JP2013194037A - Copper complex, composition for ultraviolet absorbing member containing the same, and ultraviolet absorbing member using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet absorber which has high superior light resistance and can efficiently block UV-A, conventionally been difficult to block, while retaining visible light transparency at a high level, and to provide a composition for ultraviolet absorbing member and an ultraviolet absorbing member.SOLUTION: A copper complex which is useful as an ultraviolet absorber and has a specified structure exhibited by formula (1), a composition for ultraviolet absorbing member containing the copper complex and at least one kind of matrix material and an ultraviolet absorbing member using the composition are provided.

Description

  The present invention relates to a copper complex useful as an ultraviolet absorber, a composition for an ultraviolet absorbing member containing the copper complex and at least one matrix material, and an ultraviolet absorbing member using the same.

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

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

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

  Inorganic metal oxide fine particles have excellent light resistance, but the absorption wavelength is governed by the band gap inherent to the material, so it is difficult to optimize the absorption wavelength, and the absorption spectrum is often broad. There is a limit to selectively shielding only a desired wavelength region. Inorganic metal oxide fine particles cannot be dissolved in a solvent or the like, so they are usually used in a fine particle dispersed state. However, in order to ensure transparency in the visible light region, it is necessary to reduce the particle size to the nano order. And requires a lot of labor and cost.

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

  Here, ultraviolet rays with a wavelength of 380 to 400 nm are classified as ultraviolet rays having a relatively long wavelength called UV-A, and are most often contained as ultraviolet rays of sunlight reaching the ground surface. However, the human body has a degree of penetration into the skin. Due to the depth, long exposure is known to cause pigmentation and wrinkles. With the enhancement of the functionality of ultraviolet shielding technology in various fields, a material that can sufficiently shield ultraviolet rays of 380 to 400 nm near the boundary with the visible light region and sufficiently transmit visible light of 400 to 780 nm is desired. Yes.

  However, both inorganic metal oxide fine particles and organic ultraviolet absorbers have excellent visible light transparency, a high extinction coefficient in the wavelength range of 380 to 400 nm, and almost all materials having high light resistance. unknown.

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

  The present invention is intended to solve the problems associated with the prior art as described above. It has excellent light resistance, and UV-A, which has been difficult to shield while maintaining a high level of visible light transparency. It aims at providing the ultraviolet absorber which can shield efficiently, the composition for ultraviolet absorbers containing this, and the ultraviolet absorber using the same.

  The present inventors have shown that the following copper complex has excellent light resistance and visible light transparency, and can effectively shield UV-A, which has been difficult to shield conventionally, as an ultraviolet absorber. It was found useful and the present invention was completed.

The present invention
Item 1. Formula (1):

（式中、ＸおよびＹはそれぞれ互いに独立して酸素原子または硫黄原子であり、Ｚはハロゲノ基、アセタト基、アセチルアセトナト基、ニトラト基であり、
Ｒ^１はモルホリノスルホニル基、チオモルホリノスルホニル基、ピペラジノスルホニル基またはＮ−置換ピペラジノスルホニル基であり、
Ｒ^２は、存在しないか、または存在する場合は、１つのベンゼン環の６個の炭素原子のうち５員環と共有された２個の炭素原子とＲ^１が結合した炭素原子を除いた最大３個の炭素原子に結合する水素原子のうち１ないし３個を置換することができ、ベンゼン環の水素原子を置換したＲ^２はそれぞれ互いに独立して、炭素数１〜８のアルキル基、炭素数１〜４のアルコキシ基、ハロゲノ基、モルホリノスルホニル基、チオモルホリノスルホニル基、ピペラジノスルホニル基またはＮ−置換ピペラジノスルホニル基であり、
Ｒ^３は、存在しないか、または存在する場合は、１つのベンゼン環の６個の炭素原子のうち５員環と共有された２個の炭素原子を除いた４個の炭素原子に結合する４個の水素原子のうち１ないし４個を置換することができ、ベンゼン環の水素原子を置換したＲ^３はそれぞれ互いに独立して、炭素数１〜８のアルキル基、炭素数１〜４のアルコキシ基、ハロゲノ基、モルホリノスルホニル基、チオモルホリノスルホニル基、ピペラジノスルホニル基またはＮ−置換ピペラジノスルホニル基を示す。）で表される銅錯体；

(In the formula, X and Y are each independently an oxygen atom or a sulfur atom, Z is a halogeno group, an acetate group, an acetylacetonato group or a nitrato group;
R ¹ is a morpholinosulfonyl group, a thiomorpholinosulfonyl group, a piperazinosulfonyl group or an N-substituted piperazinosulfonyl group,
R ² is absent or, if present, the maximum excluding the carbon atoms bonded to R ¹ and the two carbon atoms shared with the 5-membered ring among the six carbon atoms of one benzene ring 1 to 3 of hydrogen atoms bonded to 3 carbon atoms can be substituted, and R ² substituted with hydrogen atoms of the benzene ring are independently of each other an alkyl group having 1 to 8 carbon atoms, carbon A C 1-4 alkoxy group, a halogeno group, a morpholinosulfonyl group, a thiomorpholinosulfonyl group, a piperazinosulfonyl group or an N-substituted piperazinosulfonyl group;
R ³ is absent or, if present, 4 bonded to 4 carbon atoms, excluding the 2 carbon atoms shared with the 5-membered ring among the 6 carbon atoms of one benzene ring. 1 to 4 of the hydrogen atoms can be substituted, and each R ³ substituted with a hydrogen atom of the benzene ring is independently of each other an alkyl group having 1 to 8 carbon atoms or an alkoxy having 1 to 4 carbon atoms. A group, a halogeno group, a morpholinosulfonyl group, a thiomorpholinosulfonyl group, a piperazinosulfonyl group or an N-substituted piperazinosulfonyl group; Copper complex represented by:

Item 2. Item 4. A composition for an ultraviolet absorbing member comprising at least one copper complex according to Item 1 and at least one matrix material;

Item 3. The ultraviolet absorption member produced using the composition for ultraviolet absorption members of claim | item 2 is provided.

  ADVANTAGE OF THE INVENTION According to this invention, it has the outstanding light resistance, the ultraviolet absorber which can fully shield UV-A which was difficult to shield conventionally, maintaining visible light transparency highly, and ultraviolet rays containing this A composition for an absorbing member and an ultraviolet absorbing member using the same can be provided.

<< A. Copper complex of the present invention >>
The copper complex of the present invention has excellent light resistance and visible light transparency, and is useful as an ultraviolet absorber capable of efficiently shielding UV-A, which has been difficult to shield conventionally. 1):

（式中、ＸおよびＹはそれぞれ互いに独立して酸素原子または硫黄原子であり、Ｚはハロゲノ基、アセタト基、アセチルアセトナト基、ニトラト基であり、
Ｒ^１はモルホリノスルホニル基、チオモルホリノスルホニル基、ピペラジノスルホニル基またはＮ−置換ピペラジノスルホニル基であり、
Ｒ^２は、存在しないか、または存在する場合は、１つのベンゼン環の６個の炭素原子のうち５員環と共有された２個の炭素原子とＲ^１が結合した炭素原子を除いた最大３個の炭素原子に結合する水素原子のうち１ないし３個を置換することができ、ベンゼン環の水素原子を置換したＲ^２はそれぞれ互いに独立して、炭素数１〜８のアルキル基、炭素数１〜４のアルコキシ基、ハロゲノ基、モルホリノスルホニル基、チオモルホリノスルホニル基、ピペラジノスルホニル基またはＮ−置換ピペラジノスルホニル基であり、
Ｒ^３は、存在しないか、または存在する場合は、１つのベンゼン環の６個の炭素原子のうち５員環と共有された２個の炭素原子を除いた４個の炭素原子に結合する４個の水素原子のうち１ないし４個を置換することができ、ベンゼン環の水素原子を置換したＲ^３はそれぞれ互いに独立して、炭素数１〜８のアルキル基、炭素数１〜４のアルコキシ基、ハロゲノ基、モルホリノスルホニル基、チオモルホリノスルホニル基、ピペラジノスルホニル基またはＮ−置換ピペラジノスルホニル基を示す。）で表される。

(In the formula, X and Y are each independently an oxygen atom or a sulfur atom, Z is a halogeno group, an acetate group, an acetylacetonato group or a nitrato group;
R ¹ is a morpholinosulfonyl group, a thiomorpholinosulfonyl group, a piperazinosulfonyl group or an N-substituted piperazinosulfonyl group,
R ² is absent or, if present, the maximum excluding the carbon atoms bonded to R ¹ and the two carbon atoms shared with the 5-membered ring among the six carbon atoms of one benzene ring 1 to 3 of hydrogen atoms bonded to 3 carbon atoms can be substituted, and R ² substituted with hydrogen atoms of the benzene ring are independently of each other an alkyl group having 1 to 8 carbon atoms, carbon A C 1-4 alkoxy group, a halogeno group, a morpholinosulfonyl group, a thiomorpholinosulfonyl group, a piperazinosulfonyl group or an N-substituted piperazinosulfonyl group;
R ³ is absent or, if present, 4 bonded to 4 carbon atoms, excluding the 2 carbon atoms shared with the 5-membered ring among the 6 carbon atoms of one benzene ring. 1 to 4 of the hydrogen atoms can be substituted, and each R ³ substituted with a hydrogen atom of the benzene ring is independently of each other an alkyl group having 1 to 8 carbon atoms or an alkoxy having 1 to 4 carbon atoms. A group, a halogeno group, a morpholinosulfonyl group, a thiomorpholinosulfonyl group, a piperazinosulfonyl group or an N-substituted piperazinosulfonyl group; ).

