JP2016069645A - Composition for forming infrared shielding body and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for forming an infrared shielding body having excellent infrared shielding performance and lon-term durability, and a method for producing the same.SOLUTION: The composition for forming an infrared shielding body comprises the following components (A) to (E): (A) a hydrolysis-condensation product of silane compounds having alkoxy groups including the following components (A-1) to (A-4); (A-1) an alkoxysilane compound represented by the following formula (1) or a polyalkoxysilane compound obtained by linking of the alkoxysilane compound via a siloxane bond (Si-O bond), (R)Si(OR)(1); (A-2) an aminosilane compound represented by the following formula (2), (R)Si(OR)(2); (A-3) an epoxysilane compound represented by the following formula (3), (R)Si(OR)(3); and (A-4) a blocked (isocyanato)silane compound having an alkoxy group; (B) a curing catalyst; (C) a dispersion medium; (D) a composite tungsten oxide represented by MWO; and (E) a dispersant for the (D) component.SELECTED DRAWING: None

Description

  The present invention relates to a composition for forming an infrared shielding body and a method for producing the same.

  From the viewpoints of preventing global warming and saving energy, it is widely practiced to cut the heat rays (infrared rays) of sunlight that enters through windows of buildings, automobiles, and the like to reduce the internal temperature.

  Various materials have been proposed as infrared cut materials, and their use for laminated glass such as the inner surface of multilayer glass and the windshield of automobiles is also being studied.

  For example, one using a metal thin film (for example, see Patent Document 1) and one using an inorganic multilayer multilayer film having different refractive indexes (for example, see Patent Document 2) have been proposed. There was a problem in workability.

  Furthermore, antimony-doped tin oxide (ATO), tungsten composite oxide (MWO), etc. (Patent Document 3) and infrared reflective film (Patent Document 4) using a cholesteric liquid crystal polymer have been proposed. And there was a problem with long-term stability.

Japanese Patent Laid-Open No. 10-309767 International Publication No. 2007/020792 International Publication No. 2005/037932 JP 2014-81532 A

  The object of the present invention is to provide a composition for forming an infrared shielding body excellent in infrared shielding performance and long-term durability, and a method for producing the same.

According to the present invention, the following composition for forming an infrared shielding body, a method for producing the same, and the like are provided.
1. The composition for infrared shielding body containing the following (A)-(E) component.
(A) Hydrolysis condensate of a silane compound having an alkoxy group of the following components (A-1) to (A-4) (A-1) An alkoxysilane compound represented by the following formula (1), or the alkoxysilane Polyalkoxysilane compound in which compounds are connected by a siloxane bond (Si—O bond) (R ¹ ) _m Si (OR ² ) _4-m (1)
(In the formula, R ¹ may be the same or different, an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group, or a methacryloxy alkyl group having 1 to 3 carbon atoms which is substituted with a group .R ² Is an alkyl group having 1 to 4 carbon atoms, and m is 0, 1 or 2.)
(A-2) Aminosilane compound represented by the following formula (2) (R ¹¹ ) _n Si (OR ¹² ) _4-n (2)
(In the formula, R ¹¹ may be the same or different and substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group, or a methacryloxy group and an amino group. an alkyl group having 1 to 3 carbon atoms, at least one of R ¹¹ is an alkyl group having 1 to 3 carbon atoms substituted with an amino group. the amino group may have a substituent. R ¹² is an alkyl group having 1 to 4 carbon atoms, and n is 1 or 2.)
(A-3) Epoxysilane compound represented by the following formula (3) (R ²¹ ) _k Si (OR ²² ) _4-k (3)
(In the formula, R ²¹ may be the same or different and is selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group, or a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. An alkyl group having 1 to 3 carbon atoms substituted with one or more groups, and at least one of R ²¹ is an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group; R ²² is an alkyl group having 1 to 4 carbon atoms, and k is 1 or 2.)
(A-4) Blocked isocyanatosilane compound having an alkoxy group (B) Curing catalyst (C) Dispersion medium (D) Formula M _x W _y O _z (where M is a hydrogen atom, an alkali metal, an alkaline earth) Metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge , Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I 1 More than one kind of element or ammonium group, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1.1, and 2.2 ≦ z / y ≦ 3.0. ) Composite tungsten oxide represented by (E) (D) component dispersion Agent 2. The composition for forming an infrared shielding material according to 1, further comprising (F) organic polymer fine particles comprising a copolymer containing a monomer unit having an ultraviolet absorbing group.
3. The organic polymer fine particles include an acrylic monomer having a skeleton selected from a benzophenone skeleton, a benzotriazole skeleton, and a triazine skeleton in a side chain, acrylic acid, acrylic acid derivative, methacrylic acid, methacrylic acid derivative, styrene, and vinyl acetate. 3. The infrared shielding composition-forming composition according to 2, wherein the composition is a copolymer with a selected ethylenically unsaturated compound and has a weight average molecular weight of more than 10,000.
4). Furthermore, the composition for infrared shielding body formation in any one of 1-3 containing (G) colloidal silica.
5. After mixing the components (D) to (E) and the component (C), an external force is applied to disperse the component (D) to form a Y liquid,
The manufacturing method of the composition for infrared shielding body formation which forms the composition for infrared shielding body formation by mixing X liquid containing the following (A)-(C) component, and the said Y liquid.
(A) Hydrolysis condensate of a silane compound having an alkoxy group of the following components (A-1) to (A-4) (A-1) An alkoxysilane compound represented by the following formula (1), or the alkoxysilane Polyalkoxysilane compound in which compounds are connected by a siloxane bond (Si—O bond) (R ¹ ) _m Si (OR ² ) _4-m (1)
(In the formula, R ¹ may be the same or different, an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group, or a methacryloxy alkyl group having 1 to 3 carbon atoms which is substituted with a group .R ² Is an alkyl group having 1 to 4 carbon atoms, and m is 0, 1 or 2.)
(A-2) Aminosilane compound represented by the following formula (2) (R ¹¹ ) _n Si (OR ¹² ) _4-n (2)
(In the formula, R ¹¹ may be the same or different and substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group, or a methacryloxy group and an amino group. an alkyl group having 1 to 3 carbon atoms, at least one of R ¹¹ is an alkyl group having 1 to 3 carbon atoms substituted with an amino group. the amino group may have a substituent. R ¹² is an alkyl group having 1 to 4 carbon atoms, and n is 1 or 2.)
(A-3) Epoxysilane compound represented by the following formula (3) (R ²¹ ) _k Si (OR ²² ) _4-k (3)
(In the formula, R ²¹ may be the same or different and is selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group, or a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. An alkyl group having 1 to 3 carbon atoms substituted with one or more groups, and at least one of R ²¹ is an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group; R ²² is an alkyl group having 1 to 4 carbon atoms, and k is 1 or 2.)
(A-4) Blocked isocyanatosilane compound having an alkoxy group (B) Curing catalyst (C) Dispersion medium (D) Formula M _x W _y O _z (where M is a hydrogen atom, an alkali metal, an alkaline earth) Metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge , Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I 1 More than one kind of element or ammonium group, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1.1, and 2.2 ≦ z / y ≦ 3.0. ) Composite tungsten oxide represented by (E) (D) component dispersion Agent 6 6. The method for producing an infrared shielding composition according to 5, wherein the liquid X further comprises (F) organic polymer fine particles comprising a copolymer containing a monomer unit having an ultraviolet absorbing group.
7). The method for producing an infrared shielding body forming composition according to 5 or 6, wherein the liquid X further contains (G) colloidal silica.
8). In the mixing of the components (D) to (E) and the component (C), the component (D) is dispersed using the component (E) and the ester solvent, and then the solution containing the ester solvent is heated to obtain a solvent. The method for producing an infrared shielding composition according to any one of 5 to 7, which is carried out by evaporating and adding the above component (C) thereto.
A cured film obtained by curing the composition according to any one of 9.1 to 4 or the composition produced by the method according to 5 to 8.
10. A substrate;
The cured film according to 9, which is formed on the substrate,
A laminate having
11. The laminate according to 10, wherein the substrate is a film.
12 The laminate according to 10, wherein the substrate is glass.

