JP2014088542A - Composition for ultraviolet absorption component and ultraviolet absorption component using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for ultraviolet absorption component having excellent heat resistance and capable of sufficiently shielding UV-A, and to provide an ultraviolet absorption component using the same.SOLUTION: The composition for ultraviolet absorption component comprises at least one metal complex represented in the formula (1), a benzophenone derivative, and a matrix material.

Description

  The present invention relates to a composition for an ultraviolet absorbing member comprising at least one specific metal complex and at least one benzophenone derivative, and an ultraviolet absorbing member produced using the composition.

  2. Description of the Related Art In recent years, members that have a function of selectively blocking ultraviolet rays while simultaneously sufficiently transmitting visible 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 a function of shielding ultraviolet rays to a substrate such as glass or resin, a method using inorganic metal oxide fine particles or organic ultraviolet absorbers as an ultraviolet absorber is generally known. Yes.

  However, regardless of inorganic metal oxide fine particles and organic ultraviolet absorbers, conventionally known ultraviolet absorbers are limited to 380 nm or less, and ultraviolet rays called UV-A of 380 to 400 nm. There are few known UV absorbers that can sufficiently shield the light, do not deteriorate even when irradiated with light for a long period of time, and sufficiently transmit visible light.

  Here, UV-A is ultraviolet light (320 to 400 nm) having a relatively long wavelength, and light in this region penetrates deep into the skin, leading to skin aging and further causing skin cancer. Yes.

  Examples of the organic ultraviolet absorber capable of blocking UV-A include the complexes described in Patent Documents 1 to 3. However, this ultraviolet absorber has excellent near-ultraviolet absorption performance, but for example, thermal decomposition and absorption ability due to treatment exposed to a high temperature such as a baking step at a high temperature when producing glass. May cause degradation and coloring problems.

International publication WO2011 / 089794 pamphlet International Publication WO2012 / 008318 Pamphlet JP 2012-12476 A

  The present invention is intended to solve the problems associated with the prior art as described above, has excellent heat resistance, and further can sufficiently block UV-A. And it aims at providing the ultraviolet-absorbing member using this.

  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):

In which each of R ¹ , R ² , R ³ and R ⁴ is absent or, if present, two of the 6 carbon atoms of one benzene ring shared with a 5-membered ring 1 to 4 of the 4 hydrogen atoms bonded to the 4 carbon atoms, excluding the carbon atoms, can be substituted, and all of the substituents in which the hydrogen atoms of the 4 benzene rings are substituted with each other. Independently, 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, a halogeno group, and an optionally substituted carbon Formula 1-8 alkylaminosulfonyl group, morpholinosulfonyl group which may have a substituent, piperidinosulfonyl group which may have a substituent, pyrrolidinosulfonyl which may have a substituent Have a substituent, Have a good thiomorpholino sulfonyl group or substituent is also good piperazino sulfonyl group.
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 assigned 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 attributed 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. Group, an optionally substituted heteroaryl group having 4 to 12 carbon atoms, an optionally substituted heteroaralkyl group having 5 to 12 carbon atoms, or an optionally substituted carbon The aralkyl group of several 7-15 is shown. 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.
M represents a metal atom. )
At least one metal complex represented by formula (2):

(In formula, R < ⁷ > and R < ⁸ > is a substituent of a benzene ring, the C1-C8 alkyl group which may have a substituent, the aromatic group which may have a substituent, These are an alkoxy group having 1 to 8 carbon atoms, an amino group, a carboxyl group, a mercapto group, and a halogeno group, and all the substituents are independent of each other.
m and n are integers of 0 to 5, and p and q are integers of 0 to 5.
However, m + n ≧ 1, m + p ≦ 5, and n + q ≦ 5. )
A composition for an ultraviolet absorbing member comprising at least one benzophenone derivative represented by the formula:

Item 2: The composition for an ultraviolet absorbing member according to Item 1, wherein the metal atom M in the formula (1) is a copper atom or a cobalt atom;

Item 3: The benzophenone derivative in the formula (2) is 2,4-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 2,2′-dihydroxybenzophenone, 2,4′-dihydroxybenzophenone, 4,4′-dihydroxybenzophenone, In item 1 or 2, which is 5-tert-butyl-2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone or 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, or a combination thereof The composition for ultraviolet absorption members as described.

Item 4: An ultraviolet absorbing member produced using the ultraviolet absorbing member composition according to any one of Items 1 to 3.

  According to the present invention, there are provided a composition for an ultraviolet absorbing member that has excellent heat resistance and can sufficiently shield UV-A, which has been difficult to shield conventionally, and an ultraviolet absorbing member using the same. be able to.

Hereinafter, the present invention will be described in detail.
The present invention relates to a composition for an ultraviolet absorbing member comprising at least one metal complex represented by the formula (1), at least one benzophenone derivative represented by the formula (2), and a matrix material, and uses the composition. An ultraviolet absorbing member is provided.

Examples of 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 given below. In each ^R 1 to R ⁶ and ^Y 1 to Y ^4, as the substituent which may be possessed by each group, for example, a halogeno group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms And an aryl group having 6 to 15 carbon atoms.

In formula (1), examples of R ⁵ of NR ⁵ belonging to Y ¹ , Y ² , Y ³ or Y ⁴ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n- Alkyl groups such as butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl and n-octyl And aryl groups such as phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-chlorophenyl group, 4-bromophenyl group, 3,4-dichlorophenyl group, naphthyl group, etc. .
^{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 (1), R ⁶ of the 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-butyl group, n-pentyl group, isopentyl group, neopentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl, n-heptyl group, n-octyl group, alkyl group such as phenyl group, 2 -Aryl groups such as methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-chlorophenyl group, 4-bromophenyl group, 3,4-dichlorophenyl group, naphthyl group, 2-furyl group, 2- Thienyl group, 5-chloro-2-thienyl group, 2-pyrrolyl group, 2-oxazolyl group, 5-methyl-2-oxazolyl group, 2-thiazolyl group, etc. A heteroaryl group such as 4-pyridylmethyl group, 4-quinolylmethyl group, 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- Butyl) -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) Examples include aralkyl groups such as -n-propyl group, 4-isopropylbenzyl group and 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 (1), 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 ^(1), it is assigned to R ^1, R 2, ^{R 3} or ^{R 4,} the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, etc. tert- butoxy group can be mentioned It is done.

In the formula (1), 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 (1), examples of the alkylaminosulfonyl group having 1 to 8 carbon atoms which may have the above-described substituent belonging to R ¹ , R ² , R ³ or R ⁴ include, for example, N— Methylaminosulfonyl group, N-ethylaminosulfonyl group, N-isopropylaminosulfonyl group, Nn-propylaminosulfonyl group, Nn-butylaminosulfonyl group, N, N-dimethylaminosulfonyl group, N, N- Methylethylaminosulfonyl group, N, N-diethylaminosulfonyl group, N, N-ethylisopropylaminosulfonyl group, N, N-diisopropylaminosulfonyl group, N, N-di-n-propylaminosulfonyl group, N, N- Examples thereof include a di-n-butylaminosulfonyl group and an N, N-diisobutylaminosulfonyl group.