Z, R ¹ , R ² and R ³ in the formula (1) are exemplified below.

  In the formula, examples of the halogeno group belonging to Z include a chloro group and a bromo group. A chloro group is preferable from the viewpoint of availability of raw materials.

In the formula, examples of the N-substituted piperazinosulfonyl group belonging to R ¹ , R ² and R ³ include an N-methylpiperazinosulfonyl group, an N-ethylpiperazinosulfonyl group, and an N-propylpipepe group. Examples thereof include a radinosulfonyl group and an N-phenylpiperazinosulfonyl group. From the viewpoint of availability of raw materials, an N-methylpiperazinosulfonyl group and an N-ethylpiperazinosulfonyl group are preferable.

In the formula, examples of the alkyl group having 1 to 8 carbon atoms belonging to R ² and R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl 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, 2-ethylhexyl group, etc. An alkyl group is mentioned. From the viewpoint of availability of raw materials, a methyl group, an ethyl group, an n-butyl group, an isobutyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, and a 2-ethylhexyl group are preferable, and a methyl group, an n-butyl group, An isobutyl group, an n-hexyl group, and an n-octyl group are more preferable, and a methyl group is more preferable.

In the formula, examples of the alkoxy group having 1 to 4 carbon atoms belonging to R ² and R ³ include a methoxy group, an ethoxy group, and a tert-butoxy group. From the viewpoint of availability of raw materials, a methoxy group and an ethoxy group are preferable.

In the formula, examples of the halogeno group belonging to R ² and R ³ include a fluoro group, a chloro group, a bromo group, and an iodo group. From the viewpoint of availability of raw materials, a fluoro group and a chloro group are preferable, and a chloro group is more preferable.

From the viewpoint of achieving both the light absorption performance of the obtained copper complex and the ease of synthesis, both R ¹ and R ³ are preferably morpholinosulfonyl groups or thiomorpholinosulfonyl groups, and R ² is absent or carbon. A C 1-4 alkoxy group, a halogeno group, a morpholinosulfonyl group, or a thiomorpholinosulfonyl group is preferable.

  The copper complex represented by the formula (1) has the following formula (2):

で表される配位子と、銅（II）ハロゲン化物、銅（II）酢酸塩、銅（II）アセチルアセトン塩、銅（II）硝酸塩等の銅塩とを反応させることで合成することができる。

And a copper salt such as copper (II) halide, copper (II) acetate, copper (II) acetylacetone salt, and copper (II) nitrate can be synthesized. .

  The ligand represented by the formula (2) can be synthesized by, for example, a method disclosed in WO2011 / 089794 and WO2012 / 012476.

  For example, while dissolving the ligand represented by the formula (2) obtained by the above-mentioned known method in a solvent and stirring the solution, a solution in which a copper salt is dissolved in the solvent is added dropwise, and then a precipitate is formed. The copper complex can be obtained by filtering, and washing with an optional washing solvent as necessary, followed by drying.

  In addition, you may dripped the solution which melt | dissolved the ligand represented by Formula (2) here in a solvent, dissolving a copper salt in a solvent and stirring. It is also possible to charge the ligand represented by the formula (2), the copper salt, and the solvent in a lump and stir, and thereafter obtain a copper complex by the same procedure as described above.

  Examples of the copper (II) salt that can be used here include copper (II) halide, copper (II) acetate, copper (II) acetylacetone salt, and copper nitrate. Specifically, copper (II) chloride, copper (II) bromide, copper (II) acetate, bis (2,4-pentanedionato) copper (II), copper nitrate (II), and their hydration Things.

  It is preferable that the usage-amount of copper salt is 0.8-1.2 mol with respect to 1 mol of ligands represented by Formula (2). When the amount is less than 0.8 mol, the ligand represented by the formula (2) may be mixed as an impurity in the obtained product. It is not economical because it is discarded without being consumed.

  Examples of the solvent that can be used here include water, alcohols such as methanol, ethanol, and 2-propanol (IPA); ketones such as acetone, 2-butanone (MEK), cyclopentanone, and cyclohexanone; , Ethers such as tetrahydrofuran (THF) and diethyl ether, aromatics such as toluene and monochlorobenzene, halogenated hydrocarbons such as chloroform and dichloromethane, N, N-dimethylformamide (DMF), N-methyl Examples include amides such as pyrrolidone (NMP), esters such as ethyl acetate, dimethyl sulfoxide (DMSO), and acetonitrile. Preferred are methanol, ethanol, IPA, DMF, NMP, DMSO, and more preferred is DMF.

  In addition, you may use 2 or more types in mixture among these illustrated. In addition, the solvent for dissolving the ligand represented by the formula (2) and the solvent for dissolving the copper salt are not necessarily the same, and the above-described solubility of each solute is within the allowable range. One or more different solvents may be selected and used from those exemplified.

  The amount of these solvents used is not particularly limited, but is usually 1000 to 40000 g, preferably 2000 to 25000 g, more preferably 2500 to 1 mol of the ligand represented by the formula (2). 15000g. If the amount is less than 1000 g, the complexing reaction does not proceed sufficiently, and the purity of the resulting copper complex may be reduced. If the amount exceeds 40000 g, the yield may be reduced.

  As reaction temperature, it is 0-100 degreeC normally, Preferably it is 5-80 degreeC. Below 0 ° C., the solubility of the raw material decreases, so a large amount of solvent is required, and as a result, the volumetric efficiency decreases, which is not economical. Moreover, even if the reaction temperature is set above 100 ° C., the reaction rate cannot be further improved, and this is not economical.

  The reaction time is usually 10 minutes to 10 hours, preferably 1 to 5 hours. If it is shorter than 10 minutes, the progress of the reaction may be insufficient and the yield may be lowered, and even if the reaction is carried out for more than 10 hours, an improvement in yield corresponding to the reaction cannot be expected, which is not economical.

  After completion of the reaction, the deposited copper complex may be filtered off as it is, or after adding a poor solvent for the copper complex.

  The washing solvent after separation of the precipitate is not particularly limited, but considering the subsequent drying step, a low boiling point solvent is preferable, and examples thereof include methanol, ethanol, acetone and the like. Further, for the purpose of removing impurities by the main cleaning, a solvent having good impurity solubility may be selected and used.

  The amount of the washing solvent used is not particularly limited, and can be arbitrarily set within a range in which the required washing effect is obtained. Usually, 1 mol of the ligand represented by the formula (2) is used. It is 100-10000g with respect to.

  The copper complex represented by the formula (1) efficiently shields UV-A, which has been difficult to shield conventionally, and exhibits much better light resistance than a general organic ultraviolet absorber. Moreover, since the ultraviolet shielding ability per unit mass is superior to the conventionally known metal oxide fine particles, sufficient ultraviolet shielding ability can be imparted with a small amount of addition, and transparency in the visible light region is also provided. It is also a notable feature that it is very good.

<< B. Composition for UV Absorbing Member of the Present Invention >>
The composition for ultraviolet absorbing members of the present invention contains at least one copper complex represented by the formula (1) and at least one matrix material.

