JP2014062228A - Composition for ultraviolet absorption member and ultraviolet absorption member using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for an ultraviolet absorption member and an ultraviolet absorption member using the same, the composition having excellent heat resistance and being able to sufficiently shield ultraviolet rays in a 380 to 400 nm region which has heretofore been difficult to shield.SOLUTION: Provided is a composition for an ultraviolet absorption member, comprising at least one kind of metal complex comprising a heterocyclic ring of a specific structure; a silane compound having at least one kind of amino group, represented by the formula (2); 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 a silane compound having at least one amino group, 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 No. 2011/089794 International Publication No. 2012/008318 Japanese Unexamined Patent Publication No. 2012-12476

  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):

(Where
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 hydrogen atoms on the benzene ring are each independently substituted with a substituent. C1-C8 alkyl group which may have, hydroxyl group, carboxyl group, C1-C4 alkoxy group, halogeno group, C1-C8 alkylamino which may have a substituent A sulfonyl 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, and a substituent Thiomol you may have Have a Rinosuruhoniru group or substituent a 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):

(Where
R ⁷ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, or an aromatic group which may have a substituent,
R ⁸ is an optionally substituted alkylene group having 1 to 8 carbon atoms, in which some of the carbon atoms may be substituted with oxygen atoms or nitrogen atoms,
R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted aromatic group, It is a C1-C8 alkoxy group, Comprising: At least 1 is an alkoxy group among R < ⁹ >, R < ¹⁰ > and R < ¹¹ >. A composition for an ultraviolet absorbing member comprising a silane compound having at least one amino group represented by formula (II) and a matrix material;

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 silane compound having an amino group represented by the formula (2) is aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldimethoxysilane, or aminopropylmethyldiethoxysilane. A composition for an ultraviolet absorbing member of

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 provides an ultraviolet absorbing member composition comprising at least one metal complex represented by the formula (1), a silane compound having at least one amino group represented by the formula (2), and a matrix material, The present invention also provides an ultraviolet absorbing member using the same.

Examples of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , Y ¹ , Y ² , Y ³ and Y ⁴ , Z ¹ and Z ² and M in the 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 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, examples of 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 include, 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.

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. One to four, preferably one or two, of the four hydrogen atoms bonded to the four carbon atoms excluding the atoms can be substituted, and all of the substituents substituted with hydrogen atoms on the benzene ring are all Independently of each other, they 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, a halogeno group, or a substituent. C1-C8 alkylaminosulfonyl group, morpholinosulfonyl group which may have a substituent, piperidinosulfonyl group which may have a substituent, pyrrole which may have a substituent Dinosulfonyl group, A thiomorpholinosulfonyl group which may have a group or a piperazinosulfonyl group which may have a substituent, from the viewpoint of economy, that is, availability of raw materials and yield, It is 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 group, and is not present, or is a halogeno group or an alkoxy group having 1 to 4 carbon atoms. More preferably, it is even more preferred that it is 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.

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.

R ¹ , R ² , R ³ and R ⁴ , Y ¹ , Y ² , Y ³ and Y ⁴ and Z ¹ and Z ² are independent of each other, but the simplicity of the synthesis method 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.

  The metal complex represented by the formula (1) has the following formula (3):

で表される配位子と、金属ハロゲン化物、金属硫酸塩、金属酢酸塩、金属硝酸塩等の金属塩とを反応させることで合成することができる。

And a metal salt such as a metal halide, metal sulfate, metal acetate, or metal nitrate can be synthesized.

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

  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 silane compound having an amino group represented by the formula (2), R ⁷ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent (for example, an amino group-containing alkyl group), The aromatic group which may have a substituent is shown. Among these, a hydrogen atom is preferable.
R ⁸ in the formula (2) represents an optionally substituted alkylene group having 1 to 8 carbon atoms, and a part of the carbon atoms therein may be substituted with an oxygen atom or a nitrogen atom. Good.
R ⁹ , R ¹⁰ and R ^{11 in} formula (2) each independently have a hydrogen atom, a C 1-8 alkyl group which may have a substituent, or a substituent. An aromatic group, an alkoxy group having 1 to 8 carbon atoms, and at least one of R ⁹ , R ¹⁰ and R ¹¹ is an alkoxy group. In view of availability, R ⁹ , R ¹⁰ and R ¹¹ are preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and more preferably an alkoxy group having 1 to 4 carbon atoms. .