In formula (1), examples of the morpholinosulfonyl group optionally having a substituent belonging to R ¹ , R ² , R ³ or R ⁴ include a morpholinosulfonyl group, a 2-methylmorpholinosulfonyl group, 3-methylmorpholinosulfonyl group, 2-ethylmorpholinosulfonyl group, 3-n-propylmorpholinosulfonyl group, 3-n-butylmorpholinosulfonyl group, 2,3-dimethylmorpholinosulfonyl group, 2,6-dimethylmorpholinosulfonyl group, 3-phenylmorpholinosulfonyl group etc. are mentioned.

In the formula (1), examples of the piperidinosulfonyl group optionally having a substituent belonging to R ¹ , R ² , R ³ or R ⁴ include a piperidinosulfonyl group and 2-methyl Piperidinosulfonyl group, 3-methylpiperidinosulfonyl group, 4-methylpiperidinosulfonyl group, 2-ethylpiperidinosulfonyl group, 4-n-propylpiperidinosulfonyl group, 3-n-butylpi Examples thereof include a peridinosulfonyl group, 2,4-dimethylpiperidinosulfonyl group, 2,6-dimethylpiperidinosulfonyl group, 4-phenylpiperidinosulfonyl group and the like.

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

In formula (1), examples of the thiomorpholinosulfonyl group which may have a substituent belonging to R ¹ , R ² , R ³ or R ⁴ include a thiomorpholinosulfonyl group, 2-methylthio Morpholinosulfonyl group, 3-methylthiomorpholinosulfonyl group, 2-ethylthiomorpholinosulfonyl group, 3-n-propylthiomorpholinosulfonyl group, 3-n-butylthiomorpholinosulfonyl group, 2,3-dimethylthiomorpholinosulfonyl group, 2 , 6-dimethylthiomorpholinosulfonyl group, 3-phenylthiomorpholinosulfonyl group and the like.

In the formula (1), 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-methyl Piperazinosulfonyl group, 3-methylpiperazinosulfonyl group, 2-ethylpiperazinosulfonyl group, 3-n-propylpiperazinosulfonyl group, 3-n-butylpiperazinosulfonyl group, 2,5- Examples include dimethylpiperazinosulfonyl 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 optionally substituted alkylaminosulfonyl group having 1 to 8 carbon atoms, an optionally substituted morpholinosulfonyl group, an optionally substituted piperidinosulfonyl group, 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 , Preferably an alkyl group having 1 to 8 carbon atoms, a halogeno group, or an alkoxy group having 1 to 4 carbon atoms, which may have a substituent, is not present, or is a halogeno group or an alkoxy group having 1 to 4 carbon atoms. It is more preferably a group, and even more preferably not present.

  Moreover, it may have a C1-C8 alkylaminosulfonyl group, the morpholinosulfonyl group which may have a substituent, the piperidinosulfonyl group which may have a substituent, and a substituent. The pyrrolidinosulfonyl group, the optionally substituted thiomorpholinosulfonyl group, or the optionally substituted piperazinosulfonyl group is particularly advantageous in terms of solubility in a solvent. Of these, the alkylaminosulfonyl group having 1 to 8 carbon atoms which may have a substituent or the morpholinosulfonyl group which may have a substituent is particularly advantageous.

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, but the synthesis method is simple and the metal complex to be obtained From the viewpoint of quality (purity) control, it is 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 . From the viewpoint of solubility of the metal complex in various solvents, Y ¹ = Y ³ ≠ Y ² = Y ⁴ and Z ¹ = Z ² and R ¹ = R ³ = R ² = R ⁴ , or Y ¹ It is preferred that Y = Y ³ = Y ² = Y ⁴ and Z ¹ = Z ² and R ¹ = R ³ ≠ R ² = R ⁴ .

  In the formula (1), examples of the metal atom represented by M include a cobalt atom, a nickel atom, a copper atom, or a zinc atom.

  These metal complexes may be used alone or in combination of two or more. The mixing ratio when two or more types are used in combination can be appropriately selected as desired.

  The metal complex represented by the formula (1) is obtained by reacting a ligand represented by the following formula (3) with a metal salt such as a metal halide, metal sulfate, metal acetate, or metal nitrate. Can be synthesized.

  Formula (3):

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

  The complex represented by the formula (1) and the ligand represented by the formula (3) can be produced, for example, by the method described in Patent Document 2.

In the benzophenone derivative represented by the formula (2), R ⁷ and R ⁸ are substituents of the benzene ring, and have an optionally substituted alkyl group having 1 to 8 carbon atoms and a substituent. And an aromatic group, an alkoxy group having 1 to 8 carbon atoms, an amino group, a carboxyl group, a mercapto group, and a halogeno group. All substituents are independent of each other.
Among these, R ¹ and R ² are an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted aromatic group, and an alkoxy group having 1 to 8 carbon atoms. preferable.

  Examples of the alkyl group having 1 to 8 carbon atoms which may have the substituent 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.

  Examples of the aromatic group which may have a substituent include a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 2,5- Dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 4-biphenyl group, 1-naphthyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-chlorophenyl group, 2-fluorophenyl group, 4-fluorophenyl group, 2-trifluoromethylphenyl group, 4-trifluoromethylphenyl group Etc.

  Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a sec-butoxy group, and a t-butoxy group. N-pentoxy group, iso-pentoxy group, neo-pentoxy group, 2-methylbutoxy group, n-hexoxy group, iso-hexoxy group, n-heptoxy group, iso-heptoxy group, n-octoxy group, iso-octoxy group The group 2-ethyl-hexoxy and the like.

  Examples of the halogeno group include a bromo group, a chloro group, and a fluoro group.

In formula (2), m and n are integers of 0 to 5, and p and q are integers of 0 to 5. However, m + n ≧ 1, m + p ≦ 5, and n + q ≦ 5 Among these, m and n are preferably a combination that satisfies m + n ≧ 2, and more preferably a combination that satisfies m + n = 2.

  Examples of benzophenone derivatives include 2-hydroxybenzophenone, 4-hydroxybenzophenone, 2-hydroxy-5-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2,4-dimethoxy-4. '-Hydroxybenzophenone, 2-fluoro-4'-hydroxybenzophenone, 4-fluoro-4-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 5-chloro-2-hydroxy-4-methylbenzophenone, 3,5- Dichloro-2-hydroxybenzophenone, 5-bromo-2-hydroxybenzophenone, 4-allyloxy-2-hydroxybenzophenone, 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid, 2- (4 Dibutylamino-2-hydroxybenzoyl) benzoic acid, 2,4-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 2,2'-dihydroxybenzophenone, 2,4'-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 5 -Tert-butyl-2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,3,4-trihydroxybenzophenone, 2, , 4,4′-trihydroxybenzophenone, 2,3,4,5′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3 ′, 4,4′-tetrahydroxybenzophenone , 2, 3, 3 ', 4 4 ', 5'-hexahydroxybenzophenone and the like.