  ADVANTAGE OF THE INVENTION According to this invention, the infrared shielding body formation composition excellent in infrared shielding performance and long-term durability, and its manufacturing method can be provided.

The composition for forming an infrared shielding body of the present invention includes the following components (A) to (E). Thereby, the infrared shielding body excellent in infrared shielding performance, long-term durability, adhesion to a substrate, and film strength can be formed.
The infrared shielding body can be formed by curing the infrared shielding body forming composition to form a cured film, and is particularly excellent in water resistance.

(A) A component is a hydrolysis-condensation product of the silane compound which has the alkoxy group of (A-1)-(A-4) component.
The hydrolysis condensate may be a hydrolysis condensate of a single compound in (A-1) to (A-4), or any of (A-1) to (A-4). It may be a hydrolysis condensate of a mixture of two or more.

In the present specification, the silane compound having an alkoxy group is an alkoxysilane compound and / or a partial condensate thereof, and the partial condensate of the alkoxysilane compound is a part of the alkoxysilane compound condensed in the molecule. A polyalkoxysilane compound or a polyorganoalkoxysilane compound formed by forming a siloxane bond (Si—O bond).
The hydrolyzed condensate of the silane compound having an alkoxy group includes a silane compound having the alkoxy group before hydrolytic condensation in addition to the hydrolyzed condensate of the silane compound having an alkoxy group. is there.

The component (A-1) is an alkoxysilane compound represented by the following formula (1) or a polyalkoxysilane compound in which the alkoxysilane compound is connected by a siloxane bond (Si—O bond).
(R ¹ ) _m Si (OR ² ) _4-m (1)
(In the formula, R ¹ may be the same or different, an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group, or a methacryloxy alkyl group having 1 to 3 carbon atoms which is substituted with a group .R ² Is an alkyl group having 1 to 4 carbon atoms, and m is 0, 1 or 2.)

Examples of the alkyl group having 1 to 4 carbon atoms of R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and various butyl groups.
The alkyl group for R ² is the same as R ¹ . When there are a plurality of R ^{2 s} , they may be the same or different.
Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
m is preferably 0 or 1.

  Specific examples of the alkoxysilane compound include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltrimethoxysilane. Butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, Examples thereof include tetraisobutoxysilane.

The condensation number of the polyalkoxysilane compound is preferably an integer of 1 to 15.
Specific examples of the polyalkoxysilane compound include “MTMS-A”, “M silicate 51”, “silicate 40”, “silicate 45” manufactured by Tama Chemical Co., Ltd., and “SS-101” manufactured by Colcoat Co., Ltd. , “Methyl silicate 51”, “Methyl silicate 53A”, “Ethyl silicate 40”, “Ethyl silicate 48”, “AZ-6101”, “SR2402”, “AY42-163” manufactured by Toray Dow Corning Co., Ltd. It is done.

  (A-1) A component may be used individually by 1 type and may be used in combination of 2 or more type.

The component (A-2) is an aminosilane compound represented by the following formula (2).
(R ¹¹ ) _n Si (OR ¹² ) _4-n (2)
(In the formula, R ¹¹ may be the same or different and substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group, or a methacryloxy group and an amino group. an alkyl group having 1 to 3 carbon atoms, at least one of R ¹¹ is an alkyl group having 1 to 3 carbon atoms substituted with an amino group. the amino group may have a substituent. R ¹² is an alkyl group having 1 to 4 carbon atoms, and n is 1 or 2.)

The alkyl group having 1 to 4 carbon atoms and the alkyl group having 1 to 3 carbon atoms are the same as described above.
n is preferably 1.
When there are a plurality of R ^{12 s} , they may be the same or different.
Examples of the substituent of the amino group include a 2-aminoethyl group and a phenyl group.

Specific examples of the aminosilane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N- (2-aminoethyl).
-3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)
-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and the like.

Examples of the partial condensate of the aminosilane compound include “KBP-90” manufactured by Shin-Etsu Silicone Co., Ltd.
The number of condensation is preferably an integer of 1 to 15.

  (A-2) A component may be used individually by 1 type and may be used in combination of 2 or more type.

The component (A-3) is an epoxysilane compound represented by the following formula (3).
(R ²¹ ) _k Si (OR ²² ) _4-k (3)
(In the formula, R ²¹ may be the same or different and is selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group, or a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. An alkyl group having 1 to 3 carbon atoms substituted with one or more groups, and at least one of R ²¹ is an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group; R ²² is an alkyl group having 1 to 4 carbon atoms, and k is 1 or 2.)

The alkyl group having 1 to 4 carbon atoms and the alkyl group having 1 to 3 carbon atoms are the same as described above.
k is preferably 1.
When there are a plurality of R ^{22 s} , they may be the same or different.

