R ⁴ include a piperidinosulfonyl group, 2-methylpiperidino Sulfonyl group, 3-methylpiperidinosulfonyl group, 4-methylpiperidinosulfonyl group, 2-ethylpiperidinosulfonyl group, 4-n-propylpiperidinosulfonyl group, 3-n-butylpiperidinosulfonyl Group, 2,4-dimethylpiperidinosulfonyl group, 2,6-dimethylpiperidinosulfonyl group, 4-phenylpiperidinosulfonyl group and the like.

In the formula, examples of the pyrrolidinosulfonyl group optionally having a substituent belonging to R ¹ , R ² , R ³ or R ⁴ include a pyrrolidinosulfonyl group, a 2-methylpyrrolidinosulfonyl group, 3-methylpyrrolidinosulfonyl group, 2-ethylpyrrolidinosulfonyl group, 3-n-propylpyrrolidinosulfonyl group, 3-n-butylpyrrolidinosulfonyl group, 2,4-dimethylpyrrolidinosulfonyl group, 2,5- Examples thereof include a dimethylpyrrolidinosulfonyl group and a 3-phenylpyrrolidinosulfonyl group.

In the formula, examples of the optionally substituted thiomorpholinosulfonyl group belonging to R ¹ , R ² , R ³ or R ⁴ include a thiomorpholinosulfonyl group and a 2-methylthiomorpholinosulfonyl group. 3-methylthiomorpholinosulfonyl group, 2-ethylthiomorpholinosulfonyl group, 3-n-propylthiomorpholinosulfonyl group, 3-n-butylthiomorpholinosulfonyl group, 2,3-dimethylthiomorpholinosulfonyl group, 2,6- Examples thereof include a dimethylthiomorpholinosulfonyl group and a 3-phenylthiomorpholinosulfonyl group.

In the formula, examples of the piperazinosulfonyl group optionally having a substituent belonging to R ¹ , R ² , R ³ or R ⁴ include a piperazinosulfonyl group, 2-methylpiperazino Sulfonyl group, 3-methylpiperazinosulfonyl group, 2-ethylpiperazinosulfonyl group, 3-n-propylpiperazinosulfonyl group, 3-n-butylpiperazinosulfonyl group, 2,5-dimethylpiperazi Nosulfonyl group, 2,6-dimethylpiperazinosulfonyl group, 3-phenylpiperazinosulfonyl group, 2-pyrimidylpiperazinosulfonyl group and the like.

Each of R ¹ , R ² , R ³ and R ⁴ is absent or, if present, two carbons shared with a 5-membered ring of the six carbon atoms of one benzene ring. Substituent in which 1 to 4, preferably 1 or 2 of 4 hydrogen atoms bonded to 4 carbon atoms excluding atoms can be substituted, and hydrogen atoms of 4 benzene rings are substituted All independently have an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 4 carbon atoms, a halogeno group, and a substituent which may have a substituent. An alkylaminosulfonyl group having 1 to 8 carbon atoms, a morpholinosulfonyl group which may have a substituent, a piperidinosulfonyl group which may have a substituent, and a substituent. Pyrrolidinosulfonyl , A thiomorpholinosulfonyl group which may have a substituent or a piperazinosulfonyl group which may have a substituent, and is not present from the viewpoint of economy, that is, the availability of raw materials and the yield An optionally substituted alkyl group having 1 to 8 carbon atoms, a halogeno group, an alkoxy group having 1 to 4 carbon atoms, and an optionally substituted alkylaminosulfonyl group having 1 to 8 carbon atoms A morpholinosulfonyl group which may have a substituent, a piperidinosulfonyl group which may have a substituent, a pyrrolidinosulfonyl group which may have a substituent, and a substituent. It is preferably a thiomorpholinosulfonyl group or an optionally substituted piperazinosulfonyl group, which is absent, has a halogeno group, an alkoxy group having 1 to 4 carbon atoms, or has a substituent. Carbon atoms and optionally 1-8 alkylaminosulfonyl group, more preferably a good morpholinosulfonyl group which may have a substituent, and more preferably not present.
In addition to these, Y ¹ , Y ² , Y ³ and Y ⁴ , Z ¹ and Z ² , R ¹ , R ² , R ³ and R ⁴ are independent of each other. From the viewpoint of quality (purity) control of the metal complex to be obtained, it is particularly preferable that Y ¹ = Y ² and Y ³ = Y ⁴ and Z ¹ = Z ² and R ¹ = R ² = R ³ = R ^4. .

In the formula, examples of the metal atom represented by M include a cobalt atom, a nickel atom, or a copper atom. From the viewpoint of reducing coloration of the composition for an ultraviolet absorbing member comprising the metal complex and the silane coupling agent and the finally obtained ultraviolet absorbing member, a nickel atom is particularly preferable.

The metal complex represented by the formula (1) is obtained by reacting a ligand represented by the following formula (2) with a metal salt such as a metal halide, metal sulfate, metal acetate, or metal nitrate. Can be synthesized.
Formula (2):

In the formula (2), Y ¹ , Y ² , Z ¹ , R ¹ , R ² are Y ¹ (and / or Y ³ ), Y ² (and / or Y ⁴ ), Z in the formula (1), respectively. ¹ (and / or Z ² ), R ¹ (and / or R ³ ), R ² (and / or R ⁴ ).

Examples of the ligand represented by the formula (2) include “JP-A-56-87575”, “Synthesis 1987, 368”, “Synthesis 1982, 590”, “Synthesis 1982, 1066-1067”, “J. "Org. Chem. 2002, 67, 5753- 5772", "J. Org. Chem. 2002, 67, 5753- 5772", "J. Org. Chem. 1961, 26, 3434-3445", "Gazz. Chim. Ital. 1996, 126, 329-337, “Gazz. Chim. Ital. 1994, 124, 301-308”, and “Special Table 2007-535421”.
Hereinafter, a part of manufacturing method of the ligand represented by Formula (2) is demonstrated.