In the composition for ultraviolet absorbing members of the present invention, the copper complex represented by the formula (1) may be in a dissolved state, or the fine particles of the copper complex represented by the formula (1) may be in a dispersed state. There may be something.
In the case of the composition for an ultraviolet absorbing member containing the copper complex represented by the formula (1) in a dissolved state, it is particularly advantageous for ensuring the visible light transparency of the finally obtained ultraviolet absorbing member, In the case of the composition for ultraviolet absorbing members containing the copper complex fine particles represented by the formula (1) in a dispersed state, it is particularly advantageous for obtaining an ultraviolet absorbing member having excellent light resistance.

  The composition for an ultraviolet absorbing member of the present invention includes a case where “the copper complex represented by the formula (1) is in a dissolved state at a molecular level” in the composition for an ultraviolet absorbing member and a case represented by the formula (1). The case where the copper complex is in a fine particle dispersed state is shown. Each will be described below.

(B1) Composition for UV-absorbing member when copper complex is in dissolved state at molecular level Specifically, by using a solvent in which both the matrix material and the copper complex of the present invention have good solubility, A uniform composition for an ultraviolet-absorbing member, in which the matrix material and the copper complex are dissolved, can be obtained.

  When a polymerizable monomer is used as the matrix material, the solvent is not always necessary, and the polymerizable monomer can be used as a precursor of the matrix material and as a solvent.

  The matrix material may be any of an organic binder, an inorganic binder, and a polymerizable monomer. Here, the inorganic binder means a polymer main chain that does not contain a carbon atom, and the inorganic binder in the present invention includes an oligomer such as a silicon alkoxide sol.

  Examples of the organic binder include poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, poly (meth) acrylate cyclohexyl and the like. (Meth) acrylic acid such as (meth) acrylic ester resin, methyl (meth) acrylate- (meth) ethyl acrylate copolymer, (meth) methyl acrylate- (meth) butyl acrylate copolymer Ester copolymers, polystyrene resins such as polystyrene and poly (α-methylstyrene), styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylic acid copolymers, styrene-acrylic acid ester copolymers Such as polymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, etc. Copolymer, polyethylene succinate, polybutylene adipate, polyester resin such as polylactic acid, polyglycolic acid, polycaprolactone, polyethylene terephthalate, polyolefin resin such as polyethylene and polypropylene, polyoxymethylene, polyethylene oxide Such as polyether resins, polysulfone resins, polyamide resins, polyimide resins, polyurethane resins, polycarbonate resins, epoxy resins, phenol resins, melamine resins, urea resins, etc. And thermoplastic or thermosetting synthetic resins such as polyvinyl resins, synthetic rubbers such as ethylene-propylene copolymer rubber, polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, or natural rubber. I can get lost.

From the viewpoint of adhesion to a substrate and transparency, preferably a poly (meth) acrylate resin, a polystyrene resin, a styrene copolymer, a polyester resin, a polyolefin resin, a polyether resin, a polysulfone Resin, polyamide resin, polyimide resin, polyurethane resin, polycarbonate resin, epoxy resin, phenol resin, melamine resin, urea resin, polyvinyl resin, and other thermoplastic or thermosetting synthetic resins, and more Preferably, poly (meth) acrylate resin, polystyrene resin, styrene copolymer, polyester resin, polyolefin resin, polyether resin, polycarbonate resin, epoxy resin, phenol resin, polyvinyl resin Resin.
In addition, (meth) acryl shows methacryl and acryl.

  As the inorganic binder, a polysiloxane binder can be suitably used. For example, a silicone resin or a sol solution (siloxane oligomer solution) obtained by hydrolysis / polycondensation reaction of silicon alkoxide as a polysiloxane binder precursor can be suitably used.

  The sol solution of silicon alkoxide can be prepared by a known method. Usually, it can be prepared by adding water to silicon alkoxide in the presence of an acid catalyst in an organic solvent, followed by hydrolysis and polycondensation, but a commercially available sol solution may be used. Hereinafter, a method for preparing a sol solution of silicon alkoxide will be described in detail.

(Silicon alkoxide)
Examples of the silicon alkoxide include tetrafunctional alkoxysilanes 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, hexyltriethoxysilane, hexyltripropoxysilane, hexyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxy Silane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, methyldimethoxy (ethoxy) silane, Tildiethoxy (methoxy) silane, trimethoxysilylpropanethiol, triethoxysilylpropanethiol, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, 4- (2-aminoethylaminomethyl) phenethyltrimethoxysilane, trimethoxysilylethylenediamine, N, N′-bis [3- (trimethoxysilyl) propyl] Such as ethylenediamine, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 Glycidoxypropyltrimethoxysilane, and 3-functional alkoxysilanes such as 3-glycidoxypropyl triethoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane, bis (2-methoxyethoxy) dimethylsilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3- (dimethoxymethylsilyl) -1-propanethiol, etc. Bifunctional alkoxysilanes such as aminopropyldiethoxymethylsilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane are exemplified.

  Among these, from the viewpoint of the state and strength of the resulting film, tetrafunctional alkoxysilane and trifunctional alkoxysilane are preferable, and tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, Phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) aminopropyltri Methoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, trimethoxysilylethylenediamine, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, Idopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy More preferred is silane.

  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.

  Further, in order to impart desired physical properties to the finally obtained coating film, a metal alkoxide such as titanium alkoxide, cerium alkoxide, zirconium alkoxide, tin alkoxide, aluminum alkoxide, nickel alkoxide, zinc alkoxide, etc. You may add and use together.

(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 the acid remains after completion of the hydrolysis / polycondensation reaction, the condensation stability deteriorates. Therefore, it is preferable to use nitric acid, hydrochloric acid, formic acid, or acetic acid having a low boiling point and high volatility.

  The addition amount of the acid catalyst is not particularly limited as long as sufficient catalytic action is exhibited, but it is usually preferable to add 0.01 mol or more with respect to 100 mol of silicon alkoxide. If the amount is less than 0.01 mol, sufficient catalytic action may not be obtained, and if added excessively, the stability of the finally obtained silicon alkoxide sol solution may be deteriorated. 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 2-30 mol with respect to 1 mol of silicon alkoxide, and it is more preferable that it is 2-20 mol. If the amount is less than 2 mol, hydrolysis may not proceed sufficiently. If the amount exceeds 30 mol, the hydrolysis reaction may be accelerated and the stability of the sol solution may be deteriorated. In addition, the amount of water removed after the reaction is large. It is 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, IPA, tetrafluoropropanol, 2-methoxyethanol and 2-ethoxyethanol, ketones such as acetone, MEK, cyclopentanone and cyclohexanone, and ethers such as THF and diethyl ether Aromatics such as toluene and monochlorobenzene, halogenated hydrocarbons such as chloroform and dichloromethane, amides such as DMF and NMP, esters such as ethyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl Ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate Over preparative (PGMEA), glycol ethers such as propylene glycol monomethyl ether acetate and, or acetonitrile, sulfolane or, DMSO, and the like.

  From the viewpoint of reactivity and economy, alcohols such as methanol, ethanol, IPA, tetrafluoropropanol, 2-methoxyethanol and 2-ethoxyethanol, ketones such as acetone, MEK, cyclopentanone and cyclohexanone, THF , Ethers such as diethyl ether, amides such as DMF and NMP, esters such as ethyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether Glycol ethers such as acetate, PGMEA, and propylene glycol monoethyl ether acetate, DMSO, and the like are preferable.

  The reaction solvent is used in an amount of 10 to 3000 parts by weight, preferably 10 to 1000 parts by weight, based on 100 parts by weight of silicon alkoxide. If the amount is less than 10 parts by weight, it may be difficult to cause the hydrolysis / polycondensation reaction to proceed at an appropriate reaction rate. If the amount exceeds 3000 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 or more types of silicon alkoxide are mixed with an acid catalyst, water, and a solvent. By maintaining this solution at a temperature of 0 to 150 ° C., preferably 10 to 80 ° 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 0.5 to 48 hours, more preferably 1 to 24 hours, although it depends on temperature conditions. If the time is less than 0.5 hours, the hydrolysis / polycondensation reaction may not proceed sufficiently, and if the time exceeds 48 hours, the reaction does not proceed any further, which is not economical.

  In order to remove alcohol and water by-produced by hydrolysis / polycondensation reaction from the system, a step of distilling off the reaction solution under reduced pressure may be provided after the reaction is completed 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. In this step, if a low boiling point and highly volatile catalyst 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 silicon alkoxide as an inorganic binder can be obtained by the progress of hydrolysis and polycondensation reaction.