  Specific examples of the epoxy silane compound include 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and dimethoxy-3-glycidoxypropylmethyl. Examples include silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

As a partial condensate of an epoxy silane compound, Shin-Etsu Silicone Co., Ltd. "X-41-1053", "X-41-1059A" etc. are mentioned, for example.
The number of condensation is preferably an integer of 1 to 15.

  (A-3) A component may be used individually by 1 type and may be used in combination of 2 or more type.

The component (A-4) is a blocked isocyanatosilane compound having an alkoxy group.
A blocked isocyanatosilane compound is an isocyanatosilane compound in which an isocyanate group is protected by a blocking agent such as oxime to be inactive, and is deblocked by heating to activate (regenerate) the isocyanate group (generally Also referred to as an isocyanate silane compound).

The blocked isocyanatosilane compound is preferably a compound represented by the following formula (4).
R ³¹ _j Si (OR ³² ) _4-j (4)
(In the formula, R ³¹ may be the same or different and substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group, or a methacryloxy group and a blocked isocyanate group) And at least one of R ³¹ is an alkyl group having 1 to 3 carbon atoms substituted with a blocked isocyanate group, and R ³² is an alkyl having 1 to 4 carbon atoms. And j is 1 or 2.)

The alkyl group having 1 to 4 carbon atoms and the alkyl group having 1 to 3 carbon atoms are the same as described above.
j is preferably 1.
When there are a plurality of R ^{32 s} , they may be the same or different.

  Examples of blocked isocyanatosilane compounds include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3 -What protected the isocyanate group in compounds, such as isocyanatopropyl ethyl diethoxysilane, with the blocking agent is mentioned. Among these, 3-blocked isocyanatopropyltriethoxysilane is preferable.

  Examples of isocyanate group blocking agents include oxime compounds such as acetooxime, 2-butanone oxime, cyclohexanone oxime, methyl isobutyl ketoxime, lactams such as ε-caprolaclam, alkylphenols such as monoalkylphenol (cresol, nonylphenol, etc.), Active methylene compounds such as 3,5-xylenol, dialkylphenols such as di-t-butylphenol, trialkylphenols such as trimethylphenol, malonic acid diesters such as diethyl malonate, acetoacetates such as acetylacetone and ethyl acetoacetate , Alcohols such as methanol, ethanol, n-butanol, hydroxyl group-containing ethers such as methyl cellosolve and butyl cellosolve, hydroxyl groups such as ethyl lactate and amyl lactate Esters, mercaptans such as butyl mercaptan and hexyl mercaptan, acid amides such as acetanilide, acrylic amide and dimer acid amide, imidazoles such as imidazole and 2-ethylimidazole, pyrazoles such as 3,5-dimethylpyrazole, Triazoles such as 1,2,4-triazole, and acid imides such as succinimide and phthalimide can be used. In order to control the dissociation temperature of the blocking agent, a catalyst such as dibutyltin dilaurate may be used in combination.

As a partial condensate of a blocked isocyanatosilane compound, for example, a product obtained by partially hydrolyzing and condensing the blocked isocyanatosilane compound can be used.
The number of condensation is preferably an integer of 1 to 15.

  (A-4) A component may be used individually by 1 type and may be used in combination of 2 or more type.

Component (B) is a curing catalyst.
The curing catalyst is a catalyst for hydrolyzing and condensing (curing) the silane compounds (A-1) to (A-4) components in the component (A) described above. For example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, Inorganic acids such as nitric acid, perchloric acid and sulfamic acid, organic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, citric acid, tartaric acid, succinic acid, maleic acid, glutamic acid, lactic acid and p-toluenesulfonic acid Can be mentioned.

Lithium hydroxide, sodium hydroxide, potassium hydroxide, n-hexylamine, dimethylamine, tributylamine, diazabicycloundecene, ethanolamine acetate, dimethylaniline formate, tetraethylammonium benzoate, sodium acetate, potassium acetate Organic metal salts such as sodium propionate, sodium glutamate, potassium propionate, sodium formate, potassium formate, benzoyltrimethylammonium acetate, tetramethylammonium acetate, tin octylate, tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide include aluminum triisopropoxide, aluminum acetylacetonate, SnCl _4, TiCl _4, Lewis acids ZnCl ₄ and the like and the like

Among these curing catalysts, organic acids can be preferably used because they can be highly dispersed even if the components (F) and (G) described later are blended and the transparency of the resulting film can be improved. In particular, an organic carboxylic acid, preferably acetic acid, can be preferably used.
(B) A component may be used individually by 1 type and may be used in combination of 2 or more type.

Component (C) is a dispersion medium.
The composition for forming an infrared shielding body of the present invention is used in a state where each component particle is dispersed in a dispersion medium.
The dispersion medium is not particularly limited as long as each component particle can be uniformly mixed and dispersed, and examples thereof include organic dispersion media such as alcohols, aromatic hydrocarbons, ethers, ketones, esters, and the like. Can be mentioned.

The suitable boiling point of the dispersion medium varies depending on the coating method.
The boiling point of the dispersion medium is preferably 50 to 250 ° C.
If it is too low, uniform coating may be difficult, and if it is too high, it may take time to dry and the productivity may deteriorate.

  Specific examples of alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, ethylene glycol, diethylene glycol, Triethylene glycol, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, 1-methoxy-2-propanol (propylene glycol monomethyl ether), 1-methoxy-2-butanol, 1-ethoxy-2-propanol, diacetone alcohol, methyl cellosolve , Ethyl cellosolve, propyl cellosolve and the like.

Specific examples of other dispersion media include cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, xylene, dichloroethane, toluene, methyl acetate, ethyl acetate, ethoxyethyl acetate. Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and the like.
From the viewpoint of performance as a dispersion medium, alcohols are preferred.
(E) A component may be used individually by 1 type and may be used in combination of 2 or more type.

The component (D) has the formula M _x W _y O _z (where M is a hydrogen atom, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir , Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti , Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi and I are one or more elements selected from the group consisting of ammonium and W, W is tungsten, and O is oxygen. 0.001 ≦ x / y ≦ 1.1, and 2.2 ≦ z / y ≦ 3.0.)

From the viewpoint of stability, M is an alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au. Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be More preferably, the element is one or more elements selected from the group consisting of Hf, Os, Bi and I. From the viewpoint of improving optical properties and weather resistance as an infrared shielding material, alkali metals and alkaline earths are preferred. More preferred are elements belonging to metal elements, transition metal elements, Group 4B elements, Group 5B elements.
Alkali metals are particularly preferred and Cs is most preferred.