≪Ligand production method≫
i) In the following formula (3): in the formula (2), Y ¹ = Y ² = S, Z ¹ = N

For example, it can be synthesized according to the method described in JP-A-56-87575. That is, 2-aminobenzothiazole (when R ¹ and R ² are not present) or 2-amino-substituted benzothiazole (wherein R ¹ and R ² may have a substituent, an alkyl group having 1 to 8 carbon atoms) , Hydroxyl group, carboxyl group, alkoxy group having 1 to 4 carbon atoms or halogeno group) in the presence of an acid catalyst such as phenol, the mixture is heated to 150 to 185 ° C. and reacted to give 2,2′-iminobis Benzothiazole or 2,2′-iminobis (substituted benzothiazole) can be synthesized.

ii) In the case of Y ¹ = S, Y ² = O, and Z ¹ = N in the following formula (4):

For example, it can be synthesized according to the method described in Synthesis 1987,368. That is, 2-aminophenol (when R ² is not present) or 2-amino-substituted phenol (wherein R ² may have a substituent, an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, carbon (In the case of an alkoxy group or a halogeno group of 1 to 4) is dissolved in N, N′-dimethylformamide (DMF), an aqueous sodium hydroxide solution is added as a base, and the mixture is stirred at room temperature for 30 minutes. -Dimethyl-N- (2-benzothiazolyl) -carbonimidodithioate (if R ¹ is not present) or S, S'-dimethyl-N- [2- (substituted benzothiazolyl)]-carbonimidodithioate (where R ¹ is An optionally substituted alkyl group having 1 to 8 carbon atoms, hydroxyl group, carboxyl group, alkoxy group having 1 to 4 carbon atoms or halogeno 2- (2-benzothiazolylamino) benzoxazole or 2- [2- (substituted benzothiazolyl) amino] -substituted benzoxazole is synthesized by dropping a DMF solution in the case of a group and refluxing under a nitrogen atmosphere. be able to.

The S, S′-dimethyl-N- (2-benzothiazolyl) carbonimidodithioate or S, S′-dimethyl-N- [2- (substituted benzothiazolyl)] carbonimidodithioate is described in, for example, Synthesis 1982,590. Can be synthesized according to the methods described.

That is, 2-aminobenzothiazole (when R ¹ is not present) or 2-amino-substituted benzothiazole (wherein R ¹ may have a substituent, an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group) In the case of an alkoxy group having 1 to 4 carbon atoms or a halogeno group), an aqueous sodium hydroxide solution is added dropwise to this solution in a water bath or ice bath, carbon disulfide is then added dropwise, and water is added. An aqueous sodium oxide solution is added dropwise, followed by methyl iodide, so that S, S′-dimethyl-N- (2-benzothiazolyl) carbonimide dithioate (when R ¹ is not present) or S, S′-dimethyl is added. -N-(2-substituted-benzothiazolyl) dicarbonimide phosphorodithioate (alkyl group R ¹ is - carbon atoms 1 may have a substituent 8, hydroxy Group, a carboxyl group, can be synthesized when an alkoxy group or a halogeno group having 1 to 4 carbon atoms).

iii) In the following formula (5): in the formula (2), Y ¹ = S, Y ² = NH, Z ¹ = N

For example, it can be synthesized according to the method described in Synthesis 1982, 1066-1067. That is, o-phenylenediamine (when R ² is not present) or o- (substituted phenylene) diamine (wherein R ² may have a substituent, an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, C 1-4 alkoxy group or halogeno group) is dissolved in DMF, where S, S′-dimethyl-N- (2-benzothiazolyl) -carbonimidodithioate (if R ¹ is not present) or S, S′-dimethyl-N- [2- (substituted benzothiazolyl)]-carbonimidodithioate (wherein R ¹ may have a substituent, an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, After dropwise addition of a DMF solution of a C 1-4 alkoxy group or halogeno group), the mixture is refluxed for 10-16 hours to give 2- (2-benzothia Riruamino) benzimidazole or 2- [2- (substituted-benzothiazolyl amino)] can be synthesized substituted benzimidazol.

iv) In the case of Y ¹ = S, Y ² = NH, Z ¹ = CH in the following formula (6):

For example, J. et al. Org. Chem. It can be synthesized according to the method described in 2002, 67, 5753-5772. That is, o-phenylenediamine (when R ² is not present) or o- (substituted phenylene) diamine (wherein R ² may have a substituent, an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, An alkoxy group having 1 to 4 carbon atoms or a halogeno group) and ethyl-2-benzothiazolyl acetate (when R ¹ is not present) or ethyl-2- (substituted benzothiazolyl) acetate (where R ¹ is a substituent). (Optionally having an alkyl group having 1 to 8 carbon atoms, hydroxyl group, carboxyl group, alkoxy group having 1 to 4 carbon atoms or halogeno group) by refluxing at 160 ° C. for 6 hours in a nitrogen atmosphere ( 2-benzothiazolyl) (2-benzimidazolyl) methane or [2- (substituted benzothiazolyl)] [2- (substituted benzimi Dazolyl)] methane can be synthesized.
Examples of the ethyl-2-benzothiazolylacetate or ethyl-2- (substituted benzothiazolyl) acetate include those described in J. Org. Org. Chem. It can be synthesized according to the method described in 2002, 67, 5753-5772.

That is, ethyl 2-benzothiazolyl acetate or ethyl-2- (substituted benzothiazolyl) acetate is prepared by mixing ethyl cyanoacetate and 2-amino-substituted thiophenol and reacting at 120 ° C. for 2 hours in a nitrogen atmosphere. Can be synthesized.

v) In the case of Y ¹ = Y ² = O, Z ¹ = CH in the following formula (7):

For example, it can be synthesized according to the method described in US3250780. That is, 2-aminophenol (when R ¹ and R ² are not present) or 2-amino-substituted phenol (wherein R ¹ and R ² may have a substituent, an alkyl group having 1 to 8 carbon atoms, hydroxyl Group, carboxyl group, alkoxy group having 1 to 4 carbon atoms or halogeno group) and malonic acid are mixed, and this mixed liquid is added to polyphosphoric acid under stirring while maintaining the temperature at 70 ° C. Next, this reaction solution is heated to 175 ° C. and reacted to synthesize bis (2-benzoxazolyl) methane or bis [2- (substituted benzoxazolyl)] methane.

vi) The following formula (8): In the case of Y ¹ = Y ² = S, Z ¹ = CH in formula (2)

For example, J. et al. Org. Chem. It can be synthesized according to the method described in 1961, 26, 3434-3445. That is, 2-aminothiophenol (when R ¹ and R ² are not present) or 2-amino-substituted thiophenol (wherein R ¹ and R ² may have a substituent, an alkyl group having 1 to 8 carbon atoms) , A hydroxyl group, a carboxyl group, an alkoxy group having 1 to 4 carbon atoms or a halogeno group) and malonic acid are mixed, and this mixed solution is added to polyphosphoric acid under stirring while keeping the temperature at 70 ° C. Next, this reaction solution is reacted at 125-150 ° C. for 2 hours to synthesize bis (2-benzothiazolyl) methane or bis [2- (substituted benzothiazolyl)] methane.

vii) In the case of Y ¹ = NR ⁵ , Y ² = NR ⁵ , Z ¹ = CH in the following formula (9): Formula (2)

For example, Gazz. Chim. Ital. It can be synthesized according to the method described in 1996, 126, 329-337. That is, (N-substituted-) o-phenylenediamine (when R ¹ and R ² are not present) or (N-substituted-) [o- (substituted phenylene)] diamine (R ¹ and R ² have a substituent) An alkyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 4 carbon atoms or a halogeno group) and diethyl malonate are mixed, and the mixture is mixed under a nitrogen atmosphere. By refluxing at 155 ° C. for 11 hours, bis [2- (N-substituted) benzimidazolyl] methane or bis [2- (N-substituted) (substituted benzimidazolyl)] methane can be synthesized.

viii) In the following formula (10): In the formula (2), Z ¹ = CR ⁶

For example, Gazz. Chim. Ital. 1994, 124, 301-308. As described above, R ⁶ of CR ⁶ attributed to Z ¹ or Z ² in formula (1) is particularly preferably an aralkyl group. Here, taking the case where the aralkyl group is, for example, a 4-pyridylmethyl group, the synthesis method will be described below. Even when it is a substituent other than the 4-pyridylmethyl group, it can be synthesized according to the same synthesis method by selecting the corresponding substrate (aldehyde body corresponding to the substituent).