Examples of the silane compound having an amino group include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldimethoxysilane, aminopropylmethyldiethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxy. Silane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminopropylmethyldimethoxysilane, N-phenylaminopropylmethyldiethoxysilane, aminopropyltributoxysilane, aminopropyltripropoxysilane Etc.
Among them, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldimethoxysilane, aminopropylmethyldiethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane, N-phenylaminopropyl Trimethoxysilane and N-phenylaminopropyltriethoxysilane are preferable, and aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldimethoxysilane, and aminopropylmethyldiethoxysilane are more preferable.

  The amount of the silane compound having an amino group is desirably 500 to 20000 parts by weight, preferably 1000 to 8000 parts by weight, and more preferably 1000 to 6000 parts by weight with respect to 100 parts by weight of the metal complex. If the amount is less than 500 parts by weight, the effect of improving heat resistance may not be sufficiently exhibited. If the amount exceeds 20000 parts by weight, sufficient ultraviolet absorbing ability may not be imparted to the ultraviolet absorbing member.

Examples of the matrix material include polymetalloxanes such as polysiloxane, polytitanoxane, polyzirconoxane, polyaluminoxane, and polystannoxane. As the matrix material, a sol solution obtained by hydrolysis / polycondensation reaction of a metal alkoxide compound and / or metal alkoxide can be suitably used.
Moreover, as these matrix materials, a sol solution obtained by hydrolysis / polycondensation reaction of polysiloxane, silicon alkoxide and / or silicon alkoxide can be suitably used.

  In addition, 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 compound and / or metal alkoxide.

  A metal alkoxide sol solution can be prepared by adding water to a metal alkoxide in the presence of an acid catalyst in an organic solvent, followed by hydrolysis and polycondensation. Also good.

(Metal alkoxide)
The metal alkoxide used in the present invention is not particularly limited, but includes silicon alkoxide, titanium alkoxide, zirconia alkoxide, tin alkoxide and the like.

As silicon alkoxide,
Tetrafunctional alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyl-tris (2-methoxy) Ethoxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, ethyl-tris (2-methoxyethoxy) silane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltripropoxysilane, Hexyl riboxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane, vinyltrimethoxy Silane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, methyldimethoxy (ethoxy) silane, ethyldiethoxy (methoxy) silane, ureidopropyltriethoxysilane, mercaptopropyltrimethoxysilane, isocyanatepropyltriethoxysilane, grease Trifunctional alkoxysilanes such as sidoxypropyltrimethoxysilane and glycidoxypropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, bis (2-methoxyethoxy) dimethylsilane, diethyldiethoxysilane, diphenyldimethoxysilane, Diphenyldiethoxysilane, mercaptopropylmethyldimethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropylmethyl Bifunctional alkoxysilanes such as diethoxysilane are exemplified.

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

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

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

As tin alkoxide,
Tetramethoxytin, tetraethoxytin, tetrapropoxytin, tetrabutoxytin and the like can be mentioned.

  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 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 exhibited, but usually 0.01 mol or more, more preferably 0.3 mol or more is added per 1 mol of silicon alkoxide. It is preferable to do. If the amount is less than 0.01 mol, sufficient catalytic action may not be obtained, and if added excessively, the finally obtained silicon alkoxide sol solution may deteriorate over time due to the remaining acid. is there. 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 the hydrolysis of the said silicon alkoxide can be caused, 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 moles, the hydrolysis may not proceed sufficiently. If the amount exceeds 6 moles, the hydrolysis proceeds too quickly, hindering the progress of the subsequent polycondensation reaction, and the amount of water removed after the reaction. Increased and 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.