The composite tungsten oxide preferably has a hexagonal crystal structure, more preferably hexagonal tungsten bronze, from the viewpoint of transmission in the visible light region and absorption in the near infrared region.
Further, a tetragonal or cubic tungsten bronze structure may be used.

  The composite tungsten oxide may be crystalline or amorphous.

x / y is 0.001 or more and 1.1 or less, preferably 0.2 or more and 0.5 or less, and more preferably 0.33. When z / y = 3, the value of x / y becomes 0.33, so that the additive element M is considered to be arranged in all hexagonal voids.
When x / y is 0.001 or more, a sufficient amount of free electrons is generated, and the intended infrared shielding effect can be obtained. As the amount of M added increases, the supply amount of free electrons increases and the infrared shielding efficiency also increases. However, when the value of x / y is about 1, the effect may be saturated. If x / y is 1.1 or less, the generation of an impurity phase in the composite tungsten oxide can be avoided.

z / y is 2.2 or more and 3.0 or less, and preferably 2.45 or more and 2.999 or less.
If z / y is 2.2 or more, the appearance of a WO ₂ crystal phase in the composite tungsten oxide can be avoided, and chemical stability as a material can be obtained. On the other hand, if z / y is 3.0 or less, an appropriate amount of free electrons is generated in the composite tungsten oxide, and an efficient infrared shielding effect can be obtained.

The composite tungsten oxide is preferably fine particles.
The particle diameter is preferably 800 nm or less because light is not completely shielded by scattering, visibility in the visible light region can be maintained, and transparency can be maintained efficiently at the same time.
From the viewpoint of reducing scattering, the particle diameter is preferably 200 nm or less, and more preferably 100 nm or less.

Moreover, it is preferable from the viewpoint of improving the weather resistance that the surface of the composite tungsten oxide is coated with an oxide containing one or more of Si, Ti, Zr, and Al.
Although the coating method is not particularly limited, it is possible to coat the surface of the composite tungsten oxide fine particles by adding the metal alkoxide to the solution in which the composite tungsten oxide fine particles are dispersed.

The composite tungsten oxide is preferably Cs _0.33 WO ₃ and Rb _0.33 WO ₃ .
(D) A component may be used individually by 1 type and may be used in combination of 2 or more type.

The component (E) is a dispersant for the component (D). The dispersant is not particularly limited as long as it can disperse component (D). However, from the viewpoint of dispersion stability of component (D) in the composition for forming an infrared shielding material, the dispersant has an acid value and an amine value. What is not preferred is preferred.
Dispersants include polyacrylate-based dispersants, polyalkylene glycol-based dispersants, DISPERBYK-102 (acid value 101 mg KOH / g, no amine value), DISPERBYK-190 (acid value 10 mg KOH / g, no amine value).
(E) A component may be used individually by 1 type and may be used in combination of 2 or more type.

  The composition for forming an infrared shielding body of the present invention may further contain organic polymer fine particles made of a copolymer containing a monomer unit having an ultraviolet absorbing group as the component (F).

  The organic polymer fine particle is capable of acting as an ultraviolet absorbing group, an acrylic monomer having a skeleton selected from a benzophenone skeleton, a benzotriazole skeleton and a triazine skeleton in a side chain, and acrylic acid, an acrylic acid derivative, methacrylic acid, A copolymer with an ethylenically unsaturated compound selected from methacrylic acid derivatives, styrene and vinyl acetate is preferred.

Further, the weight average molecular weight of the organic polymer fine particles is preferably more than 10,000, more preferably 100,000 to 10,000,000.
When the weight average molecular weight exceeds 10,000, defects of conventional low molecular weight ultraviolet absorbers such as affinity with a matrix and heat resistance are improved, and weather resistance performance can be imparted over a long period of time.

  The acrylic monomer is not particularly limited as long as it is a compound having at least one ultraviolet absorbing group and acryloyl group in the molecule. Examples of such a compound include benzotriazole compounds represented by the following general formula (11) and benzophenone compounds represented by the general formula (12).

[Wherein, X is a hydrogen atom or a chlorine atom, R ¹⁰ is a hydrogen atom, a methyl group, or a tertiary alkyl group having 4 to 8 carbon atoms, and R ¹¹ is a linear or branched carbon atom having 2 to 10 carbon atoms. An alkylene group, R ¹² represents a hydrogen atom or a methyl group, and p represents 0 or 1. ]

[Wherein, R ¹³ is a hydrogen atom or a methyl group, R ¹⁴ is a substituted or unsubstituted linear or branched alkylene group having 2 to 10 carbon atoms, R ¹⁵ is a hydrogen atom or a hydroxyl group, and R ¹⁶ is hydrogen. An atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms is shown. ]

  Specific examples of the benzotriazole-based compound represented by the general formula (11) include, for example, 2- (2′-hydroxy-5 ′-(meth) acryloxyphenyl) -2H-benzotriazole, 2- (2 '-Hydroxy-3'-tert-butyl-5'-(meth) acryloxymethylphenyl) -2H-benzotriazole, 2- [2'-hydroxy-5 '-(2- (meth) acryloxyethyl) phenyl ] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-(2- (meth) acryloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [ And 2'-hydroxy-3'-methyl-5 '-(8- (meth) acryloxyoctyl) phenyl] -2H-benzotriazole.

Specific examples of the benzophenone compound represented by the general formula (12) include 2-hydroxy-4- (2- (meth) acryloxyethoxy) benzophenone and 2-hydroxy-4- (4- (meta ) Acryloxybutoxy) benzophenone, 2,2′-dihydroxy-4- (2- (meth) acryloxyethoxy) benzophenone, 2,4-dihydroxy-4 ′-(2- (meth) acryloxyethoxy) benzophenone, 2, , 2 ′, 4-trihydroxy-4 ′-(2- (meth) acryloxyethoxy) benzophenone, 2-hydroxy-4- (3- (meth) acryloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy-4 -(3- (meth) acryloxy-1-hydroxypropoxy) benzophenone and the like can be mentioned.
An acrylic monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the acrylic monomer in the organic polymer fine particles is usually 5 to 70% by mass, preferably 10 to 60% by mass, from the viewpoint of the ultraviolet absorption ability of the obtained cured film, other physical properties, and economical efficiency. .

  From the viewpoints of manufacturability, dispersibility in the coating liquid, coatability of the coating liquid, transparency of the cured film, and the like, the organic polymer fine particles preferably have an average particle diameter in the range of 1 to 200 nm. What is in the range of 100 nm is more preferable. The average particle diameter of the polymer ultraviolet absorbing resin fine particles can be measured by a laser diffraction scattering method.