(2-benzothiazolyl) (2-benzimidazolyl) methane or [2- (substituted benzothiazolyl)] [2- (substituted benzimidazolyl)] methane obtained in iv), or bis (2-benzoxazolyl) obtained in v) ) Methane or bis [2- (substituted benzoxazolyl)] methane, or bis (2-benzothiazolyl) methane or bis [2- (substituted benzothiazolyl)] methane obtained from vi), or vii) Bis [2- (N-substituted) benzimidazolyl] methane or bis [2- (N-substituted) (substituted benzimidazolyl)] methane,
Acetic acid and sodium acetate are mixed, 4-pyridinecarboxaldehyde is added and reacted therewith, and then reduced using palladium carbon or the like,

From the compound obtained in iv), the corresponding 4- [β, β- (2-benzothiazolyl) (2-benzimidazolyl) ethyl] pyridine or 4- [β, β- {2- (substituted benzothiazolyl)} {2 -(Substituted benzimidazolyl)} ethyl] pyridine,
From the compound obtained in v), the corresponding 4- [β, β-bis (2-benzoxazolyl) ethyl] pyridine or 4- [β, β-bis {2- (substituted benzoxazolyl)] } Ethyl] pyridine,
From the compound obtained in vi), the corresponding 4- [β, β-bis (2-benzothiazolyl) ethyl] pyridine or 4- [β, β-bis {2- (substituted benzothiazolyl)} ethyl] pyridine is
From the compounds obtained in vii), the corresponding 4- [β, β-bis {2- (N-substituted) benzimidazolyl} ethyl] pyridine or 4- [β, β-bis {2- (N-substituted)] (Substituted benzimidazolyl) ethyl] pyridine can be synthesized.

ix) In Formula (2), each of at least one substituent of R ¹ and R ² may have an optionally substituted alkylaminosulfonyl group having 1 to 8 carbon atoms or a substituent. A morpholinosulfonyl group, an optionally substituted piperidinosulfonyl group, an optionally substituted pyrrolidinosulfonyl group, an optionally substituted thiomorpholinosulfonyl group or a substituent; In the case of piperazinosulfonyl group which may have

For example, according to the method described in JP-A-2007-535421, the ligands obtained by the above methods i) to viii) (in the formula (2), each of R ¹ and R ² is absent, or When present, 1 to 3 of 4 hydrogen atoms bonded to 4 carbon atoms except 6 carbon atoms shared with a 5-membered ring among 6 carbon atoms of one benzene ring. The alkylaminosulfonyl group having 1 to 8 carbon atoms which may have a substituent, a morpholinosulfonyl group which may have a substituent, and a substituent. Piperidinosulfonyl group which may have, pyrrolidinosulfonyl group which may have a substituent, thiomorpholinosulfonyl group which may have a substituent or piperazinosulfonyl which may have a substituent Introducing groups It can be.

Here, taking 2,2′-iminobisbenzothiazole or 2,2′-iminobis (substituted benzothiazole) obtained in i) as an example, the synthesis method will be described below.
2,2′-Iminobisbenzothiazole or 2,2′-iminobis (substituted benzothiazole) obtained in i) is added to the chlorosulfonic acid and the mixture is stirred overnight. Further, thionyl chloride is added and stirred at 50 ° C. for 1 hour, and then cooled to room temperature. The corresponding 2,2′-iminobis (substituted benzothiazole) can be synthesized by pouring the mixture onto ice and stirring with a primary or secondary amine along with the suction-filtered ice.

<< Method for Producing Metal Complex Represented by Formula (1) >>
For example, Polyhedron 2006, 25, 2363-2374 Org. Chem. In accordance with the methods described in 2002, 67, 5753-577, etc., the ligands obtained on the basis of the above production methods i) to ix), metal halides, metal sulfates, metal acetates, metals The corresponding metal complex can be synthesized by reacting with a metal salt such as nitrate. That is, a ligand obtained on the basis of the production methods i) to ix) and a metal salt corresponding to M in the formula (1) are mixed with methanol, ethanol, water, N, N-dimethylformamide ( It can be synthesized by reacting in a solvent such as DMF).

<< At least one kind of silane coupling having at least one kind of metal complex represented by the formula (1) and one or more functional groups selected from the group consisting of thiol group, amino group, ureido group and isocyanate group For producing a composition for an ultraviolet absorbing member containing an agent >>
The composition for ultraviolet absorbing members in the present invention will be described below.

As at least one silane coupling agent having one or more functional groups selected from the group consisting of thiol groups, amino groups, ureido groups, and isocyanate groups, for example,
Trimethoxysilylpropanethiol, triethoxysilylpropanethiol, 3- (dimethoxymethylsilyl) -1-propanethiol, etc.
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 3- (N-phenyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-amino Propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 4- (2-aminoethylaminomethyl) phenethyltrimethoxysilane, trimethoxysilylethylenediamine, N, N′-bis [3 -(Trimethoxysilyl) propyl] ethylenediamine, etc.
Such as 3-ureidopropyltriethoxysilane,
Examples include 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.

From the viewpoint of easy availability and reduction in coloration of the finally obtained ultraviolet absorbing member, trimethoxysilylpropanethiol, triethoxysilylpropanethiol, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyl Triethoxysilane is preferable, and 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane are more preferable.

The amount of the silane coupling agent to be used is 1 to 500 parts by weight, preferably 3 to 350 parts by weight, more preferably 5 to 250 parts by weight with respect to 10 parts by weight of the metal complex. If the amount is less than 1 part by weight, the color reduction effect of the metal complex, which is a feature of the present invention, may not be sufficiently exerted. If the amount is more than 500 parts by weight, the concentration of the metal complex in the composition for an ultraviolet absorbing member to be obtained May decrease, and the ultraviolet absorbing member finally obtained may not be provided with sufficient ultraviolet absorbing ability.

Further, in order to adjust the concentration of the composition for ultraviolet absorbing member in the present invention, a solvent may be used separately.