  When the metal complex represented by the formula (1) is dissolved and mixed in the silicon alkoxide sol solution (siloxane oligomer solution), a solvent having good solubility of the metal complex is used as a reaction solvent in this step in advance. By doing so, the labor at the time of melt-mixing this metal complex can be reduced.

  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 weight, preferably 100 to 500 parts by weight, based on 100 parts by weight of silicon alkoxide. If the amount is less than 50 parts by weight, it may be difficult to cause the hydrolysis / polycondensation reaction to proceed at an appropriate reaction rate. If the amount exceeds 1000 parts by weight, the rate of the hydrolysis / polycondensation reaction decreases, 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 kind or two or more kinds of 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 desirably 500 to 100,000 parts by weight, and preferably 1000 to 30,000 parts by weight with respect to 100 parts by weight of the metal complex. If it is less than 500 parts by weight, the film strength may not be obtained, and if it exceeds 100,000 parts by weight, sufficient ultraviolet absorbing performance may not be imparted to the ultraviolet absorbing member.

  In the composition for ultraviolet absorbing members of the present invention, the metal complex represented by the formula (1), the silane compound having an amino group represented by the formula (2), and the matrix material are each used alone. Alternatively, 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 includes at least one metal complex represented by the above formula (1), and a silane compound having at least one amino group represented by the above formula (2), Manufactured by mixing with the matrix material. 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 silane compound having an amino group, and the matrix material, a solvent having good solubility may be used.
Examples of the solvent having good compatibility between the metal complex, the silane compound having an amino group, and the matrix material, and having good solubility of the metal complex include the metal complex and the silane having an amino group. It can be appropriately selected and used according to the kind of the compound and the matrix material.

  The above-mentioned metal complex, the silane compound having an amino group, and the solvent having good solubility for the matrix material 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 weight. If the amount is less than 50 parts by weight, 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 weight, 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 silane compound having an amino group and the matrix material are dissolved in a solvent, the silane compound having an amino group and the matrix material are dissolved in the solvent in advance, and the metal complex is added here. The metal complex may be dissolved in a solvent in advance, and the silane compound having an amino group and the matrix material may be mixed and dissolved in this solution, or the metal complex and the amino group may be dissolved. The silane compound and the matrix material may be mixed with a solvent and dissolved.

  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 a silane compound having an amino group, the metal complex and the amino group It is also possible to simply mix the silane compound having the above and the matrix material in the solution state.

Moreover, a conventionally well-known light absorber can also be used together as needed in the range which does not impair the effect of this invention.
Although it does not specifically limit as a light absorber which can be used together, For example, phthalocyanine series, quinacridone series, quinacridone quinone series, benzimidazolone series, quinone series, anthanthrone series, dioxazine series, diketopyrrolopyrrole Organic, anthanthrone, indanthrone, flavanthrone, perinone, perylene, isoindoline, isoindolinone, azo, cyanine, azacyanine, squarylium, triarylmethane, etc. And metal complex dyes such as benzenedithiol metal complex, dithiolene metal complex, azo metal, metal phthalocyanine, metal naphthalocyanine, porphyrin metal complex, benzophenone, benzotriazole, triazine, salicylate , Salicylic acid fe Glycol ester-based, hindered amines based, hindered phenol-based, benzoate-based, phosphorus-based, amide-based, amine-based, organic-based ultraviolet absorbers such as the sulfur-based, and the like. From the viewpoint of economic efficiency and light absorption performance, organic dyes such as phthalocyanine, quinone, perylene, azo, cyanine, azacyanine, squarylium, triarylmethane, benzophenone, benzotriazole Organic UV absorbers such as triazine, hindered amine, hindered phenol, benzoate, phosphorus, amine and sulfur.

  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, dip coating, spin coating, flow coating, roll coating, gravure coating, flexographic printing, screen printing 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 a polysiloxane compound is used as a matrix material, the film itself is machined 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. Strength can be improved.
That is, in the drying step, the sol (siloxane oligomer) 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 hot methanol, and 10.0 g (0.05 mol) of copper acetate monohydrate was added to 400 g of hot methanol. The dissolved solution was added dropwise. The generated precipitate was separated by filtration, washed with methanol, and dried to obtain 24.8 g of a grayish green copper complex (C1-Cu). The yield was 78.9% based on the ligand (L1).