  The polymerizable monomer may be either an organic polymerizable monomer or an inorganic polymerizable monomer. In addition, an inorganic type polymerizable monomer shows what does not contain a carbon atom in the polymer principal chain formed by a polymerization reaction.

  Examples of the organic polymerizable monomer include styrene, α-methylstyrene, β-methylstyrene, 2,4-dimethylstyrene, α-ethylstyrene, α-butylstyrene, α-hexylstyrene, 4-chlorostyrene, 3 -Styrene monomers such as chlorostyrene, 4-bromostyrene, 4-nitrostyrene, 4-methoxystyrene, vinyltoluene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (Meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-methylbutyl (meth) acrylate, 2-ethylbutyl (meth) acrylate , 3-methylbutyl (meth) Acrylate, 1,3-dimethylbutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethoxyethyl ( (Meth) acrylate, 3-ethoxypropyl (meth) acrylate, 2-ethoxybutyl (meth) acrylate, 3-ethoxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) ) Acrylate, hydroxybutyl (meth) acrylate, ethyl-α- (hydroxymethyl) (meth) acrylate, methyl-α- (hydroxymethyl) (meth) acrylate, phenyl (meth) acrylate Rate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol (Meth) acrylates such as tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl glycol di (meth) acrylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, allylcyclohexene dioxide, , 4-epoxy-4-methylcyclohexyl-2-propylene oxide and bis (3,4-epoxycyclohexyl) ether, and other alicyclic epoxy compounds, bisphenol A, bisphenol F, brominated bisphenol A, biphenol, resorcin, etc. Glycidyl etherified compounds, trimethylene oxide, 3-ethyl-3-hydroxymethyloxetane, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-ethyl-3-phenoxymethyloxetane, 3-ethyl -3-[{(3-ethyloxetanyl) methoxy} methyl] oxetane, bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] Benzene, tri [(3-ethyl- - oxetanylmethoxy) methyl] benzene, bis [(3-ethyl-3-oxetanylmethoxy) methylphenyl] ether, (3-ethyl-3-oxetanylmethoxy) oxetane compounds such as oligo dimethylsiloxanes like.

  Examples of the inorganic polymerizable monomer include the same monomers as those exemplified in the section of the sol solution of silicon alkoxide as the inorganic binder.

  These matrix materials may be used alone or in combination of two or more.

The solvent having good solubility of the matrix material and the copper complex can be appropriately selected and used according to the type of the matrix material and the copper complex to be used. Specific examples include those exemplified as the reaction solvent in the description of the method for preparing the silicon alkoxide sol solution.
Among these, more preferable from the viewpoint of the solubility of the copper complex are tetrafluoropropanol as alcohols, MEK as cycloketones, cyclopentanone, cyclohexanone, tetrahydrofuran as ethers, halogenated carbonization. Examples of hydrogens include chloroform and dichloromethane, and examples of amides include DMF, NMP, and other dimethyl sulfoxides.

  Moreover, you may use the said polymerizable monomer illustrated as a matrix material as a solvent.

  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 set within a range where both the matrix material and the copper complex are dissolved.

  The amount of the solvent used can be appropriately adjusted in consideration of the concentration of the copper complex in the desired composition for an ultraviolet absorbing member, the type of solvent used, the solubility of the matrix material used, etc. Although not limited, from the viewpoint of solubility of the copper complex, it is usually 5 to 10000 parts by weight, preferably 10 to 5000 parts by weight, more preferably 50 to 1000 parts by weight with respect to 1 part by weight of the copper complex. Parts by weight. If the amount is less than 5 parts by weight, the copper complex may not be completely dissolved, and the visible light transparency of the finally obtained ultraviolet absorbing member may be impaired. On the other hand, when the amount is more than 10,000 parts by weight, it may be difficult to obtain a desired film thickness for imparting sufficient ultraviolet absorbing ability to the ultraviolet absorbing member.

  Further, as long as the effects of the present invention are not impaired, a curing agent, a curing catalyst, a crosslinking agent, a coupling agent, a leveling agent, a lubricant, an antistatic agent, an antioxidant, a thermal stabilizer, a flame retardant, and a filler , Colorants, photocatalyst materials, rust inhibitors, water repellents, conductive materials, antiblocking materials, softeners, mold release agents, fluorescent whitening agents, ultraviolet absorbers, and the like may be added as appropriate.

  In the case where a polymerizable monomer is used, a polymerization initiator may be used in combination when a polymerization step is provided when producing an ultraviolet absorbing member described later. It does not specifically limit as a polymerization initiator, According to the kind of polymerizable monomer to be used, it can select suitably. Further, the amount used can be appropriately selected according to the activities of the polymerizable monomer and the polymerization initiator.

  Examples of the radical polymerization initiator used in the case of thermosetting include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), and 2,2′-azo. Azo compounds such as bisisovaleronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis (cyclohexanone-1-carbonitrile), methyl ethyl ketone peroxide, methyl isobutyl ketone per Examples thereof include ketone peroxides such as oxide and cyclohexanone peroxide, and diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, and 2,4-dichlorobenzoyl peroxide.

  Examples of the radical polymerization initiator used in the case of photocuring include p-isopropyl-α-hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone, 4′-methylthio-2, Examples include 2-dimethyl-2-morpholinoacetophenone, benzoin isobutyl ether, 2-chlorothioxanthone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. it can.

  Examples of the cationic polymerization initiator used in thermosetting include boron trifluoride / diethyl ether complex, boron trifluoride / amine complex, aluminum chloride, titanium tetrachloride, tin tetrachloride, iron (III) chloride. And Lewis acids such as zinc chloride, ammonium salts, sulfonium salts, oxonium salts, phosphonium salts, and the like.

  Examples of the cationic polymerization initiator used in the case of photocuring include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic phosphonium salts, and the like.

  As the curing agent, as used when using an epoxy monomer as the polymerizable monomer, for example, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, Acid anhydrides such as chlorendic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, diethylenetriamine, triethylenediamine, triethylenetetramine, tetraethylenepentamine, Aliphatic amines such as diethylaminopropylamine, N-aminoethylpiperazine, isophoronediamine, mensendiamine, piperidine, N, N-dimethylpiperazine, m-phenylenediamine, 4,4′-diaminodi Enirumetan, 4,4'-diaminodiphenyl aromatic amines diphenyl sulfone and, polymercaptans include a polysulfide and the like.

Among these, acid anhydrides are preferable in terms of improving the mechanical properties of the epoxy resin after polymerization, and in terms of operability, those which are liquid at normal temperature are preferable. Specific examples include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, and the like.
When using acid anhydrides that are solid at room temperature, such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, etc., dissolve in liquid acid anhydrides at room temperature And is preferably used as a liquid mixture at room temperature.

  In order to accelerate the curing reaction of the epoxy monomer, a curing accelerator can be further used. A hardening accelerator can be used individually or in mixture of 2 or more types. For example, 2-ethyl-4-methylimidazole, 2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, benzyldimethylamine, 2,4,6-tris (diaminomethyl) phenol, 1,8- Tertiary amines such as diazabicyclo (5,4,0) undecene-7 and its octylate, imidazoles and / or their organic carboxylates, triphenylphosphine, tributylphosphine, benzyltriphenylphosphonium bromine salt Phosphines such as benzyltributylphosphonium bromide and / or quaternary salts thereof, organic carboxylic acid metal salts such as zinc octylate, zinc laurate, zinc stearate, tin octylate, zinc and β-diketone Acetylacetone zinc chelate, benzoyl Seton zinc chelate, dibenzoylmethane zinc chelates, metal such as acetoacetic zinc chelate - organic chelate compounds and include aromatic sulfonium salts and the like.

(B2) Composition for ultraviolet absorbing member when fine particles of copper complex are in a dispersed state For example, a dispersion of the copper complex is prepared in advance and mixed with a matrix material (or a solution of a matrix material prepared separately) Thus, a composition for an ultraviolet absorbing member in which the fine particles of the copper complex are in a dispersed state can be obtained.

  As the matrix material, any of organic and inorganic binders can be used. The above-mentioned “(B1) composition for ultraviolet absorbing member when copper complex is in a dissolved state at a molecular level”. It can be used by appropriately selecting from the same range as described in the section.