Furthermore, silicon alkoxide or metal alkoxide may be added separately in order to adjust the mechanical strength, film thickness and the like of the coating film of the finally obtained ultraviolet absorbing member.

For example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyl-tris (2-methoxyethoxy) silane, ethyl Trimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, ethyl-tris (2-methoxyethoxy) silane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltripropoxysilane, hexyltributoxysilane, Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane, vinyltrimethoxysilane, vinyltri Toxisilane, γ-methacryloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, methyldimethoxy (ethoxy) silane, ethyldiethoxy (methoxy) silane, dimethyldimethoxysilane, dimethyldiethoxysilane, bis (2-methoxyethoxy) ) Silicon alkoxides such as dimethylsilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane,
Examples thereof include metal alkoxides such as titanium alkoxide, cerium alkoxide, zirconium alkoxide, tin alkoxide, aluminum alkoxide, nickel alkoxide, and zinc alkoxide.

When these silicon alkoxides and metal alkoxides are added, they may be added as they are, or silicon alkoxides and / or metal alkoxides may be hydrolyzed and polycondensed in advance to prepare sol bodies, which may be added.

Further, as long as the effects of the present invention are not impaired, a curing agent, a curing catalyst, a crosslinking agent, a coupling agent, a leveling agent, a lubricant, an antistatic agent, an antioxidant, a thermal stabilizer, a flame retardant, and a filler , A colorant, a photocatalyst material, a rust inhibitor, a water repellent, a conductive material, an anti-blocking material, a softener, a release agent, a fluorescent brightening agent, and the like may be added as appropriate.

Moreover, a conventionally well-known light absorber can be added as needed and used together in the range which does not impair the effect of this invention.
The light absorber that can be used in combination is not particularly limited. For example, organic light absorbers include phthalocyanine, quinacridone, quinacridonequinone, benzimidazolone, quinone, and anthanthrone. , Dioxazine, diketopyrrolopyrrole, ansanthrone, indanthrone, flavanthrone, perinone, perylene, isoindoline, isoindolinone, azo, cyanine, azacyanine, squarylium, Organic dyes such as triarylmethane, metal complex dyes such as benzenedithiol metal complex, dithiolene metal complex, azo metal, metal phthalocyanine, metal naphthalocyanine, porphyrin metal complex, benzophenone, benzo Triazole, triazine, saluchi Over preparative system, phenyl salicylate ester type, hindered amine type, hindered phenol type, benzoate-based, phosphorus-based, amide-based, amine-based, organic-based ultraviolet absorbers such as the sulfur-based, and the like.

Inorganic light absorbers include hexaboride, tungsten oxide, composite tungsten oxide, titanium oxide, cerium oxide, zirconium oxide, tin oxide, zinc oxide, iron oxide, tantalum oxide, aluminum oxide, scandium oxide, yttrium oxide. , Calcium oxide, gallium oxide, lithium oxide, strontium oxide, barium oxide, magnesium oxide, indium oxide, thallium oxide, nickel oxide, neodymium oxide, cobalt oxide, chromium oxide, lanthanum oxide, niobium oxide, hafnium oxide, praseodymium oxide, oxide Metal oxides such as samarium, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide, and ITO (in Um - tin composite oxide), ATO (antimony - or tin composite oxide) composite metal oxides such as titanium nitride, and metal nitrides such as chromium nitride acid.

When preparing a composition for an ultraviolet absorbing member, when using a disperser, for example, paint shaker, ball mill, nano mill, attritor, basket mill, sand mill, sand grinder, dyno mill, disper mat, SC mill, spike mill Media type dispersers such as an agitator mill, and medialess dispersers such as an ultrasonic homogenizer, a high pressure homogenizer, a nanomizer, a resolver, a disper, and a high-speed impeller disperser can be used.

When using a media-type disperser, the dispersion media that can be used include steel ball beads such as stainless steel and steel, alumina, steatite, zirconia, zircon, silica, depending on the material in the dispersion chamber of the disperser used. Examples thereof include ceramic beads such as silicon carbide and silicon nitride, glass beads such as soda glass and high bee, and carbide beads such as WC. The bead diameter is preferably in the range of 0.03 to 1.5 mmφ.

<< Ultraviolet absorbing member produced using composition for ultraviolet absorbing member >>
By mixing the composition for an ultraviolet absorbing member thus obtained with a base material, the ultraviolet absorbing member containing the metal complex represented by the formula (1) in the base material and the composition for the ultraviolet absorbing member are used as the base material. By coating and baking, an ultraviolet absorbing member having a coating film containing the metal complex represented by the formula (1) on the substrate can be produced.
A method for producing the ultraviolet absorbing member having the coating film will be described in detail below.

The method for coating the base material with the composition for ultraviolet absorbing member is not particularly limited. For example, dip coating, spin coating, flow coating, roll coating, gravure coating, flexographic printing, screen printing And known methods such as an ink jet printing method, a bar coating method, a spray method, and a reverse coating method.
The substrate may be a film or a board as desired, and the shape is not limited. The material is not particularly limited, and can be appropriately selected and used according to the application. For example, inorganic base materials such as glass, poly (cyclo) olefin resin, polycarbonate resin, (meth) acrylic resin, polyester resin, polystyrene resin, epoxy resin, polyvinyl chloride resin, polychlorinated resin Vinylidene resin, polyacetal resin, polyamide resin, polyimide resin, fluorine resin, silicone resin, polysulfone resin, polyethersulfone resin, polyetherketone resin, polyetheretherketone resin, polyphenylene sulfide resin And organic base materials such as Among these, from the viewpoint of transparency, glass, poly (cyclo) olefin resin, polycarbonate resin, (meth) acrylic resin, polyester resin, polystyrene resin, epoxy resin, polyamide resin, polyimide resin, polysulfone Of these, a resin based on a resin, a polyether sulfone resin, a polyether ketone resin, and a polyphenylene sulfide resin are preferred.

Also, the surface of the substrate may be washed before coating for the purpose of preventing delamination and coating unevenness. It does not specifically limit as a washing | cleaning method, According to the kind of base material, it can select suitably and can implement. Usually, ultrasonic cleaning, UV cleaning, seric powder cleaning, acid cleaning, alkali cleaning, surfactant cleaning, organic solvent cleaning and the like can be performed alone or in combination. After the cleaning is completed, rinsing and drying are performed so that no cleaning agent remains.

The film thickness of the coating film of the finally obtained ultraviolet absorbing member is not particularly limited and can be appropriately adjusted according to the use, but is usually 0.01 to 100 μm, preferably 0.01 to 50 μm, More preferably, the thickness is 0.01 to 30 μm. If the thickness is less than 0.01 μm, there is a possibility that sufficient ultraviolet light absorbing ability may not be obtained. If the thickness exceeds 100 μm, low molecular components such as a solvent evaporate from the inside of the film during drying and baking, resulting in unevenness on the film surface or cracks. May occur.