The organic polymer fine particles are preferably used in a form dispersed in a dispersion medium. Examples of the dispersion medium include water, lower alcohols such as methanol, ethanol, propanol and 1-methoxy-2-propanol, and methyl cellosolve. Cellosolves and the like are preferred. By using such a dispersion medium, the dispersibility of the organic polymer fine particles is improved, and sedimentation can be prevented.
More preferably, the dispersion medium is water. When the dispersion medium is water, it can also be used for the hydrolysis and condensation reaction of the silane compound, which is necessary when forming the matrix having the Si-O bond derived from the component (A).

  There is no restriction | limiting in particular in the manufacturing method of organic polymer fine particle, A conventionally well-known method, for example, an emulsion polymerization method, a fine suspension polymerization method, etc. are employable.

  Examples of the water-soluble polymerization initiator used for emulsion polymerization include water-soluble peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide, these initiators or cumene hydroperoxide, t-butyl hydroperoxide, and the like. Redox initiators that combine hydroperoxides with reducing agents such as acidic sodium sulfite, ammonium sulfite, and ascorbic acid, water-soluble azo compounds such as 2,2′-azobis (2-methylpropionamidine) dihydrochloride, etc. Can be mentioned.

  Examples of the oil-soluble polymerization initiator used in the fine suspension polymerization include oil-soluble organic peroxides such as diacyl peroxides, ketone peroxides, peroxyesters, peroxydicarbonates, 2,2′- Examples include azo compounds such as azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile).

  Specific examples of the organic polymer fine particles include, for example, a coating polymer ultraviolet absorbent ULS-700, ULS-1700, ULS-383MA, ULS-1383MA, ULS-383MG, ULS-385MG, and ULS manufactured by Yushi Co., Ltd. -1383MG, ULS-1385MG, ULS-635MH, etc., a polymer ultraviolet ray absorbing resin paint NCI-905-20EM or NCI-905-20EMA manufactured by Nikko Chemical Research Co., Ltd. (a copolymer of styrene monomer and benzotriazole monomer) Polymer ultraviolet absorbers) and the like.

  (F) A component may be used individually by 1 type and may be used in combination of 2 or more type.

The composition for forming an infrared shielding body of the present invention may further contain colloidal silica as the component (G).
Colloidal silica is also called colloidal silica or colloidal silicic acid. In water, it refers to a colloidal suspension of silicon oxide having Si—OH groups on the surface by hydration, and can be produced by adding hydrochloric acid to an aqueous solution of sodium silicate.

The colloidal silica may be dispersed in a non-aqueous solution or fine powder made by a vapor phase method.
Usually, the particle diameter is from several nm to several μm, and the average particle diameter is preferably 1 to 200 nm. The average particle diameter can be measured by a laser diffraction scattering method.

  The composition of the particles is indeterminate, and may be polymerized by forming siloxane bonds (—Si—O—, —Si—O—Si—). Usually, the particle surface is porous and is generally negatively charged in water.

  Component (G) includes “ultra-high-purity colloidal silica” Quartron PL series (product names: PL-1, PL-3, PL-7) manufactured by Fuso Chemical Industry Co., Ltd. “Colloidal Silica” (Product Name: Snowtex 20, Snowtex 30, Snowtex 40, Snowtex O, Snowtex O-40, Snowtex C, Snowtex N, Snowtex S, Snowtex 20L, Snowtex OL ") and" organosilica sol (product names: methanol silica sol, MA-ST-MS, MA-ST-L, IPA-ST, IPA-ST-MS, IPA-ST-L, IPA-ST-ZL, IPA-) ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-MS, MIB -ST, XBA-ST, PMA-ST, DMAC-ST, PGM-ST, etc.) "can be mentioned.

  (G) A component may be used individually by 1 type and may be used in combination of 2 or more type.

The composition for forming an infrared shielding body of the present invention may contain cerium oxide treated (pretreated) with a silane compound.
Pretreatment refers to changing the surface state of cerium oxide by reacting the OH group of cerium oxide with the silanol group of the silane compound to form a covalent bond. Silane-treated cerium oxide does not form aggregates or precipitates even when mixed with a sol (for example, colloidal silica) in which anionic particles are dispersed, and this silane-treated cerium oxide must be dispersed in both water and alcohol. Can do.
The cerium oxide to be used is not particularly limited, but is preferably in the form of particles and having an average particle diameter of 1 to 200 nm, and more preferably 1 to 100 nm from the viewpoint of transparency. Further, from the viewpoint of improving dispersibility, it is preferable to add after dispersing in a dispersion medium such as water or alcohol.

“Dispersed” refers to a state in which a dispersed phase (solid) is suspended and suspended in a dispersion medium (liquid). The “sol” is a colloid having a liquid as a dispersion medium and a solid as dispersed particles, and is sometimes referred to as a colloid solution. The average particle diameter of the cerium oxide fine particles can be measured by a laser diffraction scattering method.
As a dispersion medium, the same thing as the above-mentioned (C) component is mentioned, Water or alcohol is preferable. Examples of the alcohol include lower alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, and 1-methoxy-2-propanol.
A dispersion medium may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the silane compound are the same as those for the component (A). They may be used alone or in combination.
The structure of the surface treatment may be a complete two-layer structure or a structure in which each alkoxysilane, its hydrolysis condensate or polyalkoxysilane is mixed.

It is preferable that the ratio of the mass of the silane compound in the cerium oxide processed with the silane compound is 50 mass% or less, More preferably, it is 2-40 mass%.
If it is less than this, cerium oxide itself may aggregate or gel, and if it is more than this, the silane compound itself may react and aggregate or gel.

  Cerium oxide treated with a silane compound may be used alone or in combination of two or more.

The composition for forming an infrared shielding body of the present invention may contain a dispersion stabilizer.
With the dispersion stabilizer, the reaction product of the component (A) can be stably dispersed, and aggregation sedimentation and gelation can be suppressed. In the coating liquid of the present invention, the fine particles of the components (F) and (G) and the dispersion stabilizer are preferably kept in a dispersed state without causing aggregation and sedimentation or gelation. It is preferable that

An organic acid, particularly an organic carboxylic acid can be preferably used as the dispersion stabilizer. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and the like can be mentioned. Moreover, what has a boiling point of the grade which does not remain in a cured film at the time of hardening of the composition for infrared shielding body formation of this invention is preferable, More preferably, acetic acid can be utilized.
A dispersion stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type.