  When the dispersion of the copper complex is prepared in advance, examples of the dispersion medium that can be used include water, alcohols such as methanol, ethanol, IPA, 2-methoxyethanol, and 2-ethoxyethanol, ethylene glycol, Glycols such as 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, ketones such as acetone, MEK, cyclopentanone, cyclohexanone, esters such as ethyl acetate, , Ethers such as THF, diethyl ether, aromatics such as toluene and monochlorobenzene, hydrocarbons such as n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, cycloheptane, and ethylene glycol Monomethyl ether acetate, diethyl Glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono -n- butyl ether acetate, PGMEA, glycol ethers and acetonitrile and propylene glycol monoethyl ether acetate and include exemplary polymerizable monomer before.

From the viewpoint of the dispersibility of the copper complex and the stability of the resulting dispersion, alcohols such as water, methanol, ethanol, IPA, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol, 1,2-propane Diols, 1,3-propanediol, 1,4-butanediol, glycols such as diethylene glycol, aromatics such as toluene, monochlorobenzene, n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane , Hydrocarbons such as cycloheptane, 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, glycol ethers such as propylene glycol monomethyl ether acetate are preferable, and particularly preferable is water.
These dispersion media may be used alone or in combination of two or more. The mixing ratio in the case of using a mixed dispersion medium in which two or more types are combined can be appropriately selected.

  The amount of the dispersion medium to be used should be appropriately set in consideration of the desired concentration of the copper complex in the composition for ultraviolet absorbing members, the solubility of the matrix material used, the compatibility with the solution of the matrix material, and the like. Although not particularly limited, from the viewpoint of the dispersibility of the copper complex and the stability of the resulting dispersion, it is usually 150 to 9900 parts by weight, preferably 100 parts by weight of the copper complex, 250 to 4900 parts by weight. If the amount is less than 150 parts by weight, the dispersibility may be deteriorated and the particles may not be atomized. On the other hand, when the amount is more than 9900 parts by weight, the solid content concentration is lowered, so that a sufficient shearing force cannot be applied, and it takes a long time to atomize the copper complex, which may cause a reduction in efficiency.

  The average particle diameter of the copper complex fine particles in the composition for an ultraviolet absorbing member is 10 nm to 400 nm, preferably 10 nm to 300 nm, more preferably 10 nm to 200 nm, and still more preferably 10 nm to 150 nm. When the average particle diameter is larger than 400 nm, the visible light transparency is impaired, and the mechanical strength of the finally obtained coating film may be lowered. Further, when the particle diameter is larger than 400 nm, the ultraviolet absorption capacity corresponding to the amount added cannot be obtained due to the decrease in the surface area of the particles, which is disadvantageous in terms of cost. On the other hand, when the average particle size is 10 nm or less, it is close to a dissolved state and the visible light transparency is improved, but the light resistance is lowered, and the merit of using in a dispersion system may be impaired.

(Dispersing machine)
A dispersing machine that can be used for atomizing the copper complex is not particularly limited. Examples thereof include media-type dispersers such as mills, spike mills, agitator mills, and media-less dispersers such as ultrasonic homogenizers, high-pressure homogenizers, nanomizers, resolvers, dispersers, and high-speed impeller dispersers.
Among these, it is preferable to use a media type disperser from the viewpoint of cost and processing capability. One of these may be used alone, or two or more devices may be used in combination.

(Distributed media)
As dispersion media, depending on the material in the dispersion chamber of the disperser used, steel ball beads such as stainless steel and steel, ceramic beads such as alumina, steatite, zirconia, zircon, silica, silicon carbide, and silicon nitride, In addition, glass beads such as soda glass and hi-be, carbide beads such as WC, and the like can be appropriately selected and used, and the bead diameter is preferably in the range of 0.03 to 1.5 mmφ.

  In this dispersion step for atomizing and dispersing the copper complex, a sufficient shearing force is applied to the copper complex due to collision between the copper complex and the dispersion medium, and the copper complex is atomized and dispersed. Here, since the liquid temperature of the dispersion rises due to the collision energy between the copper complex and the dispersion medium, the dispersion is preferably carried out while cooling the dispersion with a known cooling device. Although cooling temperature is not specifically limited, Usually, -50-120 degreeC, Preferably it is -30-80 degreeC, More preferably, it is -20-60 degreeC.

(Dispersant)
The dispersant is blended as necessary in order to stably disperse the copper complex in the dispersion medium. Examples of the dispersant include cationic dispersants such as alkylamine salts, dialkylamine salts, tetraalkylammonium salts, benzalkonium salts, alkylpyridinium salts, imidazolium salts, fatty acid salts, alkyl sulfate salts, and alkylaryls. Anionic dispersants such as sulfonate, alkylnaphthalene sulfonate, dialkyl sulfonate, dialkyl sulfosuccinate, alkyl diaryl disulfonate, alkyl phosphate, amphoteric dispersants such as alkyl betaine and amide betaine, Nonionic dispersants, fluorine-based dispersants, silicon-based dispersants, polymer-based dispersants, and the like can be used. Among these, nonionic dispersants and polymer dispersants as exemplified below are particularly preferable.

  Nonionic dispersants include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene Polyoxyethylene alkylphenyl ethers such as oxyethylene nonylphenyl ether, polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate, and sorbitan fatty acid esters are preferably used. From the viewpoint of dispersibility and economy, more preferred are polyoxyethylene alkyl ethers and polyoxyethylene alkylphenyl ethers.

Examples of the polymer dispersant include polyurethane, poly (meth) acrylic acid ester, unsaturated polyamide, polycarboxylic acid and its salt, styrene-acrylic acid copolymer, acrylic acid-acrylic acid ester copolymer, and styrene. -A water-soluble resin such as a maleic acid copolymer, polyvinyl alcohol, or polyvinylpyrrolidone, a water-soluble polymer compound, a polyester, a modified polyacrylate, an ethylene oxide / propylene oxide adduct, or the like is preferably used.
These dispersants may be used alone or in combination of two or more.

  The amount of the dispersant used is usually 0 to 100 parts by weight, preferably 0 to 60 parts by weight, based on 100 parts by weight of the copper complex. When the amount exceeds 100 parts by weight, a dispersion effect corresponding to the amount added cannot be obtained, which is not economical.

  After obtaining the composition for ultraviolet absorbing members in which the fine particles of the copper complex are dispersed by the above method, the composition may be diluted to a desired concentration.

  Moreover, it is also possible to mix and use together a conventionally well-known light absorber with this copper complex as needed in the range which does not impair the effect of this invention.

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

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

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

  In the case where a polymerizable monomer is used, a polymerization initiator may be used in combination when a polymerization step is provided when producing an ultraviolet absorbing member described later. It does not specifically limit as a polymerization initiator, According to the kind of polymerizable monomer to be used, it can select suitably. Further, the amount used can be appropriately selected according to the activities of the polymerizable monomer and the polymerization initiator. Examples of the polymerization initiator are as described above.

<< C. UV absorbing member of the present invention >>
The ultraviolet absorbing member of the present invention can be produced using the ultraviolet absorbing member composition thus obtained. The ultraviolet absorbing member of the present invention mainly has the following two types.

(C1) Ultraviolet-absorbing member as a laminate having a matrix material film containing a copper complex on a base material The above-obtained composition for an ultraviolet-absorbing member is coated on a base material and dried and / or cured. Thereby, the ultraviolet-absorbing member as a laminated body which has the film | membrane (henceforth a matrix film | membrane) of the matrix material containing this copper complex on a base material is producible.

  The coating method is not particularly limited. For example, dip coating method, spin coating method, flow coating method, roll coating method, gravure coating method, flexographic printing method, screen printing method, ink jet printing method, bar coating method, spray method. And known methods such as 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 base materials such as glass, poly (cyclo) olefin resin, polycarbonate resin, (meth) acrylic resin, polyester resin, polystyrene resin, epoxy resin, polyvinyl chloride resin, polychlorinated resin Vinylidene resin, polyacetal resin, polyamide resin, polyimide resin, fluorine resin, silicone resin, polysulfone resin, polyethersulfone resin, polyetherketone resin, polyetheretherketone resin, polyphenylene sulfide resin And organic base materials such as Among these, from the viewpoint of transparency, glass, poly (cyclo) olefin resin, polycarbonate resin, (meth) acrylic resin, polyester resin, polystyrene resin, epoxy resin, polyamide resin, polyimide resin, polysulfone Of these, a resin based on a resin, a polyether sulfone resin, a polyether ketone resin, and a polyphenylene sulfide resin are preferred.