Calcination temperature is 80 to 500 ° C, preferably 90 to 400 ° C, more preferably 100 to 300 ° C. If the temperature is lower than 80 ° C, polycondensation of a silane coupling agent or a silicon alkoxide or metal alkoxide (sol body, etc.) used in combination separately as necessary may not proceed sufficiently, and sufficient film strength may not be obtained. And the decomposition of the metal complex represented by the formula (1) starts, and there is a possibility that the ultraviolet absorbing ability is lowered.

Calcination time is usually 10 minutes to 5 hours, preferably 30 minutes to 3 hours. If it is shorter than 10 minutes, polycondensation of the silane coupling agent, an inorganic polymerizable monomer that is used in combination separately as required, or an inorganic polymer material does not proceed and sufficient film strength may not be obtained. If the length is too long, the effect corresponding to the time cannot be obtained and it is not economical.

When the composition for an ultraviolet absorbing member contains a non-polymerizable low-molecular volatile component such as a solvent, a drying step may be provided before the firing step, and the drying temperature and drying time depend on the type of solvent used. Can be set as appropriate.

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these examples.

Production Example 1
18.8 g (0.2 mol) of phenol was heated to 50 ° C. and melted, and 45.1 g (0.3 mol) of 2-aminobenzothiazole was added thereto, and then further heated to 180 ° C. and kept for 20 hours. did. Thereafter, the reaction solution was cooled to 80 ° C., 60 g of ethanol was added dropwise, and the temperature was further kept for 1 hour. Thereafter, the mixture was cooled to room temperature, the precipitate was filtered off, washed with ethanol and dried to obtain 32.1 g of white 2,2′-iminobisbenzothiazole (L1: see Table 1 below) as a ligand. It was. The yield was 75.5% based on 2-aminobenzothiazole.

Production Example 2
In Production Example 1, except that 53.5 g (0.3 mol) of 2-amino-5,6-dimethylbenzothiazole was used instead of 45.1 g (0.3 mol) of 2-aminobenzothiazole, Similarly, 42.1 g of white 2,2′-iminobis (5,6-dimethylbenzothiazole) (L2: see Table 1 below) was obtained as a ligand. The yield was 82.7% based on 2-amino-5,6-dimethylbenzothiazole.

Production Example 3
In the same manner as in Production Example 1, except that 55.4 g (0.3 mol) of 2-amino-6-chlorobenzothiazole was used instead of 45.1 g (0.3 mol) of 2-aminobenzothiazole in Production Example 1. As a ligand, 37.2 g of white 2,2′-iminobis (6-chlorobenzothiazole) (L3: see Table 1 below) was obtained. The yield was 70.4% based on 2-amino-6-chlorobenzothiazole.

Production Example 4
In the same manner as in Production Example 1, except that 54.1 g (0.3 mol) of 2-amino-6-methoxybenzothiazole was used instead of 45.1 g (0.3 mol) of 2-aminobenzothiazole in Production Example 1. As a ligand, 41.7 g of white 2,2′-iminobis (6-methoxybenzothiazole) (L4: see Table 1 below) was obtained. The yield was 81.0% based on 2-amino-6-methoxybenzothiazole.

Production Example 5
90.1 g (0.60 mol) of 2-aminobenzothiazole was dissolved in 566 g of DMF, and 36 mL of a 20 mol / L aqueous sodium hydroxide solution (corresponding to 0.72 mol of sodium hydroxide) was added dropwise in an ice bath. After 91.4 g (1.2 mol) of carbon sulfide was added dropwise and 36 mL of a 20 mol / L aqueous sodium hydroxide solution (corresponding to 0.72 mol of sodium hydroxide) was added dropwise, 178.8 g of methyl iodide (1. 26 mol) was added dropwise. After stirring at room temperature for 2 hours, the reaction solution was dropped into 3000 g of water. The precipitate was separated by filtration, washed with water and dried to obtain 107.2 g of S, S′-dimethyl-N- (2-benzothiazolyl) carbonimidodithioate. The yield was 70.2% based on 2-aminobenzothiazole.

21.8 g (0.20 mol) of 2-aminophenol was dissolved in 944 g of DMF, 40 mL of a 5 mol / L sodium hydroxide aqueous solution (corresponding to 0.20 mol of sodium hydroxide) was added thereto, and the mixture was stirred at room temperature for 30 minutes. Then, a solution prepared by dissolving 50.9 g (0.20 mol) of the obtained S, S′-dimethyl-N- (2-benzothiazolyl) carbonimide dithioate in 1416 g of DMF was added dropwise thereto. Next, the temperature was raised to 153 ° C., and the mixture was refluxed for 6 hours under a nitrogen atmosphere, then cooled to room temperature, and this reaction solution was dropped into 2000 g of water. The precipitate was separated by filtration, washed with water and dried to obtain 30.0 g of 2- (2-benzothiazolylamino) benzoxazole (L5: see Table 1 below). The yield was 56.1% based on 2-aminophenol.

Production Example 6
In the same manner as in Production Example 5, except that 98.5 g (0.60 mol) of 2-amino-6-methylbenzothiazole was used instead of 90.1 g (0.60 mol) of 2-aminobenzothiazole in Production Example 5. As a result, 114.2 g of S, S′-dimethyl-N- [2- (6-methylbenzothiazolyl)] carbonimide dithioate was obtained. The yield was 70.9% based on 2-amino-6-methylbenzothiazole.

Subsequently, instead of 50.9 g (0.20 mol) of S, S′-dimethyl-N- (2-benzothiazolyl) carbonimidodithioate in Production Example 5, S, S′-dimethyl-N obtained here was used. 2- [2- (6-Methylbenzothiazolyl)] 2- [2- (6-methylbenzothiazolyl)] was prepared in the same manner as in Production Example 5 except that 53.7 g (0.20 mol) of carbonimidodithioate was used. 29.4 g of thiazolyl) amino] benzoxazole (L6: see Table 1 below) was obtained. The yield was 52.3% based on S, S'-dimethyl-N- [2- (6-methylbenzothiazolyl)] carbonimidodithioate.

Production Example 7
In the same manner as in Production Example 5, except that 28.7 g (0.20 mol) of 2-amino-4-chlorophenol was used instead of 21.8 g (0.20 mol) of 2-aminophenol in Production Example 5. Thus, 32.4 g of 5-chloro-2- (2-benzothiazolylamino) benzoxazole (L7: see Table 1 below) was obtained. The yield was 53.7% based on 2-amino-4-chlorophenol.