The composition for forming an infrared shielding body of the present invention may contain a leveling agent.
The leveling agent can improve the smoothness of the resulting cured film and the flowability during coating.

  Examples of the leveling agent include a silicone leveling agent, a fluorine leveling agent, an acrylic leveling agent, a vinyl leveling agent, and a leveling agent in which a fluorine type and an acrylic type are combined. All work on the surface of the coating film and reduce the surface tension. The leveling agent can be used depending on the purpose. The ability to decrease the surface tension is advantageous because silicone and fluorine are strong, and acrylic and vinyl are less susceptible to poor wetting when recoating.

  As a specific example of the silicone leveling agent, a copolymer of polyoxyalkylene and polydimethylsiloxane can be used. Commercially available silicone leveling agents include FZ-2118, FZ-77, FZ-2161, etc. manufactured by Toray Dow Corning Co., Ltd., KP321, KP323, KP324, KP326, KP340, KP341, etc. manufactured by Shin-Etsu Chemical Co., Ltd., etc. -Performance Materials Japan GK TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, TSF4453, TSF4460, BYK-300, BYK-302, BYK-306, BYK-307, BYK, etc. -320, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-345, BYK-346, BY -348, may be mentioned BYK-377, BYK-378, BYK-UV3500, BYK-3510, BYK-3570 and the like polyether-modified silicone oil (polyoxyalkylene-modified silicone oil) and the like.

  Moreover, when heat resistance of 150 degreeC or more is calculated | required, the aralkyl modified silicone oil which has polyester modification and a benzene ring is suitable. As a commercially available product of polyester-modified silicone oil, BYK-310, BYK-315, BYK-370 manufactured by BYK Japan Japan Co., Ltd., as a commercially available product of aralkyl-modified silicone oil having a benzene ring, BYK manufactured by BYK Japan Japan Co., Ltd. -322, BYK-323, and the like.

As the fluorine leveling agent, a copolymer of polyoxyalkylene and fluorocarbon can be used.
Examples of commercially available fluorine leveling agents include MEGAFAC series manufactured by DIC Corporation, FC series manufactured by Sumitomo 3M Corporation, and the like.
Examples of commercially available acrylic leveling agents include BYK-350, BYK-352, BYK-354, BYK-355, BYK358N, BYK-361N, BYK-380N, BYK-382, BYK-392 manufactured by BYK-Chemie Japan. And BYK-340 into which fluorine is introduced.

By blending the leveling agent, the finished appearance of the cured film is improved and can be uniformly applied as a thin film. The amount of the leveling agent used is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, based on the total amount of the infrared shielding body forming composition.
As a method of blending the leveling agent, it may be blended when preparing the infrared shielding body forming composition, or may be blended into the infrared shielding body forming composition immediately before forming the cured film. May be blended at both stages of preparation of the composition for forming an infrared shielding body and immediately before the formation of the cured film.

The composition for forming an infrared shielding body of the present invention may contain a flexibility imparting agent.
As the flexibility imparting agent, for example, a silicone resin or the like can be used.
Examples of commercially available silicone resins include Wasin Resin MK series, for example, Belsil PMS MK (a polymer containing repeating units (unit T) of CH ₃ SiO _3/2 , up to 1% by mass (CH ₃ )). ₂ containing SiO _2/2 unit (unit D)) or KR-242A manufactured by Shin-Etsu Chemical Co., Ltd. (containing 98 mass% unit T and 2 mass% dimethyl unit D and containing Si—OH end groups) ), KR-251 (containing 88% by mass of unit T and 12% by mass of dimethyl unit D and containing Si—OH end groups), KR-220L (comprising unit T of the formula CH ₃ SiO _3/2 , Si -OH (silanol) end group).

  The composition for forming an infrared shielding body of the present invention may contain a colorant (color tone adjusting agent). By including the colorant, the color tone of the infrared shielding body can be adjusted.

For example, the composite tungsten oxide Cs _0.33 WO ₃ exhibits a blue color, but the color tone of the infrared shielding body can be made green by blending a color tone adjusting agent that absorbs blue light therein.

As the colorant, organic dyes, organic pigments, inorganic pigments, and the like can be used.
Specific examples include coumarin dyes, rhodamine dyes, perylene dyes, phthalocyanine pigments, diketopyrrolopyrrole pigments, chromium oxide pigments, zinc cobalt oxide pigments and iron oxide pigments.

  The amount of the colorant to be used is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total amount of the infrared shielding body forming composition.

  The composition for forming an infrared shielding body of the present invention further includes a lubricity imparting agent, an antioxidant, a bluing agent, an antistatic agent, an antifoaming agent (antifoaming agent), a light stabilizer, a weather resistance imparting agent, Fine particle dispersants (anti-settling agents), fine particle surface activity modifiers, and the like can be included.

The content of the component (A-1) is preferably 0.01 to 70% by mass and more preferably 0.1 to 60% by mass in the component (A). The content of the component (A-2) is preferably 0.1 to 30% by mass and more preferably 0.3 to 20% by mass in the component (A). 0.1-30 mass% is preferable and, as for content of (A-3) component, 0.3-20 mass% is more preferable. The content of the component (A-4) is preferably 0.1 to 50% by mass, and more preferably 1 to 40% by mass.
In addition, although there is no restriction | limiting in particular as a compounding molar ratio of (A-2) component and (A-4) component, Preferably it is 1: 1-1: 5, More preferably, it is 1: 2-1: 4. is there. When the blending molar ratio of the component (A-2) and the component (A-4) is within the above range, the durability of the obtained cured film is further improved.

  0.001-30 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of (B) component, 0.001-20 mass parts is more preferable.

As for content of (C) component, 5-1000 mass parts is preferable with respect to 100 mass parts of (A) component, and 20-800 mass parts is more preferable.
When the content of the component (C) is less than 5 parts by mass, the binder component may be cured during storage of the composition. When the content of the component (C) exceeds 1000 parts by mass, drying may take time, and productivity may be deteriorated.

The total content of the components (D) and (E) is preferably 25 to 150 parts by mass and more preferably 40 to 100 parts by mass with respect to 100 parts by mass of the component (A).
When the total content of the components (D) and (E) is less than 25 parts by mass, the infrared shielding performance may be deteriorated. When the total content of the components (D) and (E) exceeds 150 parts by mass, the film strength may be reduced.