  Moreover, you may wash | clean the base-material surface before application | coating in order to prevent delamination and a coating nonuniformity. It does not specifically limit as a washing | cleaning method, According to the kind of base material, it can select suitably and can implement. Usually, ultrasonic cleaning, UV cleaning, seric powder cleaning, acid cleaning, alkali cleaning, surfactant cleaning, organic solvent cleaning and the like can be performed alone or in combination. After the cleaning is completed, rinsing and drying are performed so that no cleaning agent remains.

  The thickness of the matrix film formed by coating is not particularly limited and can be appropriately adjusted according to the use, but is usually 0.01 to 100 μm, preferably 0.1 to 50 μm, and more preferably 1. ˜30 μm. If the thickness is less than 0.01 μm, there is a risk that sufficient ultraviolet light absorption ability may not be obtained. If the thickness exceeds 100 μm, the solvent or dispersion medium evaporates from the inside of the film during drying, resulting in unevenness on the film surface or cracks. There is sex.

  The drying temperature and drying time can be appropriately set depending on the type of solvent and dispersion medium used.

  After drying, a curing process and a baking process may be provided in order to control physical properties such as mechanical strength of the matrix film to meet the purpose.

  For example, when a silicon alkoxide sol body is used as the matrix material, 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. Mechanical strength can be improved. If the temperature is lower than 80 ° C, the mechanical strength may not be sufficiently improved. If the temperature is higher than 500 ° C, the copper complex contained in the matrix film may be thermally decomposed.

  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 matrix film can be controlled by the size of the siloxane network (polysiloxane molecular weight).

  The firing time can be appropriately adjusted according to the desired physical properties of the matrix film, but is usually 10 minutes to 5 hours, preferably 30 minutes to 3 hours. If it is shorter than 10 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.

  In addition, when a polymerization process is provided, a process such as heat treatment or UV irradiation can be provided. Heating conditions and UV irradiation conditions can be appropriately selected according to the type of polymerization initiator and polymerizable monomer to be used.

In addition, the laminate obtained by using a peelable substrate described later, coating the substrate, and transferring the coating layer to another desired substrate is also included in the form (C1). The above-mentioned base material is illustrated as another base material.
As a specific method, for example, a composition for an ultraviolet absorbing member is coated on a peelable substrate (for example, a polyethylene terephthalate film) and dried, and then another substrate (for example, a glass substrate) using a laminator or the like. And then peeling off the peelable substrate, whereby an ultraviolet absorbing member as a laminate having a matrix film containing the copper complex on another substrate can be produced. Also in this case, the polymerization treatment may be provided as necessary.

  For example, such a transfer method can be used in the case of producing a laminate in which matrix films made of different components are multilayered on a desired substrate. That is, when the multilayer film is formed by applying the composition for an ultraviolet absorbing member directly on the substrate as described above and forming a coating layer, for example, the n + 1th layer (n represents a natural number) The composition for ultraviolet absorbing member used for forming must be such that the constituent component of the nth layer does not dissolve or swell, and the constituent component of the composition for ultraviolet absorbing member constituting the (n + 1) th layer However, these limitations can be avoided by using such a transfer method.

(C2) Ultraviolet absorbing member in the form of a thin film in which a copper complex is contained in a matrix film The composition for ultraviolet absorbing member obtained above is coated on a peelable substrate, dried and / or cured, and then peeled off. It is possible to produce a UV-absorbing member in the form of a thin film in which the copper complex is contained in the matrix film, which is obtained by peeling the matrix film from the conductive substrate.
The coating method is the same as that exemplified in the above (C1).

  The peelable substrate may be a film or a board as desired, and the shape is not limited. The releasable substrate may be a substrate alone as long as the material constituting the substrate has releasability, or when the material constituting the substrate does not have releasability, or when the releasability is poor. What laminated | stacked the peelable layer on the base material may be used. When the material constituting the former base material is peelable, a polyolefin resin such as a polyethylene resin or a polypropylene resin, a polyester resin such as a polyethylene terephthalate resin, or the like can be used.

  In the latter case where the peelable layer is laminated on the base material, the base material exemplified in the above (C1) can be used as the base material. On the surface of these base materials, the base material has adhesiveness, and the thin film layer containing the copper complex prepared from the composition for ultraviolet absorbing member is laminated with a peelable layer having peelability. Can be used.

  The peelable layer is composed of a fluorine resin, a silicone resin, or a material in which a peelable substance is dissolved or dispersed in a binder resin.

  The releasable substance is not particularly limited, and examples thereof include long-chain alkyl compounds, synthetic waxes such as carnauba wax, montan wax, oxidized polyethylene, and non-oxidized polyethylene.

  By dissolving, dispersing or diluting at least one selected from these in a solvent (dispersion medium), applying or printing the obtained composition on a substrate by a known method, and then drying or curing. A peelable layer can be formed on the substrate. The thickness of the peelable layer is preferably about 0.5 μm to 10 μm.

  The film thickness of the thin film in which the copper complex formed by coating the composition for ultraviolet absorbing member on the peelable substrate is contained in the matrix film is not particularly limited, and is appropriately adjusted according to the application. The thickness is usually 0.1 to 100 μm, preferably 1 to 50 μm. If the thickness is less than 0.1 μm, the mechanical strength of the ultraviolet absorbing member may be insufficient in practice. If the thickness exceeds 100 μm, the solvent or dispersion medium evaporates from the inside of the film during drying, resulting in unevenness on the film surface. Cracks can occur.

  The drying temperature and drying time can be appropriately set depending on the type of solvent and dispersion medium used.

  In order to control the physical properties such as mechanical strength of the thin film containing the copper complex after drying, a curing step and a baking step may be provided.

  For example, when a silicon alkoxide sol body is used as the matrix material, 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. Mechanical strength can be improved. If the temperature is lower than 80 ° C, the mechanical strength may not be sufficiently improved. If the temperature is higher than 500 ° C, the copper complex contained in the matrix film may be thermally decomposed.

  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 matrix film can be controlled by the size of the siloxane network (polysiloxane molecular weight).

  The firing time can be appropriately adjusted according to the desired physical properties of the thin film, but is usually 10 minutes to 5 hours, preferably 30 minutes to 3 hours. If it is shorter than 10 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.

  In addition, when a polymerization process is provided, a process such as heat treatment or UV irradiation can be provided. Heating conditions and UV irradiation conditions can be appropriately selected according to the type of polymerization initiator and polymerizable monomer to be used.

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

  In addition, identification of each ligand and each copper complex obtained in the following production examples and examples was carried out by the methods described in the following methods (1), (2) and (3).

(1) ¹ H-nuclear magnetic resonance spectrum measurement NMR apparatus: AV400 type measurement solvent manufactured by BRUKER: dimethyl sulfoxide-d ₆ (DMSO-d ₆ )
Resonance frequency: 400 MHz

(2) Elemental analysis CHN: Oxygen circulation combustion / TCD detection method NCH quantification device S: Flask combustion / ion chromatography Cu: Microwave decomposition / ICP-AES method (3) Infrared spectrum measurement Device: JIR-6500 manufactured by JEOL Type FT-IR
Measuring method: KBr method

  Moreover, evaluation of each composition for ultraviolet absorbing members and each ultraviolet absorbing member obtained in the following Examples and Comparative Examples was performed by the methods described in the following methods (4) to (7).

(4) Measurement of average particle diameter The average particle diameter was measured using “Zetasizer Nano ZS” manufactured by Sysmex Corporation, light source: He—Ne laser (633 nm), cell: glass angle cell, measurement temperature: 25 ° C., Measurement position. : Measured under the condition of 0.85 (mm). Moreover, it measured 3 times about each sample, and showed the average value of the obtained value.

(5) Ultraviolet (UV-A) absorption ability of the ultraviolet absorbing member About the ultraviolet absorbing member obtained in Examples and Comparative Examples, λ = using a spectrophotometer (manufactured by Hitachi, Ltd., model number: U-4100) The transmittance at 380 nm and λ = 400 nm was measured, and the ultraviolet absorption ability (UV-A absorption ability) was evaluated.
In addition, the measurement was performed by performing baseline correction using the base material used in each ultraviolet absorbing member.

(6) Visible light transparency of ultraviolet absorbing member The total light transmittance was measured using a turbidimeter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.), and the visible light transparency was evaluated. In addition, standard alignment was performed using the base material used in each ultraviolet absorbing member.