  Among these, 2,4-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 2,2′-dihydroxybenzophenone, 2,4′-dihydroxybenzophenone, 4,4′-dihydroxybenzophenone, 5-tert-butyl-2, 4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,4′-tri Hydroxybenzophenone, 2,3,4,5′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3 ′, 4,4′-tetrahydroxybenzophenone are preferred, 2,4- Dihydroxybenzophenone, 3,4- Hydroxybenzophenone, 2,2'-dihydroxybenzophenone, 2,4'-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 5-tert-butyl-2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxy Benzophenone and 2,2′-dihydroxy-4,4′-dimethoxybenzophenone are more preferred.

  These benzophenone derivatives may be used alone or in combination of two or more. The mixing ratio when two or more types are used in combination can be appropriately selected as desired.

  The benzophenone derivative is used in an amount of 0.1 to 10000 parts by weight, preferably 1.0 to 100 parts by weight, and more preferably 2.5 to 50 parts by weight with respect to 100 parts by weight of the metal complex. preferable. If it is less than 0.1 part by mass, the effect of improving the heat resistance may not be sufficiently exhibited, and even if it is added in excess of 10000 parts by mass, an effect commensurate with the amount added cannot be obtained and it is not economical.

Examples of the matrix material include polymetalloxanes such as polysiloxane, polytitanoxane, polyzirconoxane, polyaluminoxane, and polystannoxane. In this case, a metal alkoxide and / or a sol solution obtained by hydrolysis / polycondensation reaction of a metal alkoxide as a precursor of polymetalloxane can be suitably used.
Further, polysiloxane can be preferably used as these matrix materials, and in this case, a sol solution obtained by hydrolysis / polycondensation reaction of silicon alkoxide and / or silicon alkoxide can be preferably used.

  The expression “matrix material” used in the present invention includes a matrix precursor such as a sol solution obtained by hydrolysis / polycondensation reaction of the metal alkoxide and / or metal alkoxide.

  The metal alkoxide sol solution can usually be prepared by adding water to the metal alkoxide in the presence of an acid catalyst in an organic solvent, followed by hydrolysis and polycondensation. However, a commercially available sol solution is used. May be.

(Metal alkoxide)
Examples of the metal alkoxide include silicon alkoxide, titanium alkoxide, zirconia alkoxide, aluminum alkoxide, and tin alkoxide.

  Examples of the silicon alkoxide include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, Methyl-tris (2-methoxyethoxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, ethyl-tris (2-methoxyethoxy) silane, hexyltrimethoxysilane, hexyltriethoxy Silane, hexyltripropoxysilane, hexyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyl Tributoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, methyldimethoxy (ethoxy) silane, ethyldiethoxy (methoxy) silane, ureidopropyltriethoxysilane, mercaptopropyltrimethoxysilane, Trifunctional alkoxysilanes such as isocyanatepropyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, bis (2-methoxyethoxy) dimethylsilane, diethyldi Ethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, mercaptopropylmethyldimethoxysilane, glycidoxypropylmethyldimeth Bifunctional alkoxysilanes such as xysilane and glycidoxypropylmethyldiethoxysilane are exemplified.

  Examples of the titanium alkoxide include tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, tetra (2-ethylhexoside) titanium, and the like.

  Examples of the zirconia alkoxide include tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetrabutoxyzirconium, tetra (1-methoxy-2-methyl-2-propoxy) zirconium and the like.

  Examples of the aluminum alkoxide include trimethoxyaluminum, triethoxyaluminum, tripropoxyaluminum, tributoxyaluminum, diethylethoxyaluminum and the like.

  Examples of the tin alkoxide include tetramethoxytin, tetraethoxytin, tetrapropoxytin, and tetrabutoxytin.

  These metal alkoxides may be used alone or in combination of two or more. The mixing ratio when two or more types are used in combination can be appropriately selected as desired.

  In the matrix material, from the viewpoint of the state, strength, and economical efficiency of the obtained film, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxy Silane, phenyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, glycidoxypropylmethyldimethoxysilane, A sol solution obtained by using one or more silicon alkoxides selected from cidoxypropylmethyldiethoxysilane is more preferable.

  These silicon alkoxides may be used alone or in combination of two or more. The mixing ratio when two or more types are used in combination can be appropriately selected as desired.

  Hereinafter, a method for preparing a metal alkoxide sol solution will be described in detail by taking a silicon alkoxide sol solution (siloxane oligomer solution) as an example.

(Acid catalyst)
The acid catalyst is not particularly limited, and examples thereof include inorganic acids such as nitric acid, hydrochloric acid, and sulfuric acid, and organic acids such as formic acid, acetic acid, and oxalic acid. If acid remains after completion of the hydrolysis / polycondensation reaction, condensation stability deteriorates. Formic acid having a low boiling point and high volatility and a small pKa is preferably used.

  The addition amount of the acid catalyst is not particularly limited as long as sufficient catalytic action is exerted, but usually 0.01 mol or more, more preferably 0.3 mol or more per 1 mol of silicon alkoxide. preferable. If the amount is less than 0.01 mol, sufficient catalytic action may not be obtained, and if excessively added, the finally obtained silicon alkoxide sol solution may deteriorate over time due to the remaining acid. . Therefore, it is preferable to mix | blend in the ratio of 1 mol or less with respect to 1 mol of silicon alkoxides.

(water)
Although it does not specifically limit as long as it can cause the hydrolysis of the said silicon alkoxide, It is preferable to add water in the ratio of 2-6 mol with respect to 1 mol of silicon alkoxide. If the amount is less than 2 mol, the hydrolysis may not proceed sufficiently. If the amount exceeds 6 mol, the hydrolysis proceeds too quickly, preventing the subsequent polycondensation reaction from proceeding, and increasing the amount of water removed after the reaction. Not efficient.

(Reaction solvent)
By using a reaction solvent in addition to silicon alkoxide, water, and an acid catalyst, the hydrolysis rate can be moderately reduced, and hydrolysis and polycondensation can proceed reliably. Further, it also serves as a diluent for adjusting the viscosity of the finally obtained silicon alkoxide sol solution (siloxane oligomer solution) to a level that is easy to handle.