Production Example 2: Metal Complex C1-Co
The same as Production Example 1 except that instead of 10.0 g (0.05 mol) of copper acetate monohydrate in Production Example 1, 12.5 g (0.05 mol) of cobalt acetate tetrahydrate was used. As a result, 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. , 28.4 g of a grey-green copper complex (C2-Cu) was obtained. The yield was 76.7% based on the ligand (L2).

Production Example 4: Metal Complex C2-Co
Similar to Production Example 3 except that instead of 10.0 g (0.05 mol) of copper acetate monohydrate in Production Example 3, 12.5 g (0.05 mol) of cobalt acetate tetrahydrate was used. 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 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. , 26.9 g of a grey-green copper complex (C3-Cu) was obtained. The yield was 70.2% based on the ligand (L3).

Production Example 6: Metal Complex C3-Co
Similar to Production Example 5 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. As a result, 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. , 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 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. , 23.1 g of a grey-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. , 23.6 g of a grey-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. , 26.6 g of a grey-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. 16.6 g of a grey-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 copper acetate monohydrate 0. The yellow cobalt complex (C10-Co) 3 was prepared 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 .60 g (0.003 mol). .14 g was obtained. The yield was 85.8% based on the ligand (L10).
The structural formula of the ligand is shown in Table 1.

(Matrix material: Preparation of sol solution of silicon alkoxide)
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 wt% 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 wt% 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 the matrix material (1) 2.0 g obtained in Production Example 14, 0.008 g of the metal complex C1-Cu, and 0.11 g (0.0006 mol) of aminopropyltrimethoxysilane (KBM-903 manufactured by Shin-Etsu Silicone) were added. It added, stirring, and mixing, and obtained the composition for ultraviolet absorption members.
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 thickness of the coating film was 10 μm.

Example 2
Instead of 0.11 g (0.0006 mol) of aminopropyltrimethoxysilane (Shin-Etsu Silicone KBM-903) in Example 1, 0.21 g (0.0012 mol) of aminopropyltrimethoxysilane (Shin-Etsu Silicone KBM-903) Except that was used, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained in the same manner as in Example 1. The thickness of the coating film was 10 μm.

Example 3
Instead of 0.11 g (0.0006 mol) of aminopropyltrimethoxysilane (Shin-Etsu Silicone KBM-903) in Example 1, 0.43 g (0.0024 mol) of aminopropyltrimethoxysilane (Shin-Etsu Silicone KBM-903) Except that was used, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained in the same manner as in Example 1. The coating film thickness was 11 μm.

Example 4
In Example 1, instead of 0.11 g (0.0006 mol) of aminopropyltrimethoxysilane (KBM-903 made by Shin-Etsu Silicone), N-phenyl-3-aminopropyltrimethoxysilane (KBM-573 made by Shin-Etsu Silicone) Except having used 15g (0.0006 mol), it carried out similarly to Example 1, and obtained the composition for ultraviolet absorbers, and an ultraviolet absorber. The coating film thickness was 11 μm.

Example 5
In Example 1, instead of 0.11 g (0.0006 mol) of aminopropyltrimethoxysilane (KBM-903 made by Shin-Etsu Silicone), N-phenyl-3-aminopropyltrimethoxysilane (KBM-573 made by Shin-Etsu Silicone) Except having used 31g (0.0012mol), it carried out similarly to Example 1, and obtained the composition for ultraviolet absorbers, and an ultraviolet absorber. The thickness of the coating film was 10 μm.

Example 6
In Example 1, instead of 0.11 g (0.0006 mol) of aminopropyltrimethoxysilane (KBM-903 made by Shin-Etsu Silicone), N-phenyl-3-aminopropyltrimethoxysilane (KBM-573 made by Shin-Etsu Silicone) Except having used 61 g (0.0024 mol), it carried out similarly to Example 1, and obtained the composition for ultraviolet absorbers, and an ultraviolet absorber. The coating film thickness was 11 μm.