Production Example 8
21.6 g (0.2 mol) of o-phenylenediamine was dissolved in 944 g of DMF, and 50.9 g (0.20 mol) of S, S′-dimethyl-N- (2-benzothiazolyl) -carbonimidodithioate was added thereto. A solution dissolved in 1258 g of DMF was added dropwise. Next, the temperature was raised to 153 ° C., refluxed for 13 hours in a nitrogen atmosphere, and then cooled to 0 ° C. To this was added 2000 g of water dropwise, and the precipitate was filtered off, washed with water and dried to obtain 32.0 g of 2- (2-benzothiazolylamino) benzimidazole (L8: see Table 1 below). . The yield was 60.1% with respect to o-phenylenediamine.

Production Example 9
101.8 g (0.90 mol) of ethyl cyanoacetate and 112.7 g (0.90 mol) of 2-aminothiophenol were mixed and kept at 120 ° C. for 2 hours under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, 185.7 g of ethyl-2-benzothiazolylacetate was obtained as a yellow oil. The yield was 93.2% based on 2-aminothiophenol.

N-methyl-o-phenylenediamine (73.3 g, 0.60 mol) and the ethyl-2-benzothiazolylacetate (132.8 g, 0.60 mol) obtained above were mixed and mixed under a nitrogen atmosphere. The mixture was refluxed at 160 ° C. for 6 hours. At this time, the ethanol by-produced was refluxed while being distilled off. The reaction solution was cooled to room temperature, 900 g of diethyl ether was added, and the precipitated yellow solid was separated by filtration. To the yellow solid separated by filtration, 1500 g of 20% hydrochloric acid was added and dissolved. Activated carbon was added thereto, and the mixture was stirred at room temperature for 30 minutes and then filtered. A sodium bicarbonate aqueous solution was added dropwise to neutralize the obtained filtrate until pH = 8, whereby a precipitate was obtained. This was separated by filtration, 600 g of water and 600 g of chloroform were added and stirred, and the chloroform layer was taken out by liquid separation treatment. Chloroform was distilled off and further dried to obtain 36.9 g of slightly yellow (2-benzothiazolyl) (2- (N-methylbenzimidazolyl) methane (L9: see Table 1 below). It was 22.0% with respect to methyl-o-phenylenediamine.

Production Example 10
22.7 g (0.30 mol) of 2-aminophenol and 15.6 g (0.15 mol) of malonic acid are mixed, and this mixed solution is added to 390 g of stirred polyphosphoric acid while keeping the temperature at 70 ° C. Next, the temperature of the reaction solution was raised to 150 ° C., kept warm for 3 hours, cooled to room temperature, and then water was added dropwise. The precipitate was filtered off, washed with water and dried to obtain 25.3 g of bis (2-benzoxazolyl) methane (L10: see Table 1 below). The yield was 67.4% based on 2-aminophenol.

Production Example 11
In the same manner as in Production Example 10 except that 37.6 g (0.30 mol) of 2-aminothiophenol was used instead of 32.7 g (0.30 mol) of 2-aminophenol in Production Example 10, bis ( 28.2 g of 2-benzothiazolyl) methane (L11: see Table 1 below) was obtained. The yield was 90.2% based on 2-aminothiophenol.

Production Example 12
110.0 g (0.90 mol) of N-methyl-o-phenylenediamine and 72.1 g (0.45 mol) of diethyl malonate were mixed, and the mixture was refluxed at 155 ° C. for 11 hours in a nitrogen atmosphere. The precipitate was separated by filtration, washed with diethyl ether, and dissolved by adding 900 mL of 20% hydrochloric acid. Activated carbon was added thereto, and the mixture was stirred at room temperature for 30 minutes and then filtered. A sodium hydrogen carbonate aqueous solution was dropped until the obtained filtrate had a pH of 8, resulting in precipitation. This was filtered off to obtain a gray solid. The gray solid was purified by recrystallization from IPA and dried to obtain 38.1 g of white bis [2- (N-methylbenzimidazolyl)] methane (L12: see Table 1 below). The yield was 30.6% based on N-methyl-o-phenylenediamine.

Production Example 13
10 g (0.035 mol) of 2,2′-iminobisbenzothiazole (L1: see Table 1 below) obtained in Production Example 1 was added to 70.1 g (0.602 mol) of chlorosulfonic acid, and the mixture was added. Stir at room temperature for 18 hours. Further, 10 g (0.084 mol) of thionyl chloride was added and stirred at 50 ° C. for 1 hour, and then cooled to room temperature. The mixture was poured onto 400 g of ice and stirred immediately with 13.1 g (0.101 mol) of diisobutylamine together with the ice which had been suction filtered. After warming to room temperature, the mixture was made alkaline with about 1 mL of 50 wt% sodium hydroxide solution. The solid was filtered off with suction, washed with water, and dried to give pale yellow 2,2′-iminobis [6- (N, N-diisobutylaminosulfonyl) benzothiazole] (L13: see Table 1 below) 18.6 g Got. The yield was 80.0% with respect to 2,2′-iminobisbenzothiazole.

Production Example 14
In the same manner as in Production Example 13 except that 8.8 g (0.101 mol) of morpholine was used instead of 13.1 g (0.101 mol) of diisobutylamine in Production Example 13, 2,2′-iminobis (6 -Morpholinosulfonylbenzothiazole) (L14: see Table 1 below) 15.4 g was obtained. The yield was 75.5% based on 2,2′-iminobisbenzothiazole.

Table 1 shows the structural formulas of the obtained ligands.

Production Example 15
28.3 g (0.1 mol) of the ligand (L1) obtained in Production Example 1 was dissolved in 2250 g (60 ° C.) of hot methanol, and 12.5 g (0.05) of cobalt acetate tetrahydrate was added thereto. Mol) was dissolved dropwise in 400 g of warm methanol. The resulting precipitate was filtered off, washed with methanol, and dried to obtain 28.5 g of an orange cobalt complex (C1-Co). The yield was 91.4% based on the ligand (L1).

Production Example 16
Similar to Production Example 15 except that 12.4 g (0.05 mol) of nickel acetate tetrahydrate was used instead of 12.5 g (0.05 mol) of cobalt acetate tetrahydrate in Production Example 15. As a result, 23.5 g of a reddish purple nickel complex (C1-Ni) was obtained. The yield was 75.4% based on the ligand (L1).

Production Example 17
Similar to Production Example 15 except that 10.0 g (0.05 mol) of copper acetate monohydrate was used instead of 12.5 g (0.05 mol) of cobalt acetate tetrahydrate in Production Example 15. As a result, 24.8 g of a grey-green copper complex (C1-Cu) was obtained. The yield was 78.9% based on the ligand (L1).

Production Example 18
In the same manner as in Production Example 15, except that 33.9 g (0.1 mol) of ligand (L2) was used instead of 28.3 g (0.1 mol) of ligand (L1) in Production Example 15. As a result, 32.3 g of an orange cobalt complex (C2-Co) was obtained. The yield was 87.8% based on the ligand (L2).