20-90 mass% is preferable with respect to 100 mass% of (D) and (E) component, and, as for content of (D) component, 40-80 mass% is more preferable.
The content of the component (E) is preferably 10 to 80% by mass and more preferably 20 to 60% by mass with respect to 100% by mass of the components (D) and (E).
When the content of the component (E) is less than 10% by mass, the infrared shielding component may not be stably dispersed. When the content of the component (E) exceeds 80% by mass, an excessive dispersion component may ooze out from the film.

When (F) component is contained, 0.1-50 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of (F) component, 1-40 mass parts is more preferable.
When (G) component is contained, 0.1-70 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of (G) component, 1-50 mass parts is more preferable.
The components (F) and (G) that are preferably used as the dispersion state are calculated using only the respective solid contents, and the dispersion medium included in each component is included in the component (C).

  In the composition for forming an infrared shielding body of the present invention, the components (A) to (E) or the components (A) to (G) are 90% by mass or more, 95% by mass or more, 98% by mass or more, It may be 100% by mass.

  In the method for producing the infrared shielding body forming composition of the present invention, after mixing the components (D) to (E) and the component (C), an external force is applied to disperse the component (D), The X liquid containing the components (A) to (C) is mixed with the Y liquid. Thereby, the composition for infrared shielding body formation can be formed.

  The X liquid may contain the above-mentioned components (F) to (G). In addition, the liquid X is cerium oxide treated with the above silane compound (pretreatment), leveling agent, flexibility imparting agent, lubricity imparting agent, antioxidant, bluing agent, antistatic agent, antifoaming agent. (Antifoaming agent), light stabilizer, weather resistance imparting agent, colorant, fine particle dispersing agent (precipitating agent), fine particle surface activity modifier and the like may be included.

Since the (D) component and the (C) component can be mixed more finely, the (D) component can be dispersed using the (E) component and the ester solvent. After that, it is preferable to carry out by heating the solution containing the ester solvent, evaporating the solvent, and adding the above-mentioned component (C) thereto.
Thereby, Y liquid can be mixed with X liquid more uniformly.

  The external force is preferably applied using a bead mill, a sand grinder, a ball mill, a jet mill, an ultrasonic dispersion device, or the like.

Examples of ester solvents include butyl acetate and 2-acetoxy-1-methoxypropane.
The heating temperature of the solution is preferably 70 to 150 ° C.
The heating time is preferably 120 minutes or less. When the heating time exceeds 120 minutes, the component (D) may be aggregated.
Evaporation may completely remove the solvent of the solution or leave some solvent.
Mixing of the X liquid and the Y liquid can be performed by a known method.

The cured film of this invention can be obtained by hardening | curing the composition for infrared shielding body formation.
Curing is preferably performed at 100 to 280 ° C. 130-250 degreeC is more preferable. The curing time is preferably 1 to 60 minutes.

The laminated body of this invention has a base material and the said cured film formed on the base material.
Examples of the substrate include glass, film, metal, wood, rubber, concrete, stone, ceramics, leather, paper, cloth, and fiber.

  Examples of the film include polyethylene, polypropylene, cycloolefin resin (eg, “ARTON” manufactured by JSR Corporation, “ZEONOR” “ZEONEX” manufactured by Nippon Zeon Co., Ltd.), polyolefin resins such as polymethylpentene, polyethylene terephthalate ( PET), polyester resins such as polybutylene terephthalate and polyethylene naphthalate, cellulose resins such as diacetyl cellulose, triacetyl cellulose and acetyl cellulose butyrate, polystyrene, syndiotactic polystyrene, acrylonitrile butadiene styrene resin (ABS resin) Styrene resin such as polyimide, imide resin such as polyimide, polyetherimide, polyamideimide, polyamide resin such as nylon, polyether ketone, Ketone resins such as ether ether ketone, sulfone resins such as polysulfone and polyethersulfone, vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride, acrylic resins such as methyl polymethacrylate, polycarbonate resins, polyphenylene sulfide , Polyacetal, modified polyphenylene ether, polyvinyl alcohol, epoxy resin, fluororesin and the like, and a polymer alloy / polymer blend in which a plurality of the above polymers are mixed may be used. Further, a laminated structure in which a plurality of the above resins are laminated may be used. Among the above resins, polyester resins, polyolefin resins, and polycarbonate resins are preferable.

The visible light transmittance of the laminate of the present invention is preferably 60% or more. It may be 100%.
The shielding coefficient is preferably 0.80 or less. 0 is also acceptable.

Example 1
(1) Production of liquid X In a sample tube having a volume of 50 ml, organic polymer fine particle ULS-1385MG (manufactured by Yushi Kogyo Co., Ltd., UV-absorbing skeleton species: benzotriazole, water dispersion / solid content concentration 30% by mass) 0 .80 g was charged while stirring at 500 rpm, 4.25 g of 1-methoxy-2-propanol, 0.50 g of water, 0.50 g of acetic acid, M silicate 51 (manufactured by Tama Chemical Industry Co., Ltd., “partial condensate of tetramethoxysilane” (Polyalkoxysilane which is (average 3 to 5 mer) ") 0.40 g, 1.51 g of methyltrimethoxysilane, 0.55 g of dimethoxy-3-glycidoxypropylmethylsilane, 20% by mass methanol of p-toluenesulfonic acid Each solution was added dropwise over 1 minute in the order of 0.05 g. Subsequently, after stirring at room temperature and 500 rpm for 60 minutes, the mixture was allowed to stand for one day, which was designated as X1 solution.
A sample tube with a volume of 20 ml was charged with 1.10 g of 3-isocyanatopropyltriethoxysilane and 0.35 g of 2-butanone oxime (isocyanate group blocking agent), stirred at room temperature at 500 rpm for 10 minutes, and then allowed to stand for one day. This was designated as X2 liquid. The blocking of the isocyanate group was confirmed by the disappearance of the isocyanate group signal by ¹³ C-NMR. The total amount of 3-isocyanatopropyltriethoxysilane and 2-butanone oxime was taken as the amount of blocked isocyanatosilane compound: (A-4) component.

Into a 200 ml three-necked flask equipped with a condenser tube, the X1 liquid and a stirring bar were placed, and while stirring at 500 rpm, IPA-ST-L (Nissan Chemical Industries, Ltd. (colloidal silica, isopropanol dispersion, colloidal silica concentration 30 mass) %, Average particle size 40-50 nm (manufacturer's published value)) was added dropwise over 5 minutes and stirred at room temperature for 60 minutes, followed by heating at 600 rpm and 80 ° C. for 3 hours in a nitrogen stream. , X2 liquid was added, and it stirred at 80 degreeC on the same conditions for 4 hours, and left still at room temperature overnight.
Further, 0.40 g of 3-aminopropyltrimethoxysilane was added dropwise thereto over 2 minutes. After stirring at room temperature for 10 minutes, the mixture was further heated at 700 rpm and 80 ° C. for 3 hours under a nitrogen stream.
Subsequently, the solution was allowed to stand for 1 week to obtain a solution X.