Example 7
Instead of 0.11 g (0.0006 mol) of aminopropyltrimethoxysilane (KBM-903 manufactured by Shin-Etsu Silicone) in Example 1, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (KBM manufactured by Shin-Etsu Silicone) was used. -603) A composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained in the same manner as in Example 1 except that 0.25 g (0.0011 mol) was used. The coating film thickness was 9 μm.

Example 8
In Example 2, it replaced with metal complex C1-Cu0.008g, and except having used metal complex C2-Cu0.008g, it carried out similarly to Example 1, and obtained the composition for ultraviolet absorbers, and an ultraviolet absorber. The coating film thickness was 11 μm.

Example 9
Example 2 Except that the metal complex C3-Cu 0.008 g was used instead of the metal complex C1-Cu 0.008 g, and that 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 1, a composition for ultraviolet absorbing member and an ultraviolet absorbing member were obtained. The thickness of the coating film was 10 μm.

Example 10
In Example 2, it replaced with metal complex C1-Cu0.008g, and except having used metal complex C4-Cu0.008g, it carried out similarly to Example 1, and obtained the composition for ultraviolet absorbers, and an ultraviolet absorber. The thickness of the coating film was 10 μm.

Example 11
In Example 2, instead of the metal complex C1-Cu 0.008 g, a metal complex C5-Cu 0.008 g was used, and 2.0 g of the matrix material (2) was used instead of 2.0 g of the matrix material (1). In the same manner as in Example 1, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained. The thickness of the coating film was 10 μm.

Example 12
In Example 2, it replaced with metal complex C1-Cu0.008g, and except having used metal complex C6-Cu0.008g, it carried out similarly to Example 1, and obtained the composition for ultraviolet absorbers, and an ultraviolet absorber. The thickness of the coating film was 10 μm.

Example 13
Instead of metal complex C1-Cu0.008g in Example 2, metal complex C7-Cu0.008g. Furthermore, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained in the same manner as in Example 1 except that 2.0 g of the matrix material (2) was used instead of 2.0 g of the matrix material (1). The coating film thickness was 11 μm.

Example 14
In Example 2, it replaced with metal complex C1-Cu0.008g, and except having used metal complex C8-Cu0.008g, it carried out similarly to Example 1, and obtained the composition for ultraviolet absorbers, and an ultraviolet absorber. The thickness of the coating film was 10 μm.

Example 15
In Example 2, instead of the metal complex C1-Cu0.008g, the metal complex C9-Cu0.008g was used, and the matrix material (2) 2.0g was used instead of the matrix material (1) 2.0g. 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 9 μm.

Example 16
In Example 2, it replaced with metal complex C1-Cu0.008g, and except having used metal complex C1-Co0.008g, it carried out similarly to Example 1, and obtained the composition for ultraviolet absorbers, and an ultraviolet absorber. The coating film thickness was 11 μm.

Example 17
In Example 2, instead of the metal complex C1-Cu0.008g, a metal complex C2-Co0.008g was used, and in addition, the matrix material (1) 2.0g was used instead of the matrix material (2) 2.0g. 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 11 μm.

Example 18
In Example 2, it replaced with metal complex C1-Cu0.008g, and except having used metal complex C3-Co0.008g, it carried out similarly to Example 1, and obtained the composition for ultraviolet absorbers, and an ultraviolet absorber. The coating film thickness was 11 μm.

Example 19
In Example 2, instead of the metal complex C1-Cu 0.008 g, a metal complex C10-Co 0.008 g was used, and 2.0 g of the matrix material (2) was used instead of the matrix material (1) 2.0 g. In the same manner as in Example 1, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained. The thickness of the coating film was 10 μm.