Production Example 19
In the same manner as in Production Example 16, except that 35.2 g (0.1 mol) of ligand (L3) was used instead of 28.3 g (0.1 mol) of ligand (L1) in Production Example 16. As a result, 28.0 g of a reddish purple nickel complex (C3-Ni) was obtained. The yield was 73.6% based on the ligand (L3).

Production Example 20
In the same manner as in Production Example 17, except that 34.3 g (0.1 mol) of ligand (L4) was used instead of 28.3 g (0.1 mol) of ligand (L1) in Production Example 17. As a result, 26.2 g of a grey-green copper complex (C4-Cu) was obtained. The yield was 70.0% based on the ligand (L4).

Production Example 21
In the same manner as in Production Example 16, except that 26.7 g (0.1 mol) of ligand (L5) was used instead of 28.3 g (0.1 mol) of ligand (L1) in Production Example 16. As a result, 25.2 g of a reddish brown nickel complex (C5-Ni) was obtained. The yield was 85.2% based on the ligand (L5).

Production Example 22
In the same manner as in Production Example 15, except that 28.1 g (0.1 mol) of ligand (L6) was used instead of 28.3 g (0.1 mol) of ligand (L1) in Production Example 15. 16.3 g of an orange cobalt complex (C6-Co) was obtained. The yield was 52.6% based on the ligand (L6).

Production Example 23
In the same manner as in Production Example 16, except that 30.2 g (0.1 mol) of ligand (L7) was used instead of 28.3 g (0.1 mol) of ligand (L1) in Production Example 16. As a result, 22.5 g of a reddish purple nickel complex (C7-Ni) was obtained. The yield was 68.2% based on the ligand (L7).

Production Example 24
In the same manner as in Production Example 17, except that 26.6 g (0.1 mol) of ligand (L8) was used instead of 28.3 g (0.1 mol) of ligand (L1) in Production Example 17. As a result, 16.6 g of a green copper complex (C8-Cu) was obtained. The yield was 55.9% based on the ligand (L8).

Production Example 25
In the same manner as in Production Example 16, except that 27.9 g (0.1 mol) of ligand (L9) was used instead of 28.3 g (0.1 mol) of ligand (L1) in Production Example 16. As a result, 24.4 g of a reddish brown nickel complex (C9-Ni) was obtained. The yield was 79.3% based on the ligand (L9).

Production Example 26
In the same manner as in Production Example 15, except that 25.0 g (0.1 mol) of ligand (L10) was used instead of 28.3 g (0.1 mol) of ligand (L1) in Production Example 15. As a result, 20.3 g of a red cobalt complex (C10-Co) was obtained. The yield was 72.8% based on the ligand (L10).

Production Example 27
In the same manner as in Production Example 15, except that 28.2 g (0.1 mol) of ligand (L11) was used instead of 28.3 g (0.1 mol) of ligand (L1) in Production Example 15. To obtain 22.1 g of a purple cobalt complex (C11-Co). The yield was 71.1% based on the ligand (L11).

Production Example 28
In the same manner as in Production Example 16, except that 28.2 g (0.1 mol) of the ligand (L11) was used instead of 28.3 g (0.1 mol) of the ligand (L1) in Production Example 16. 13.5 g of a black-green nickel complex (C11-Ni) was obtained. The yield was 43.4% based on the ligand (L11).

Production Example 29
In the same manner as in Production Example 17, except that 28.2 g (0.1 mol) of ligand (L11) was used instead of 28.3 g (0.1 mol) of ligand (L1) in Production Example 17. As a result, 18.6 g of a green copper complex (C11-Cu) was obtained. The yield was 59.4% based on the ligand (L11).

Production Example 30
In the same manner as in Production Example 16, except that 27.6 g (0.1 mol) of ligand (L12) was used instead of 28.3 g (0.1 mol) of ligand (L1) in Production Example 16. 20.8 g of a gray nickel complex (C12-Ni) was obtained. The yield was 68.3% based on the ligand (L12).

Production Example 31
4.00 g (0.006 mol) of the ligand (L13) obtained in Production Example 13 was dissolved in 24 g (70 ° C.) of warm DMF, and 0.75 g (0.003 mol) of nickel acetate tetrahydrate was dissolved therein. ) Was added. The mixture was stirred at 70 ° C. for 1 hour, cooled to room temperature, and 20 g of methanol was added dropwise. The resulting precipitate was filtered off, washed with methanol, and dried to obtain 3.58 g of a yellowish green nickel complex (C13-Ni). The yield was 85.9% based on the ligand (L13).

Production Example 32
3.49 g (0.006 mol) of the ligand (L14) obtained in Production Example 14 was dissolved in 24 g (70 ° C.) of warm DMF, and 0.75 g (0.003 mol) of cobalt acetate tetrahydrate was dissolved therein. ) Was added. The mixture was stirred at 70 ° C. for 1 hour, cooled to room temperature, and 20 g of methanol was added dropwise. The resulting precipitate was filtered off, washed with methanol, and dried to obtain 3.14 g of a yellow cobalt complex (C14-Co). The yield was 85.8% based on the ligand (L14).

Table 2 shows the structural formulas of the obtained metal complexes.

(Preparation of composition for ultraviolet absorbing member)
Using the metal complexes obtained in Production Examples 15 to 32, compositions for ultraviolet absorbing members were obtained at the composition ratios shown in Table 3 below. The acrylic resin in Table 3 was a methyl acrylate-ethyl methacrylate copolymer (trade name; Paraloid B-72, manufactured by Rohm and Haas). PGMEA in Table 3 is an abbreviation for propylene glycol monomethyl ether acetate.
[Use of disperser]
Existence: Each component and 0.1 mmφ zirconia balls are added to a pulverization container (product name manufactured by Fritsch: premium line pulverization vessel (made by interior zirconia)), and a planetary ball mill (product name manufactured by Fritsch: premium) line P-7) for 5 minutes at 600 rpm, cooled for 10 minutes, and further dispersed at 1100 rpm for 5 minutes.
None: Each component and stirrer piece were added to a glass sample bottle and stirred for 20 minutes using a magnetic stirrer.
[Coloring degree]
The degree of coloring was evaluated visually. Comparative Examples 1 to 3 are systems that do not contain a silane coupling agent having one or more functional groups selected from the group consisting of thiol groups, amino groups, ureido groups, and isocyanate groups. △ was set, and comparative evaluation was made based on this.
◎ ・ ・ ・ Coloring is very small 〇 ・ ・ ・ Coloring is small △ ・ ・ ・ Coloring is relatively large

Comparative Examples 1 to 4 are systems that do not contain a silane coupling agent having one or more functional groups selected from the group consisting of thiol groups, amino groups, ureido groups, and isocyanate groups. In the production of the ultraviolet absorbing member described later, in Examples 1 to 20, the contained silane coupling agent undergoes hydrolysis and polycondensation reaction in the firing step to form a matrix, thereby serving as a binder for the metal complex. work. Since Comparative Examples 1 to 4 did not contain such a matrix precursor, an acrylic resin was added separately.
As a result, in the systems containing the silane coupling agents of Examples 1 to 20, the coloring is clearly reduced as compared with Comparative Examples 1 to 4.