(7) Light resistance of ultraviolet absorbing member After measuring the transmittance of the ultraviolet absorbing members obtained in Examples and Comparative Examples according to the procedure of (5), a xenon weather meter (manufactured by Suga Test Instruments Co., Ltd., model number: X25) These ultraviolet absorbing members were irradiated with light having a radiation intensity of 60 W / m ² (integrated in the region of 300 to 400 nm) for 1000 hours. About the ultraviolet absorption member after light irradiation, the transmittance | permeability was measured similarly to (5), respectively, and light resistance was evaluated from the change of the ultraviolet absorptivity by light irradiation.

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

Production Example 2 (Ligand Synthesis 1)
10 g (0.035 mol) of 2,2′-iminobisbenzothiazole obtained in Production Example 1 was added to 70.1 g (0.602 mol) of chlorosulfonic acid, and the reaction was stirred for 18 hours. Further, 10 g (0.084 mol) of thionyl chloride was added and stirred at 50 ° C. for 1 hour, and then cooled to 20 ° C. The reaction was poured onto 400 g of ice, filtered off with suction and immediately stirred with 8.8 g (0.101 mol) of morpholine along with the remaining ice. After the temperature was raised to 20 ° C., the reaction solution was made alkaline with about 1 ml of 50 wt% sodium hydroxide aqueous solution. The precipitate was separated by filtration, washed with water, washed with methanol, and dried to obtain 15.4 g of light yellow 2,2′-iminobis (6-morpholinosulfonylbenzothiazole). The yield was 75.5% based on 2,2′-iminobisbenzothiazole. The purity was measured by high performance liquid chromatography and was 98.5%.
¹ H-nuclear magnetic resonance spectrum (400 MHz, DMSO-d ₆ ) δ (ppm): 2.90 (m, 8H), 3.64 (m, 8H), 7.76 (m, 2H), 7.86 (Br, 2H), 8.47 (s, 2H), 13.46 (br, 1H)
FT-IR (cm < ^-1 >): 1446, 1462, 1533, 1566, 1608

Production Example 3 (Ligand Synthesis 2)
A pale yellow 2,2′-iminobis (6-thio) was prepared in the same manner as in Production Example 2 except that 10.4 g (0.101 mol) of thiomorpholine was used instead of 8.8 g (0.101 mol) of morpholine. 15.5 g of (morpholinosulfonylbenzothiazole) was obtained. The yield was 72.1% with respect to 2,2′-iminobisbenzothiazole. The purity was measured by high performance liquid chromatography and was 98.2%.
¹ H-nuclear magnetic resonance spectrum (400 MHz, DMSO-d ₆ ) δ (ppm): 2.68 (m, 8H), 3.23 (m, 8H), 7.77 (m, 4H), 8.46 (S, 2H), 13.44 (br, 1H)
FT-IR (cm < ^-1 >): 1442, 1469, 1543, 1603

Example 1 (Production of copper complex 1)
14.5 g (0.025 mol) of 2,2′-iminobis (6-morpholinosulfonylbenzothiazole) obtained in Production Example 2 and 135 g of DMF were mixed and dissolved. A solution prepared by previously dissolving 5.24 g (0.026 mol) of copper acetate monohydrate in 170 g of DMF was added dropwise thereto at 20 ° C. over 1 hour. After the addition, the solution was further stirred at 20 ° C. for 1 hour. did. Thereafter, the precipitate was separated by filtration, washed with DMF and methanol, dried, and dried with a beige powder of acetate {6- (morpholinosulfonyl) -N- [6- (morpholinosulfonyl) -2-benzothiazolyl-κ3N] -2- 16.3 g of benzothiazole aminato-κ3N} copper was obtained. The yield was 93.0% with respect to 2,2′-iminobis (6-morpholinosulfonylbenzothiazole).
Elemental analysis: C; 40.2%, H; 3.4%, Cu; 8.6%, N; 9.7%, S; 16.8% (theoretical value: C; 40.99%, H; (3.58%, Cu; 9.04%, N; 9.96%, S; 18.24%)
FT-IR (cm < ^-1 >): 1406, 1477 (br)

Example 2 (Production of copper complex 2)
In place of 14.5 g (0.025 mol) of 2,2′-iminobis (6-morpholinosulfonylbenzothiazole), 15.3 g (0.025 mol) of 2,2′-iminobis (6-thiomorpholinosulfonylbenzothiazole) Acetate {6- (thiomorpholinosulfonyl) -N- [6- (thiomorpholinosulfonyl) -2-benzothiazolyl-κ3N] -2-benzothiazole a beige powder in the same manner as in Example 1 except that 17.4 g of Minato-κ3N} copper was obtained. The yield was 94.5% with respect to 2,2′-iminobis (6-thiomorpholinosulfonylbenzothiazole).
Elemental analysis: C; 39.5%, H; 3.4%, Cu; 8.5%, N; 9.7%, S; 27.3% (theoretical value: C; 39.20%, H; (3.43%, Cu; 8.64%, N; 9.52%, S; 26.16%)
FT-IR (cm < ^-1 >): 1404, 1473 (br)

Production Example 4 (Inorganic binder: Preparation of silicon alkoxide sol solution)
Tetraethoxysilane 97.3 g (0.28 mol), 3-glycidoxypropyltrimethoxysilane 47.1 g (0.10 mol), 2-propanol 15.2 g, 2-ethoxyethanol 15.2 g, water 47.3 g was mixed. Here, 2.2 g of 1 wt% nitric acid aqueous solution (0.00035 mol as nitric acid) was added and stirred at 20 ° C. for 1 hour to obtain a sol solution of silicon alkoxide as an inorganic binder: polysiloxane binder precursor. (Solid content concentration: 17.8% by weight: in terms of SiO ₂ ).

Production Example 5 (Preparation 1 of copper complex fine particle dispersion)
As a dispersion medium, 50 g of 0.1 mmφ zirconia balls (trade name: YTZ balls manufactured by Nikkato) was placed in a pulverization container (trade name, manufactured by Fritsch: pulverization container for premium line (made by interior zirconia)). Here, 2.0 g of the copper complex obtained in Example 1, 17.1 g of water as a dispersion medium, 0.8 g of DISPERBYK-2015 (manufactured by Big Chemie Japan) as a dispersant, and 0.1 g of polyoxyethylene lauryl ether are added. Using a planetary ball mill (trade name: premium line P-7, manufactured by Fritsch), dispersed at 600 rpm for 5 minutes, cooled for 10 minutes, and further dispersed at 1100 rpm for 5 minutes to obtain a copper complex dispersion. It was. The average particle size was 107 nm.

Production Example 6 (Preparation 2 of Copper Particle Fine Particle Dispersion)
A copper complex dispersion was obtained in the same manner as in Production Example 5 except that 2.0 g of the copper complex obtained in Example 2 was used instead of 2.0 g of the copper complex obtained in Example 1. The average particle size was 123 nm.

Example 3 (Composition for ultraviolet absorbing member containing copper complex and ultraviolet absorbing member A)
While stirring 0.35 g of the dispersion of the copper complex obtained in Production Example 5, 2.0 g of the silicon alkoxide sol solution obtained in Production Example 4 was added and mixed, thereby dispersing the ultraviolet ray in the form of a dispersion. The composition A for absorbent members was obtained. The average particle size was 111 nm.

  30 × 30 mm cover glass (MICRO COVER GLASS No, manufactured by MATSANAMI), which was previously surface-washed with acetone using a spin coater (manufactured by Active Co., Ltd., model number: ACT-300A), was obtained. .3) After being applied onto the substrate, preliminarily dried at 20 ° C. for 10 minutes in a nitrogen atmosphere and then baked at 180 ° C. for 1 hour to obtain an ultraviolet absorbing member A. The coating film thickness was 3 μm.

  About the obtained ultraviolet-absorbing member A, the ultraviolet-ray (UV-A) absorption ability, visible light transparency, and light resistance were evaluated. The evaluation results are shown in Table 1.

Example 4 (Composition for ultraviolet absorbing member containing copper complex and ultraviolet absorbing member B)
As an organic binder, 1.34 g of an acrylic resin solution (trade name, manufactured by Soken Chemical Co., Ltd .; Foret GS-1000, solid content 30 wt% MEK solution) is placed in a 100 ml eggplant flask, and MEK is distilled off under reduced pressure using a rotary evaporator. As a result, 0.40 g of an acrylic resin was obtained. To this, 0.93 g of DMF was added and stirred to obtain an acrylic resin solution (solid content 30 wt% DMF solution). To this was added 9.5 mg of the copper complex obtained in Example 1, and after ultrasonication in a 70 ° C. hot water bath, the solution was filtered with a membrane filter (DISMIC25HP045AN manufactured by ADVANTEC) to absorb ultraviolet rays in the form of a solution. The composition B for members was obtained.