  The reaction solvent is not particularly limited as long as it can dissolve the silicon alkoxide, and can be appropriately selected and used. For example, alcohols such as methanol, ethanol, isopropanol (IPA), butanol and tetrafluoropropanol, halogenated hydrocarbons such as chloroform and dichloromethane, ethylene glycol, 1,2-propanediol and 1,3-propanediol Glycols such as 1,4-butanediol and diethylene glycol; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 3-heptanone and 3-octanone; and acetic acid Ethyl, ethyl 2-hydroxypropionate, 3-methyl-3-methoxypropionate-n-butyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, vinegar Esters such as n-butyl, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, γ-butyrolactone, and ethyl lactate And ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, aromatics such as toluene, xylene, monochlorobenzene, dichlorobenzene, n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, cyclo Hydrocarbons such as heptane, lactams such as 2-pyrrolidone, N-methyl-2-pyrrolidone, and ε-caprolactam, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol monomethyl ether acetate, diethylene glycol mono Glycol ethers such as chill ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and other acetonitrile, sulfolane, dimethyl sulfoxide, DMF, etc. Is mentioned.

  From the viewpoint of reactivity and economy, preferably alcohols such as methanol, ethanol, IPA, butanol, tetrafluoropropanol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butane Diols, glycols such as diethylene glycol, ethyl acetate, ethyl 2-hydroxypropionate, n-butyl 3-methyl-3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, propionate-n-butyl, ethyl butyrate, isopropyl butyrate, butyric acid n-butyl, ethyl pyruvate, γ-butyrolactone, ethyl lactate Esters such as diethyl Ethers such as ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether acetate, PGMEA, And glycol ethers such as propylene glycol monoethyl ether acetate.

  In the subsequent step, when the metal complex represented by the formula (1) is dissolved and mixed in the sol solution (siloxane oligomer solution) of the silicon alkoxide, a solvent having good solubility of the metal complex is previously added to the silicon alkoxide. By using it as a reaction solvent in the preparation of the sol solution, it is possible to reduce labor when dissolving and mixing the metal complex.

  However, even when the silicon alkoxide sol solution (siloxane oligomer solution) in this step is prepared using a poor solvent for the metal complex, the sol solution of the silicon alkoxide is dissolved before the metal complex is dissolved and mixed. It is also possible to dissolve and mix the solvent by substituting the good solvent for the metal complex or by adding the good solvent for the metal complex to the silicon alkoxide sol solution (siloxane oligomer solution).

  The reaction solvent is used in an amount of 50 to 1000 parts by mass, preferably 100 to 500 parts by mass with respect to 100 parts by mass of silicon alkoxide. If the amount is less than 50 parts by mass, the hydrolysis / polycondensation reaction may be difficult to proceed at an appropriate reaction rate. If the amount exceeds 1000 parts by mass, the rate of the hydrolysis / polycondensation reaction is reduced, which is efficient. In addition to this, there is a possibility that a long time is required for the pressure reduction / distillation step described later.

  First, one or more silicon alkoxides are mixed with an acid catalyst, water, and a solvent. By maintaining this solution at a temperature of 0 to 150 ° C., preferably 50 to 100 ° C., the hydrolysis / polycondensation reaction proceeds. If it is less than 0 degreeC, there exists a possibility that a hydrolysis and a polycondensation reaction may become difficult to advance. On the other hand, when the temperature exceeds 150 ° C., the hydrolysis / polycondensation reaction proceeds rapidly, so that an unreacted alkoxy group may remain or cause gelation or coloring. The time for the hydrolysis / polycondensation reaction is usually 1 to 24 hours, more preferably 2 to 8 hours, although it depends on temperature conditions. If it is less than 1 hour, there is a possibility that the hydrolysis / polycondensation reaction does not proceed sufficiently, and even if it exceeds 24 hours, the reaction does not proceed any further, which is not economical.

  In order to remove alcohol and water by-produced by the hydrolysis / polycondensation reaction from the system, it is preferable to distill off the reaction solution under reduced pressure after completion of the reaction or during the reaction. If the reaction is allowed to proceed while distilling off under reduced pressure, the effect of improving the reaction rate of the polycondensation reaction can be expected, which is more preferable. In this step, if a low-boiling and highly volatile catalyst such as formic acid is used as the acid catalyst, the acid catalyst can be removed from the system together with the solvent, and the stability of the sol solution after completion of the reaction can be ensured.

  Thus, a sol solution of metal alkoxide as polymetalloxane can be obtained by the progress of hydrolysis and polycondensation reaction. Other metal alkoxides can be similarly prepared.

  The amount of the matrix material used is preferably in the range of 500 to 100,000 parts by mass, preferably 1000 to 30000 parts by mass with respect to 100 parts by mass of the metal complex. If the amount is less than 500 parts by mass, the film strength may not be obtained, and if it exceeds 100000 parts by mass, sufficient ultraviolet absorbing performance may not be imparted to the ultraviolet absorbing member.

  In the composition for ultraviolet absorbing member of the present invention, the metal complex represented by the formula (1), the benzophenone derivative represented by the formula (2), and the matrix material may be used alone, Two or more types may be used in combination. The mixing ratio when two or more types are used in combination can be appropriately selected as desired.

≪Method for producing composition for ultraviolet absorbing member≫
The composition for ultraviolet absorbing members of the present invention comprises at least one metal complex represented by the above formula (1), at least one benzophenone derivative represented by the above formula (2), and the matrix material. It is manufactured by mixing. The method for mixing these components is not particularly limited, and includes conventionally known mixing methods including the use of mixing devices and instruments.

In the mixing of the metal complex, the benzophenone derivative, and the matrix material, a solvent having good solubility may be used.
The solvent having good compatibility between the metal complex, the benzophenone derivative and the matrix material, and the solubility of the metal complex is good depending on the type of the metal complex, the benzophenone derivative and the matrix material. Can be appropriately selected and used.

  As a solvent with good solubility of the sol solution obtained by hydrolysis / polycondensation reaction of metal alkoxide and / or metal alkoxide as the metal complex, benzophenone derivative, polymetalloxane and / or polymetalloxane precursor, It can be appropriately selected and used according to the type of the metal complex. For example, alcohols such as methanol, ethanol, IPA, butanol, tetrafluoropropanol, glycols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, Halogenated hydrocarbons such as chloroform and dichloromethane; ketones such as acetone, MEK, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and 3-octanone; ethyl acetate, ethyl 2-hydroxypropionate, 3 -Methyl-3-methoxypropionate-n-butyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoacetate , Esters of propionate-n-butyl, ethyl butyrate, isopropyl butyrate, butyrate-n-butyl, ethyl pyruvate, γ-butyrolactone, ethyl lactate, ethers such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, Aromatics such as toluene, xylene, monochlorobenzene, dichlorobenzene, hydrocarbons such as n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, cycloheptane, 2-pyrrolidone, N-methyl Lactams such as 2-pyrrolidone and ε-caprolactam, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethyl Glycol monoethyl ether, diethylene glycol mono -n- butyl ether acetate, PGMEA, glycol ethers such as propylene glycol monomethyl ether acetate and other acetonitrile, sulfolane, dimethyl sulfoxide, DMF, and the like.