Comparative Example 1
In the same manner as in Example 1 except that 0.11 g (0.0006 mol) of aminopropyltrimethoxysilane (KBM-903 manufactured by Shin-Etsu Silicone) was not used in Example 1, a composition for ultraviolet absorbing member and an ultraviolet absorbing member were used. Obtained. The thickness of the coating film was 10 μm.

Comparative Example 2
In Example 1, 0.11 g (0.0006 mol) of aminopropyltrimethoxysilane (KBM-903 manufactured by Shin-Etsu Silicone) was not used, and 2.0 g of matrix material (2) was substituted for 2.0 g of matrix material (1). Except that was used, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were obtained in the same manner as in Example 1. The thickness of the coating film was 10 μm.

Comparative Example 3
In the same manner as in Example 16 except that 0.11 g (0.0006 mol) of aminopropyltrimethoxysilane (KBM-903 manufactured by Shin-Etsu Silicone) was not used in Example 16, a composition for an ultraviolet absorbing member and an ultraviolet absorbing member were used. Obtained. The thickness of the coating film was 10 μm.

[Evaluation of UV absorbing member]
The ultraviolet absorbing members obtained in Examples 1 to 19 and Comparative Examples 1 to 3 were evaluated by the following procedure.

(1) Evaluation of heat resistance (metal complex remaining rate)
The heat resistance is evaluated by the residual ratio (%) of the metal complex after heating at 200 ° C. for 10 minutes. About the ultraviolet-absorbing member obtained in Examples 1-19 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 corrected transmittance value does not reflect the transmission performance of the film itself, and can be regarded as being derived solely from the concentration of the UV absorber.

  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 1-19 and Comparative Examples 1-3, the hue before and behind a heat resistance test (200 degreeC for 10 minutes) was evaluated by visual observation.

※実施例及び比較例における金属錯体は１００重量部、マトリックス材料は２５０００重量部用いた。
アミノプロピルトリメトキシシラン：ＡＰＴＭＳ
Ｎ−フェニル−３−アミノプロピルトリメトキシシラン：ＰＡＰＴＭＳ
Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン：ＡＥＡＰＴＭＳ

* In the examples and comparative examples, 100 parts by weight of the metal complex and 25,000 parts by weight of the matrix material were used.
Aminopropyltrimethoxysilane: APTMS
N-phenyl-3-aminopropyltrimethoxysilane: PAPTMS
N-2- (aminoethyl) -3-aminopropyltrimethoxysilane: AEAPTMS

Examples 1 to 3 and 8 to 19 are systems using aminopropyltrimethoxysilane as the amino group-containing silane compound, and it can be seen that both the residual ratio and the hue change are excellent.
In Examples 4 to 7, although slight hue change was observed, the residual ratio was greatly improved, and although the degree of hue change was slightly inferior to the above system, UV-A was It was confirmed that it was sufficiently shielded.
Comparative Examples 1 to 3 are systems in which no amino group-containing silane compound 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):

(Where
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 hydrogen atoms on the benzene ring are each independently substituted with a substituent. C1-C8 alkyl group which may have, hydroxyl group, carboxyl group, C1-C4 alkoxy group, halogeno group, C1-C8 alkylamino which may have a substituent A sulfonyl 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, and a substituent Thiomol you may have Have a Rinosuruhoniru group or substituent a 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):

(Where
R ⁷ is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted aromatic group;
R ⁸ is an optionally substituted alkylene group having 1 to 8 carbon atoms, in which some of the carbon atoms may be substituted with oxygen atoms or nitrogen atoms,
R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted aromatic group, It is a C1-C8 alkoxy group, Comprising: At least 1 is an alkoxy group among R < ⁹ >, R < ¹⁰ > and R < ¹¹ >. The composition for ultraviolet absorption members containing the silane compound which has at least 1 type of amino group represented by this, 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 ultraviolet ray according to claim 1 or 2, wherein the silane compound having an amino group represented by the formula (2) is aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropylmethyldimethoxysilane, or aminopropylmethyldiethoxysilane. Composition for absorbent member.   The ultraviolet absorption member produced using the composition for ultraviolet absorption members in any one of Claims 1-3.