(Preparation of UV absorbing member)
Ultraviolet absorbing members were produced using the compositions for ultraviolet absorbing members obtained in Examples 1 to 20 and Comparative Examples 1 to 4.

[Production method]
The composition for ultraviolet absorbing member was applied on a soda lime glass substrate using a spin coater, and then preliminarily dried at room temperature in a nitrogen atmosphere for 10 minutes and then baked at 200 ° C. for 1 hour to obtain an ultraviolet absorbing member. Obtained.
In Example 39 and Comparative Example 8, a polycarbonate base material (manufactured by Sumitomo Bakelite, trade name: Polycaace ECK-100) was used instead of soda lime glass, and the firing conditions were 120 ° C./1 hour.

[Evaluation of UV absorbing member]
(1) Coloring degree The degree of coloring was evaluated visually. As shown below, the coloring degree of Comparative Examples 5 to 7 was set as Δ, and comparative evaluation was performed based on this.
◎ ・ ・ ・ Coloring is very small ○ ・ ・ ・ Coloring is small △ ・ ・ ・ Coloring is relatively large × ・ ・ ・ Coloring is very large (has turbidity)

(2) Light resistance After measuring the absorbance at λ = 380 nm using a spectrophotometer (manufactured by Hitachi, Ltd., model number: U-4100), the xenon weather meter (manufactured by Suga Test Instruments Co., Ltd., model number) X25) was used to irradiate these ultraviolet absorbing members with light having a radiation intensity of 60 W / m ² (integration in the region of λ = 300 to 400 nm) for 1000 hours. About the ultraviolet absorption member after light irradiation, the light absorbency in (lambda) = 380nm was measured again, and the change of the ultraviolet absorptivity by light irradiation was computed and evaluated as a residual absorption rate.
The residual absorption rate was calculated by the following formula.

Absorption residual ratio (%) = (Absorbance at λ = 380 nm after light irradiation / Absorbance at λ = 380 nm before light irradiation) × 100

The results are shown in Table 4 below.

The ultraviolet absorbing members obtained in Examples 21 to 40 are clearly less colored than the ultraviolet absorbing members obtained in Comparative Examples 5 to 8. In addition, any of Examples 21 to 40 has the same level of light resistance as Comparative Examples 5 to 8 not containing the silane coupling agent.
That is, according to the present invention, by combining the metal complex and the silane coupling agent, excellent light resistance, which is an advantage of the metal complex, and sufficient shielding of ultraviolet rays in the range of 380 to 400 nm are maintained for a long time. As it is, only coloring which was a disadvantage can be reduced.
Further, comparing Example 39 with a coating on a polycarbonate substrate and Comparative Example 8, in Comparative Example 8, the polycarbonate was invaded and clouded by DMF, but in Example 39, no erosion of the polycarbonate was observed. A good film was obtained as in the case of coating on the material.
In recent years, polycarbonate has attracted attention as a glass substitute material for window glass and the like, but has a major drawback of poor chemical resistance. If the composition for ultraviolet absorbing members in the present invention is used, a coating film having low coloring and high ultraviolet absorbing ability can be formed without eroding the polycarbonate. Further, since the polysiloxane film formed by the silane coupling agent has not only chemical resistance but also high mechanical strength, it is not difficult to imagine that it is effective for imparting hard coat characteristics.

According to the present invention, it is possible to sufficiently shield ultraviolet rays in the region of 380 to 400 nm, which has been difficult to shield while maintaining excellent light resistance for a long period of time and maintaining a high visible light transmittance. And the composition for ultraviolet absorbers which reduced coloring, and the ultraviolet absorber produced using this can be provided.

Claims (4)

1. Formula (1):
   

   

   Wherein Y ¹ , Y ² , Y ³ and Y ⁴ are each independently NH, NR ⁵ , an oxygen atom or a sulfur atom,
   R ⁵ of NR ⁵ belonging to Y ¹ , Y ² , Y ³ or Y ⁴ is an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms which may have a substituent. ^{Incidentally,} Y ^1, Y 2, when ^{Y 3} and at least two of ^{Y 4} is represented by NR ^5, the ^{R 5} of NR ⁵ represent a substituent independent of each other, respectively.
   Z ¹ and Z ² are each independently a nitrogen atom, CH or CR ⁶ ;
   R ⁶ of CR ⁶ assigned to Z ¹ or Z ² is an optionally substituted alkyl group having 1 to 8 carbon atoms or optionally substituted aryl having 6 to 15 carbon atoms. And a heteroaryl group having 4 to 12 carbon atoms which may have a substituent, a heteroaralkyl group having 5 to 12 carbon atoms or an aralkyl group having 7 to 15 carbon atoms which may have a substituent. . Incidentally, a substituent case, ^{R 6} of CR ⁶ is that each independently of one another ^{that Z 1} and ^{Z 2} are both represented by CR ^6.
   Each of R ¹ , R ² , R ³ and R ⁴ is absent or, if present, represents two carbon atoms shared with a 5-membered ring of the six carbon atoms of one benzene ring. 1 to 4 of the 4 hydrogen atoms bonded to the removed 4 carbon atoms can be substituted, and all of the substituents substituted with 4 hydrogen atoms of the benzene ring are independent of each other. An optionally substituted alkyl group having 1 to 8 carbon atoms, hydroxyl group, carboxyl group, alkoxy group having 1 to 4 carbon atoms, halogeno group, and optionally having 1 to 8 carbon atoms An alkylaminosulfonyl group, a morpholinosulfonyl group which may have a substituent, a piperidinosulfonyl group which may have a substituent, a pyrrolidinosulfonyl group which may have a substituent, a substituent You may have A morpholinosulfonyl group, or may have a substituent group piperazino sulfonyl group,
   M represents a metal atom. )
   At least one metal complex represented by:
   A composition for an ultraviolet absorbing member, comprising at least one silane coupling agent having at least one functional group selected from the group consisting of a thiol group, an amino group, a ureido group, and an isocyanate group.
2. The composition for ultraviolet absorbing members according to claim 1, wherein the metal atom M in the formula (1) is a cobalt atom, a nickel atom, or a copper atom.
3. An ultraviolet absorbing member produced by using the composition for ultraviolet absorbing member according to claim 1 or 2.
4. The ultraviolet absorbing member according to claim 3, wherein the composition for an ultraviolet absorbing member is coated on an organic or inorganic substrate.