  Among these, more preferable from the viewpoint of solubility of the metal complex, alcohols such as methanol, ethanol, IPA, butanol and tetrafluoropropanol, halogenated hydrocarbons such as chloroform and dichloromethane, Ketones such as acetone, MEK, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 3-octanone, ethyl acetate, ethyl 2-hydroxypropionate, n-butyl 3-methyl-3-methoxypropionate , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, butyric acid Isopropyl, butyric acid-n-but , Esters such as ethyl pyruvate, γ-butyrolactone and ethyl lactate, ethers such as diethyl ether, cyclopentyl methyl ether and tetrahydrofuran, aromatics such as toluene, xylene, monochlorobenzene and dichlorobenzene, 2- Lactams such as pyrrolidone, N-methyl-2-pyrrolidone, ε-caprolactam, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono- glycol ethers such as n-butyl ether acetate, PGMEA, propylene glycol monoethyl ether acetate, Other acetonitrile, sulfolane, dimethyl sulfoxide, DMF and the like.

  More preferably, the alcohols are tetrafluoropropanol, the halogenated hydrocarbons are chloroform, dichloromethane, etc., the ketones are MEK, cyclopentanone, cyclohexanone, etc., and the esters are γ-butyrolactone, lactic acid. Ethyl, n-butyl acetate, etc., ethers such as cyclopentyl methyl ether, tetrahydrofuran and the like, aromatics such as toluene, xylene, monochlorobenzene and dichlorobenzene, lactams as 2-pyrrolidone, N-methyl- Examples include 2-pyrrolidone, ε-caprolactam, and glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, and PGMEA, and other sulfolanes, dimethyl sulfoxide, DMF, and the like.

  The amount of the solvent used may be appropriately adjusted in consideration of the concentration of the metal complex in the desired composition for ultraviolet absorbing members, the type of solvent used, the solubility of the precursor of the matrix material used, and the like. Although not particularly limited, from the viewpoint of solubility of the metal complex, it is usually 50 to 100,000 parts by weight, preferably 100 to 5000 parts by weight, more preferably 100 parts by weight of the metal complex. 200 to 3000 parts by mass. If the amount is less than 50 parts by mass, the metal complex may not be completely dissolved, and the visible light transmittance of the finally obtained ultraviolet absorbing member may be lowered. On the other hand, when the amount is more than 100000 parts by mass, the concentration of the metal complex in the composition for ultraviolet absorbing member is lowered, and there is a possibility that sufficient ultraviolet absorbing ability cannot be imparted to the finally obtained ultraviolet absorbing member.

  These solvents may be used alone or in combination of two or more. The mixing ratio in the case of using a mixed solvent in which two or more types are combined can be appropriately selected.

  When the sol solution and the benzophenone derivative obtained by hydrolysis / polycondensation reaction of the metal complex and the metal alkoxide and / or metal alkoxide as the polymetalloxane and / or polymetalloxane precursor are dissolved in a solvent, A sol solution obtained by hydrolysis / polycondensation reaction of a benzophenone derivative and a metal alkoxide and / or metal alkoxide as a polysiloxane and / or polymetalloxane precursor in advance is dissolved in a solvent, and the metal complex is added thereto. The metal complex may be dissolved in a solvent in advance, and a benzophenone derivative and polymetalloxane and / or metal alkoxide and / or metal alkoxide as a polymetalloxane precursor may be hydrolyzed in this solution.・ Obtained by polycondensation reaction The sol solution may be mixed and dissolved, or obtained by hydrolysis / polycondensation reaction of the metal complex, the benzophenone derivative, polymetalloxane and / or metal alkoxide and / or metal alkoxide as a polymetalloxane precursor. The resulting sol solution may be mixed and dissolved simultaneously with the solvent.

  Here, when the matrix material to be used is in a solution state and the solvent in the solution state is a good solvent for the metal complex and benzophenone derivative, the metal complex, the benzophenone derivative and the solution state It is also possible to simply mix the matrix material with

  Moreover, as long as the effect of the present invention is not impaired, a light absorber, 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, Flame retardants, fillers, colorants, photocatalytic materials, rust inhibitors, water repellents, conductive materials, antiblocking materials, softeners, mold release agents, fluorescent whitening agents, and the like may be added as appropriate.

<< Ultraviolet absorbing member produced using composition for ultraviolet absorbing member >>
An ultraviolet absorbing member can be produced using the composition for an ultraviolet absorbing member thus obtained.

An ultraviolet absorbing member as a laminate having a film of a matrix material containing the metal complex (hereinafter referred to as a matrix film) on the substrate, the ultraviolet absorbing member composition obtained above is applied to the substrate, dried and By curing by baking / or curing, an ultraviolet absorbing member as a laminate having a matrix film containing the metal complex on a substrate can be produced.

  The method for applying the composition for an ultraviolet absorbing member to a substrate is not particularly limited. For example, a dip coating method, a spin coating method, a flow coating method, a roll coating method, a gravure coating method, a flexographic printing method, a screen printing method. And known coating methods such as inkjet printing, bar coating, spraying, and reverse coating.

  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 substrates such as glass, metal plates and ceramics, poly (cyclo) olefin resins, polycarbonate resins, (meth) acrylic resins, polyester resins, polystyrene resins, epoxy resins, polyvinyl chloride Resin, polyvinylidene chloride resin, polyacetal resin, polyamide resin, polyimide resin, fluorine resin, silicone resin, polysulfone resin, polyethersulfone resin, polyetherketone resin, polyetheretherketone resin Examples thereof include organic base materials such as resins and polyphenylene sulfide resins. Among them, from the viewpoint of transparency, glass, poly (cyclo) olefin resin, polycarbonate resin, (meth) acrylic resin, polyester resin, polystyrene resin, epoxy resin, polyvinyl chloride resin, polyvinylidene chloride Of these, a resin based on polyacetal, a resin based on polyacetal, a polyamide based resin, a polyimide based resin, a polysulfone based resin, a polyether sulfone based resin, a polyether ketone based resin, a polyether ether ketone based resin and a polyphenylene sulfide resin are preferred.

  The film thickness of the coating film formed by coating is not particularly limited and can be appropriately adjusted according to the application, but is usually 0.05 to 500 μm, preferably 0.5 to 100 μm, and more preferably 1. ˜100 μm. If the thickness is less than 0.05 μm, there is a risk that sufficient UV absorption ability may not be obtained. If the thickness exceeds 500 μm, the solvent (dispersion medium) evaporates from the inside of the film during drying, resulting in unevenness on the film surface or cloudiness of the film. Or cracks, and transparency in the visible light range may be impaired.

The drying temperature and drying time can be appropriately set depending on the type of solvent and dispersion medium used.
After drying, in order to control the physical properties such as mechanical strength of the thin film containing the metal complex so as to meet the purpose, a curing process and a baking process may be provided.