  The obtained composition B for ultraviolet absorbing member was applied onto a PET film (film thickness 100 μm) using a bar coater (manufactured by Nippon Cedars Co., Ltd., 100 μm), and then pre-dried for 10 minutes in a nitrogen atmosphere at 20 ° C. Then, it was dried at 160 ° C. for 5 minutes to obtain an ultraviolet absorbing member B. The thickness of the coating film was 10 μm.

  About the obtained ultraviolet-absorbing member B, the ultraviolet-ray (UV-A) absorption ability, visible light transparency, and light resistance were evaluated. The evaluation results are shown in Table 1.

Example 5 (Composition for ultraviolet absorbing member containing copper complex and ultraviolet absorbing member C)
While stirring 0.35 g of the dispersion of the copper complex obtained in Production Example 6, 2.0 g of the sol solution of silicon alkoxide obtained in Production Example 4 was added thereto and mixed, whereby ultraviolet rays in the form of dispersion were obtained. Absorbent member composition C was obtained. The average particle size was 125 nm.

30 × 30 mm cover glass (MICRO COVER GLASS No, manufactured by MATSANAMI), which was previously surface-washed with acetone using a spin coater (manufactured by Active Co., Ltd., model number: ACT-300A), was obtained. .3) After that, it was preliminarily dried at 20 ° C. in a nitrogen atmosphere for 10 minutes and then baked at 180 ° C. for 1 hour to obtain an ultraviolet absorbing member C. The coating film thickness was 3 μm.
The obtained ultraviolet absorbing member C was evaluated for ultraviolet (UV-A) absorption ability, visible light transparency and light resistance. The evaluation results are shown in Table 1.

Comparative Example 1 (Composition for ultraviolet absorbing member containing inorganic ultraviolet absorber and ultraviolet absorbing member D)
Zinc oxide fine particle dispersion (manufactured by Hakusuitec Co., Ltd., product name: passette GK-water dispersion, powder primary particle size: 20 to 40 nm, zinc oxide concentration: 20% by weight) manufactured here with stirring 0.35 g By adding and mixing 2.0 g of the silicon alkoxide sol solution obtained in Example 4, a composition D for ultraviolet absorbing member in the form of a dispersion was obtained.

  Using a spin coater (manufactured by Active Co., Ltd., model number: ACT-300A), the obtained composition D for ultraviolet absorbing member was 30 × 30 mm cover glass (MICRO COVER GLASS No, manufactured by MATSANAMI), which was previously surface-washed with acetone. .3) After being applied on the substrate, preliminarily dried at 20 ° C. for 10 minutes in a nitrogen atmosphere and then baked at 180 ° C. for 1 hour to obtain an ultraviolet absorbing member D. The coating film thickness was 4 μm.

  About the obtained ultraviolet-absorbing member D, ultraviolet-ray (UV-A) absorptivity, visible light transparency, and light resistance were evaluated. The evaluation results are shown in Table 1.

Comparative Example 2 (Composition for UV absorbing member containing organic UV absorber and UV absorbing member E)
As an organic binder, 1.34 g of an acrylic resin solution (trade name, manufactured by Soken Chemical Co., Ltd .; Foret GS-1000, solid content 30 wt% MEK solution) is placed in a 100 ml eggplant flask, and MEK is distilled off under reduced pressure using a rotary evaporator. As a result, 0.40 g of an acrylic resin was obtained. To this, 0.93 g of DMF was added and stirred to obtain an acrylic resin solution (solid content 30 wt% DMF solution). It was dissolved in 2.5 g of DMF, and 12 mg of Tinuvin 326 (manufactured by BASF) was added thereto. Ultrasonic treatment was performed in a 60 ° C. hot water bath, followed by filtration with a membrane filter (DISMIC25HP045AN manufactured by ADVANTEC) to obtain a composition E for ultraviolet absorbing member in the form of a solution.

  The obtained composition E for ultraviolet absorbing member was applied onto a PET film (film thickness 100 μm) using a bar coater (manufactured by Nippon Cedars Co., Ltd., 100 μm), and then pre-dried for 10 minutes in a nitrogen atmosphere at 20 ° C. Then, it was dried at 160 ° C. for 5 minutes to obtain an ultraviolet absorbing member E. The coating film thickness was 11 μm.

  About the obtained ultraviolet-absorbing member E, ultraviolet-ray (UV-A) absorptivity, visible light transparency, and light resistance were evaluated. The evaluation results are shown in Table 1.

Evaluation Results Ultraviolet absorbing members A and C are systems using a copper complex represented by the formula (1) in a dispersion system, and the ultraviolet absorbing member D is a conventionally known zinc oxide fine particle (Hux Itec Co., Ltd.) as an inorganic ultraviolet absorber. Manufactured, product name: passette GK-water dispersion). Although the ultraviolet absorbing member D has very good light resistance, the ultraviolet absorbing ability is clearly insufficient, the total light transmittance is low, and the visible light transparency is impaired. On the other hand, although the ultraviolet absorbing members A and C are slightly inferior in light resistance to D, the transmittance at λ = 380 nm and λ = 400 nm is sufficiently low, and in addition to having excellent ultraviolet absorbing ability, visible light Transparency is also sufficiently secured.

  The ultraviolet absorbing member B is a system in which the copper complex represented by the formula (1) is used in a dissolution system, and the ultraviolet absorbing member E is a conventionally known benzotriazole ultraviolet absorber (manufactured by BASF) as an organic ultraviolet absorber. , Product name: Tinuvin 326) in a dissolution system. Although the ultraviolet absorbing member E has a high total light transmittance, both the light resistance and the ultraviolet absorbing ability are insufficient. On the other hand, the ultraviolet absorbing member B has a sufficiently low transmittance at λ = 380 nm and a high total light transmittance, and thus has been confirmed to have excellent visible light transparency.

  That is, according to this invention, UV-A in 380-400 nm which was difficult to shield conventionally can be effectively shielded by using the copper complex represented by Formula (1).

  In particular, when it is desired to shield λ = 400 nm of UV-A and / or when excellent light resistance is required, these objects can be obtained by using the copper complex represented by the formula (1) in a dispersion system. Can be achieved.

  In addition, when it is desired to shield UV-A of λ = 380 nm or less and / or when high visible light transparency is required, these copper complexes represented by the formula (1) are used in a dissolution system. Aim can be achieved.

  Since the copper complex of the present invention has excellent light resistance as an ultraviolet absorber and can efficiently shield UV-A, which has been conventionally difficult to shield while maintaining high transparency to visible light, In various fields, it is possible to manufacture a highly functional material for ultraviolet shielding.

Claims (3)

Formula (1):

(In the formula, X and Y are each independently an oxygen atom or a sulfur atom, Z is a halogeno group, an acetate group, an acetylacetonato group or a nitrato group;
R ¹ is a morpholinosulfonyl group, a thiomorpholinosulfonyl group, a piperazinosulfonyl group or an N-substituted piperazinosulfonyl group,
R ² is absent or, if present, the maximum excluding the carbon atoms bonded to R ¹ and the two carbon atoms shared with the 5-membered ring among the six carbon atoms of one benzene ring 1 to 3 of hydrogen atoms bonded to 3 carbon atoms can be substituted, and R ² substituted with hydrogen atoms of the benzene ring are independently of each other an alkyl group having 1 to 8 carbon atoms, carbon A C 1-4 alkoxy group, a halogeno group, a morpholinosulfonyl group, a thiomorpholinosulfonyl group, a piperazinosulfonyl group or an N-substituted piperazinosulfonyl group;
R ³ is absent or, if present, 4 bonded to 4 carbon atoms, excluding the 2 carbon atoms shared with the 5-membered ring among the 6 carbon atoms of one benzene ring. 1 to 4 of the hydrogen atoms can be substituted, and each R ³ substituted with a hydrogen atom of the benzene ring is independently of each other an alkyl group having 1 to 8 carbon atoms or an alkoxy having 1 to 4 carbon atoms. A group, a halogeno group, a morpholinosulfonyl group, a thiomorpholinosulfonyl group, a piperazinosulfonyl group or an N-substituted piperazinosulfonyl group; A copper complex represented by:   The composition for ultraviolet absorption members containing the at least 1 type of copper complex of Claim 1, and at least 1 type of matrix material.   The ultraviolet absorption member produced using the composition for ultraviolet absorption members of Claim 2.