For example, when polysiloxane is used as the matrix material, the mechanical strength of the film itself is provided by providing a baking step at 80 to 500 ° C., preferably 90 to 400 ° C., more preferably 100 to 300 ° C. after the drying step. Can be improved.
In other words, in the drying step, the sol (siloxane oligomer) solution undergoes a polycondensation reaction to expand the siloxane network and form a skeleton structure of a gel body. By baking this gel body, the siloxane network further expands. The mechanical strength of the resulting coating film can be controlled by the size of the siloxane network (polysiloxane molecular weight).
If the temperature is lower than 80 ° C, the mechanical strength may not be sufficiently improved, and if the temperature is higher than 500 ° C, the metal complex contained in the coating film may be thermally decomposed.

  The firing time can be appropriately adjusted according to the desired physical properties of the coating film, but is usually 5 minutes to 5 hours, preferably 10 minutes to 3 hours. If it is shorter than 5 minutes, the mechanical strength may not be sufficiently improved, and if it is longer than 5 hours, an effect commensurate with the time cannot be obtained and it is not economical.

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

  Each ligand (L1 to L10) of the metal complex used in the examples was produced by the method described in Patent Document 2.

<Method for producing metal complex>
Production Example 1: Metal Complex C1-Cu
28.3 g (0.1 mol) of the ligand (L1) was dissolved in 2250 g (60 ° C.) of warm methanol, and 10.0 g (0.05 mol) of copper acetate monohydrate was dissolved in 400 g of warm methanol. The solution was added dropwise. The resulting precipitate was filtered, washed with methanol, and dried to obtain 24.8 g of a grey-green copper complex (C1-Cu). The yield was 78.9% based on the ligand (L1).

Production Example 2: Metal Complex C1-Co
In the same manner as in Production Example 1, except that 12.5 g (0.05 mol) of cobalt acetate tetrahydrate was used instead of 10.0 g (0.05 mol) of copper acetate monohydrate in Production Example 1. 28.5 g of an orange cobalt complex (C1-Co) was obtained. The yield was 91.4% based on the ligand (L1).

Production Example 3: Metal Complex C2-Cu
In the same manner as in Production Example 1 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 1, ash 28.4 g of a green copper complex (C2-Cu) was obtained. The yield was 76.7% based on the ligand (L2).

Production Example 4: Metal Complex C2-Co
In the same manner as in Production Example 2, except that 12.5 g (0.05 mol) of cobalt acetate tetrahydrate was used instead of 10.0 g (0.05 mol) of copper acetate monohydrate in Production Example 3. , 32.3 g of an orange cobalt complex (C2-Co) was obtained. The yield was 87.8% based on the ligand (L2).

Production Example 5: Metal Complex C3-Cu
In the same manner as in Production Example 1 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 1, ash 26.9 g of a green copper complex (C3-Cu) was obtained. The yield was 70.2% based on the ligand (L3).

Production Example 6: Metal Complex C3-Co
In the same manner as in Production Example 2, except that instead of 10.0 g (0.05 mol) of copper acetate monohydrate in Production Example 5, 12.5 g (0.05 mol) of cobalt acetate tetrahydrate was used. , 34.3 g of an orange cobalt complex (C3-Co) was obtained. The yield was 90.2% based on the ligand (L3).

Production Example 7: Metal Complex C4-Cu
In the same manner as in Production Example 1 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 1, ash 26.2 g of a green copper complex (C4-Cu) was obtained. The yield was 70.0% based on the ligand (L4).

Production Example 8: Metal Complex C5-Cu
In the same manner as in Production Example 1 except that 28.2 g (0.1 mol) of ligand (L5) was used instead of 28.3 g (0.1 mol) of ligand (L1) in Production Example 1, ash 23.1 g of a green copper complex (C5-Cu) was obtained. The yield was 77.4% based on the ligand (L5).

Production Example 9: Metal Complex C6-Cu
In the same manner as in Production Example 1 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 1, ash 23.6 g of a green copper complex (C6-Cu) was obtained. The yield was 75.5% based on the ligand (L6).

Production Example 10: Metal complex C7-Cu
In the same manner as in Production Example 1 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 1, ash 26.6 g of a green copper complex (C7-Cu) was obtained. The yield was 79.9% based on the ligand (L7).

Production Example 11: Metal Complex C8-Cu
In the same manner as in Production Example 1 except that 28.2 g (0.1 mol) of ligand (L8) was used instead of 28.3 g (0.1 mol) of ligand (L1) in Production Example 1, ash 16.6 g of a green copper complex (C8-Cu) was obtained. The yield was 55.9% based on the ligand (L8).

Production Example 12: Metal Complex C9-Cu
4.0 g (0.006 mol) of the ligand (L9) was dissolved in 24 g (70 ° C.) of warm DMF, and 0.60 g (0.003 mol) of copper acetate monohydrate was added thereto. The mixture was stirred at 70 ° C. for 1 hour, cooled to room temperature, and 20 g of methanol was added dropwise. The generated precipitate was separated by filtration, washed with methanol, and dried to obtain 2.9 g of a grayish green copper complex (C9-Cu). The yield was 68.5% based on the ligand (L9).

Production Example 13: Metal complex C10-Co
Instead of 4.0 g (0.006 mol) of ligand (L9) in Production Example 12, 3.49 g (0.006 mol) of ligand (L10) was further added to 0.60 g of copper acetate monohydrate. 3.14 g of yellow cobalt complex (C10-Co) was obtained in the same manner as in Production Example 12 except that 0.75 g (0.003 mol) of cobalt acetate tetrahydrate was used instead of (0.003 mol). It was. The yield was 85.8% based on the ligand (L10).

  Table 1 shows the structural formula of each ligand in the metal complex.

Production Example 14: Matrix material (1)
61.3 g (0.255 mol) of phenyltriethoxysilane (PTES), 10.6 g (0.045 mol) of glycidoxypropyltrimethoxysilane (GPTMS) and 30 g of isopropanol were mixed and stirred at room temperature. A solution was obtained. To this solution, 4.2 g (0.091 mol) of formic acid and 16.2 g of water were added as catalysts, and the mixture was stirred at room temperature for 30 minutes for hydrolysis. Next, the temperature of the hydrolyzed solution is raised to 70 ° C. and kept for 2 hours to allow the hydrolysis and polycondensation reaction to proceed. Further, under reduced pressure, by-produced alcohol and water are distilled off, and further 2 hours Hydrolysis / polycondensation reaction was allowed to proceed. Thereafter, 60.7 g of tetrahydrofuran (THF) was added to obtain a 40 mass% sol / THF solution of silicon alkoxide as a polysiloxane component.

Production Example 15: Matrix material (2)
Phenyltriethoxysilane (PTES) 54.1 g (0.225 mol), methyltriethoxysilane (MTES) 6.7 g (0.038 mol) and glycidoxypropyltrimethoxysilane (GPTMS) 8.9 g (0. 038 mol) and 30 g of isopropanol were mixed and stirred at room temperature to obtain a solution. To this solution, 4.2 g (0.091 mol) of formic acid and 16.2 g of water were added as catalysts, and the mixture was stirred at room temperature for 30 minutes for hydrolysis. Next, the temperature of the hydrolyzed solution is raised to 70 ° C. and kept for 2 hours to allow the hydrolysis and polycondensation reaction to proceed. Further, under reduced pressure, by-produced alcohol and water are distilled off, and further 2 hours Hydrolysis / polycondensation reaction was allowed to proceed. Thereafter, 66.8 g of tetrahydrofuran (THF) was added to obtain a 40 mass% sol / THF solution of silicon alkoxide as a polysiloxane component.

(Composition for ultraviolet absorbing member and ultraviolet absorbing member using the same)
Example 1
To 2.0 g of the matrix material (1) obtained in Production Example 14, 8.0 mg of metal complex C1-Cu and 0.2 mg (0.0010 mmol) of 4-hydroxybenphenone are added with stirring and mixed. Thus, a composition for an ultraviolet absorbing member was obtained.
The obtained composition for ultraviolet absorbing member was applied onto a cover glass substrate using a spin coater (manufactured by Active Co., Ltd., model number: ACT-300A), and then pre-dried in a nitrogen atmosphere at room temperature for 5 minutes. And then baked at 150 ° C. for 1 hour to obtain an ultraviolet absorbing member. The coating film thickness was 9 μm.

Example 2
In Example 1, instead of 0.2 mg (0.0010 mmol) of 4-hydroxybenphenone, 0.2 mg (0.0009 mmol) of 2-hydroxy-4-methoxybenzophenone (Seeprob 101 manufactured by Cypro Kasei) was used. In the same manner as in Example 1, an ultraviolet absorbing member composition and an ultraviolet absorbing member were obtained. The thickness of the coating film was 8 μm.

Example 3
In Example 1, instead of 0.2 mg (0.0010 mmol) of 4-hydroxybenphenone, 0.2 mg (0.0006 mmol) of 2-hydroxy-4-octyloxybenzophenone (Cypro Kasei Seesorb 102) was used. In the same manner as in Example 1, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained. The coating film thickness was 7 μm.

Example 4
In Example 1, instead of 0.2 mg (0.0010 mmol) of 4-hydroxybenphenone, 0.08 mg (0.0004 mmol) of 2,4-dihydroxybenzophenone (Seeprob 100 manufactured by Cypro Kasei) was used. Similarly, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained. The thickness of the coating film was 8 μm.

Example 5
In Example 1, instead of 0.2 mg (0.0010 mmol) of 4-hydroxybenphenone, 0.2 mg (0.0009 mmol) of 2,4-dihydroxybenzophenone (Seeprob 100 manufactured by Cypro Kasei) was used. Similarly, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained. The thickness of the coating film was 8 μm.

Example 6
In Example 1, instead of 0.2 mg (0.0010 mmol) of 4-hydroxybenphenone, 0.4 mg (0.0019 mmol) of 2,4-dihydroxybenzophenone (Seeprob 100 manufactured by Cypro Kasei) was used. Similarly, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained. The thickness of the coating film was 8 μm.

Example 7
In Example 1, instead of 0.2 mg (0.0010 mmol) of 4-hydroxybenphenone, 2.0 mg (0.0093 mmol) of 2,4-dihydroxybenzophenone (Seeprob 100 manufactured by Cypro Kasei) was used. Similarly, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained. The coating film thickness was 7 μm.

Example 8
In Example 1, instead of 0.2 mg (0.0010 mmol) of 4-hydroxybenphenone, 4.0 mg (0.0187 mmol) of 2,4-dihydroxybenzophenone (Seeprob 100 manufactured by Cypro Kasei) was used. Similarly, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained. The thickness of the coating film was 8 μm.

Example 9
In the same manner as in Example 1 except that 0.2 mg (0.0009 mmol) of 2,4′-dihydroxybenzophenone was used instead of 0.2 mg (0.0010 mmol) of 4-hydroxybenphenone in Example 1, ultraviolet rays were used. A composition for an absorbing member and an ultraviolet absorbing member were obtained. The thickness of the coating film was 8 μm.

Example 10
In the same manner as in Example 1 except that 0.2 mg (0.0009 mmol) of 4,4′-dihydroxybenzophenone was used instead of 0.2 mg (0.0010 mmol) of 4-hydroxybenphenone in Example 1, ultraviolet rays were used. A composition for an absorbing member and an ultraviolet absorbing member were obtained. The thickness of the coating film was 8 μm.

Example 11
Instead of 0.2 mg (0.0010 mmol) of 4-hydroxybenphenone in Example 1, 0.2 mg (0.0007 mmol) of 2,2′-dihydroxy-4,4′-dimethoxybenzophenone (Seeprob 107 manufactured by Cypro Kasei) was used. Except having used, it carried out similarly to Example 1, and obtained the composition for ultraviolet absorbers, and an ultraviolet absorber. The coating film thickness was 7 μm.

Example 12
Example 1 except that 0.2 mg (0.0008 mmol) of 2,2 ′, 4,4′-tetrahydroxybenzophenone was used instead of 0.2 mg (0.0010 mmol) of 4-hydroxybenphenone in Example 1. In the same manner as above, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained. The coating film thickness was 7 μm.

Example 13
Example 1 except that 0.2 mg (0.0008 mmol) of 2,3,4,4′-tetrahydroxybenzophenone was used instead of 0.2 mg (0.0010 mmol) of 4-hydroxybenphenone in Example 1. Similarly, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained. The coating film thickness was 7 μm.

Example 14
A composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained in the same manner as in Example 5, except that 8.0 mg of the metal complex C2-Cu was used instead of 8.0 mg of the metal complex C1-Cu in Example 5. The thickness of the coating film was 8 μm.

Example 15
In Example 5, instead of using 8.0 mg of the metal complex C1-Cu, 8.0 mg of the metal complex C3-Cu, and further using 2.0 g of the matrix material (2) instead of 2.0 g of the matrix material (1). In the same manner as in Example 5, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained. The thickness of the coating film was 8 μm.

Example 16
A composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained in the same manner as in Example 5, except that 8.0 mg of the metal complex C4-Cu was used instead of 8.0 mg of the metal complex C1-Cu in Example 5. The coating film thickness was 9 μm.

Example 17
Example 5 except that in place of metal complex C1-Cu 8.0 mg, metal complex C5-Cu 8.0 mg was used, and in addition to 2.0 g of matrix material (1), 2.0 g of matrix material (2) was used. In the same manner as in Example 5, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained. The thickness of the coating film was 8 μm.

Example 18
In Example 5, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained in the same manner as in Example 5 except that 8.0 mg of the metal complex C6-Cu was used instead of 8.0 mg of the metal complex C1-Cu. The coating film thickness was 7 μm.

Example 19
Example 5 except that in place of metal complex C1-Cu 8.0 mg, metal complex C7-Cu 8.0 mg was used, and in addition to 2.0 g of matrix material (1), 2.0 g of matrix material (2) was used. In the same manner as in Example 5, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained. The thickness of the coating film was 8 μm.

Example 20
In Example 5, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained in the same manner as in Example 5 except that 8.0 mg of the metal complex C8-Cu was used instead of 8.0 mg of the metal complex C1-Cu. The coating film thickness was 7 μm.

Example 21
In Example 5, the metal complex C1-Cu 8.0 mg was used instead of the metal complex C1-Cu 8.0 mg, and the matrix material (2) 2.0 g was used instead of the matrix material (1) 2.0 g. In the same manner as in Example 5, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained. The thickness of the coating film was 8 μm.

Example 22
In Example 5, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained in the same manner as in Example 5, except that 8.0 mg of the metal complex C1-Co was used instead of 8.0 mg of the metal complex C1-Cu. The coating film thickness was 7 μm.

Example 23
A composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained in the same manner as in Example 5, except that 8.0 mg of the metal complex C2-Co was used instead of 8.0 mg of the metal complex C1-Cu in Example 5. The coating film thickness was 7 μm.

Example 24
A composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained in the same manner as in Example 5 except that 8.0 mg of the metal complex C3-Co was used instead of 8.0 mg of the metal complex C1-Cu in Example 5. The thickness of the coating film was 8 μm.

Example 25
A composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained in the same manner as in Example 5, except that 8.0 mg of the metal complex C10-Co was used instead of 8.0 mg of the metal complex C1-Cu in Example 5. The coating film thickness was 7 μm.

Comparative Example 1
A composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained in the same manner as in Example 1 except that 0.2 mg (0.0010 mmol) of 4-hydroxybenphenone was not used in Example 1. The thickness of the coating film was 8 μm.

Comparative Example 2
Example 1 except that 0.2 mg (0.0010 mmol) of 4-hydroxybenphenone was not used in Example 1, and 2.0 g of matrix material (2) was used instead of 2.0 g of matrix material (1). In the same manner as above, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained. The thickness of the coating film was 8 μm.

Comparative Example 3
A composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained in the same manner as in Example 1 except that 0.2 mg (0.0010 mmol) of 4-hydroxybenphenone was not used in Example 23. The thickness of the coating film was 8 μm.

[Evaluation of UV absorbing member]
About the ultraviolet-absorbing member obtained in Examples 1-25 and Comparative Examples 1-3, it implemented by the following procedures.
(1) Evaluation of heat resistance (metal complex remaining rate)
About the ultraviolet-absorbing member obtained in Examples 1-25 and Comparative Examples 1-3, specific wavelength ((lambda) = 376nm: ultraviolet-ray UV-A is used using a spectrophotometer (the Hitachi, Ltd. make, model number: U-4100). ) Was measured, and ultraviolet absorption ability (UV-A absorption ability) was evaluated. Thereafter, the ultraviolet absorbing member was heated at 200 ° C. for 10 minutes on a hot plate (manufactured by ASONE) and sufficiently cooled to room temperature, and then the transmittance was measured.
For the measurement, separately prepare a test piece in which a glass substrate is coated with a matrix layer (not including the UV absorber, use the same matrix as the sample to be measured, and prepare the test piece under the same conditions). This was used as a blank to perform background correction. That is, the permeation performance of the membrane itself is not reflected, and can be regarded as originating exclusively from the ultraviolet absorber.
As a heat resistance evaluation method, the metal complex residual ratio (%) was calculated from the transmittance at λ = 376 nm before and after heating at 200 ° C. for 10 minutes using the following formula.

(2) Heat resistance evaluation (color change)
About the ultraviolet-absorbing member obtained in Examples 1-25 and Comparative Examples 1-3, the hue before and behind a heat resistance test (200 degreeC for 10 minutes) was evaluated by visual observation. The results are shown in Table 4.

※実施例および比較例における金属錯体は１００質量部、マトリックス材料は２５０００質量部用いた。

* In the examples and comparative examples, 100 parts by mass of the metal complex and 25000 parts by mass of the matrix material were used.

Examples 1 to 3 are systems using a benzophenone derivative, and it can be seen that both the residual rate and the hue change are excellent.
Further, Examples 4 to 11 are 2,4-dihydroxybenzophenone, 2,4′-dihydroxybenzophenone, 4,4′-dihydroxybenzophenone, 2,2′-dihydroxy-4, benzophenone derivatives having two hydroxyl groups. 4'-dimethoxybenzophenone is a system, and among them, in Examples 5 to 11 in which the compounding amount is 2.5 parts by mass or more with respect to 100 parts by mass of the metal complex, It can be seen that the remaining rate and hue change are even better.
On the other hand, Comparative Examples 1 to 3 are systems in which no benzophenone derivative was used. It can be seen that both the residual ratio and the hue change are greatly deteriorated after the heat resistance test.

Claims (4)

Formula (1):

In which each of R ¹ , R ² , R ³ and R ⁴ is absent or, if present, two of the 6 carbon atoms of one benzene ring shared with a 5-membered ring 1 to 4 of the 4 hydrogen atoms bonded to the 4 carbon atoms, excluding the carbon atoms, can be substituted, and all of the substituents in which the hydrogen atoms of the 4 benzene rings are substituted with each other. Independently, 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, a halogeno group, and an optionally substituted carbon Formula 1-8 alkylaminosulfonyl group, morpholinosulfonyl group which may have a substituent, piperidinosulfonyl group which may have a substituent, pyrrolidinosulfonyl which may have a substituent Have a substituent, Have a good thiomorpholino sulfonyl group or substituent is also good piperazino sulfonyl group.
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 assigned 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 attributed 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. Group, an optionally substituted heteroaryl group having 4 to 12 carbon atoms, an optionally substituted heteroaralkyl group having 5 to 12 carbon atoms, or an optionally substituted carbon The aralkyl group of several 7-15 is shown. 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.
M represents a metal atom. )
At least one metal complex represented by formula (2):

(In formula, R < ⁷ > and R < ⁸ > is a substituent of a benzene ring, the C1-C8 alkyl group which may have a substituent, the aromatic group which may have a substituent, These are an alkoxy group having 1 to 8 carbon atoms, an amino group, a carboxyl group, a mercapto group, and a halogeno group, and all the substituents are independent of each other.
m and n are integers of 0 to 5, and p and q are integers of 0 to 5.
However, m + n ≧ 1, m + p ≦ 5, and n + q ≦ 5. )
A composition for an ultraviolet absorbing member comprising at least one benzophenone derivative represented by the formula (1) and a matrix material.   The composition for ultraviolet absorbing members according to claim 1, wherein the metal atom M in the formula (1) is a copper atom or a cobalt atom.   The benzophenone derivative in formula (2) is 2,4-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 2,2′-dihydroxybenzophenone, 2,4′-dihydroxybenzophenone, 4,4′-dihydroxybenzophenone, 5-tert. The butyl-2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone or 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, or a combination thereof. Composition for ultraviolet absorbing member.   The ultraviolet absorption member produced using the composition for ultraviolet absorption members in any one of Claims 1-3.