(2) Production of Y liquid Cesium tungsten complex oxide dispersion YMS-01A-2 (manufactured by Sumitomo Metal Mining, cesium tungsten complex oxide (Cs _0.33 WO ₃ ) and dispersant (polyalkylene glycol dispersant) Containing, solid content concentration 40%, cesium tungsten composite oxide: dispersant = 100: 60) was heated to 100 ° C. to evaporate the solvent, and concentrated to 2.7 g. 1-methoxy-2-propanol was added there until it became 6g, and it stirred and mixed until it became uniform using the sand grinder (Imex Co., Ltd. BSG-01 type | mold), and Y liquid was obtained.

  6 g of Y solution was added to 6 g of X solution and mixed by stirring to obtain an infrared shielding body fluid.

(3) Production of Glass with Infrared Shielding Film The obtained infrared shielding body fluid was applied onto a 3 mm thick soda lime glass substrate using a bar coater so that the cured film had a thickness of 3 μm. After drying at 50 ° C. for 1 minute, the temperature was raised to 250 ° C. and held for 5 minutes to obtain a glass with an infrared shielding film (cured film).

(4) Evaluation of glass with infrared shielding film The transmittance of glass with infrared shielding film is measured using a spectrophotometer UV-3600 (manufactured by Hitachi, Ltd.), and the visible light transmittance and shielding coefficient are calculated according to JIS R3106. did.
The visible light transmittance was 65% and the shielding coefficient was 0.62.

Moreover, the glass with an infrared shielding film was immersed in 200 ml of boiling water for 60 minutes.
There was no change in appearance, and the visible light transmittance remained at 65%.

Example 2
Except that 10g of cesium tungsten complex oxide dispersion was concentrated to 4.3g and replaced with 6g using 1-methoxy-2-propanol, 10g using 1-methoxy-2-butanol was carried out. In the same manner as in Example 1, Y liquid was produced.
Moreover, the infrared shielding body liquid was manufactured like Example 1 except having added the said Y liquid 10g to the X liquid 10g.
Infrared shielding film as in Example 1, except that a PET film (manufactured by Toyobo Cosmo Shine A4100, thickness 100 μm) was used in place of the soda-lime glass substrate, the temperature was raised to 100 ° C., and the holding time was 10 minutes. The attached film was manufactured and evaluated.

The visible light transmittance was 78% and the shielding coefficient was 0.77.
After immersion in boiling water, the appearance did not change and the visible light transmittance remained at 78%.

Comparative Example 1
An infrared shielding liquid and an infrared shielding glass-coated glass were produced and evaluated in the same manner as in Example 1 except that the X2 liquid was not blended and methyltrimethoxysilane was changed from 1.51 g to 2.12 g.

The visible light transmittance was 65% and the shielding coefficient was 0.62.
After immersion in boiling water, the appearance was cloudy and the visible light transmittance was reduced to 53%.

Example 3
(1) Production of solution X In a sample tube with a volume of 50 ml, organic polymer fine particle ULS-1385MG (manufactured by Yushi Kogyo Co., Ltd., UV-absorbing skeleton species: benzotriazole, water dispersion / solid content concentration 30% by mass) 2 While charging 40 g and stirring at 500 rpm, 12.75 g of 1-methoxy-2-propanol, 1.50 g of water, 1.50 g of acetic acid, M silicate 51 (manufactured by Tama Chemical Industry Co., Ltd., “partial condensate of tetramethoxysilane” (Polyalkoxysilane which is (average 3 to 5 mer) ”) 1.20 g, 4.53 g of methyltrimethoxysilane, 1.65 g of dimethoxy-3-glycidoxypropylmethylsilane, 20% by mass of p-toluenesulfonic acid methanol Each solution was added dropwise over 1 minute in the order of 0.15 g. Subsequently, the mixture was stirred at room temperature and 500 rpm for 60 minutes, and then allowed to stand for one day, which was designated as X1a solution.
A sample tube with a volume of 20 ml was charged with 3.30 g of 3-isocyanatopropyltriethoxysilane and 1.05 g of 2-butanone oxime (isocyanate group blocking agent), stirred at room temperature at 500 rpm for 10 minutes, and then allowed to stand for one day. This was designated as X2a liquid. The blocking of the isocyanate group was confirmed by the disappearance of the isocyanate group signal by ¹³ C-NMR. The total amount of 3-isocyanatopropyltriethoxysilane and 2-butanone oxime was taken as the amount of blocked isocyanatosilane compound: (A-4) component.

Into a 200 ml three-necked flask equipped with a condenser, the solution X1a and a stirrer were placed, and while stirring at 500 rpm, 13.65 g of isopropyl alcohol was added dropwise over 5 minutes and stirred at room temperature for 60 minutes. Then, it heated at 600 rpm and 80 degreeC under nitrogen stream for 3 hours. Subsequently, the solution X2a was added, stirred at 80 ° C. for 4 hours under the same conditions, and allowed to stand overnight at room temperature.
Further, 1.20 g of 3-aminopropyltrimethoxysilane was added dropwise thereto over 2 minutes. After stirring at room temperature for 10 minutes, the mixture was further heated at 700 rpm and 80 ° C. for 3 hours under a nitrogen stream.
Subsequently, the solution was allowed to stand for 1 week to obtain a solution X.

(2) Production of Y liquid Cesium tungsten complex oxide dispersion YMS-01A-2 (manufactured by Sumitomo Metal Mining, cesium tungsten complex oxide (Cs _0.33 WO ₃ ) and dispersant (polyalkylene glycol dispersant) Containing, solid content concentration 40%, cesium tungsten composite oxide: dispersant = 100: 60) was heated to 100 ° C. to evaporate the solvent, and concentrated to 2.7 g. 1-methoxy-2-propanol was added there until it became 6g, and it stirred and mixed until it became uniform using the sand grinder (Imex Co., Ltd. BSG-01 type | mold), and Y liquid was obtained.

  4 g of Y liquid and 2 g of 1-methoxy-2-butanol were added to 2 g of X liquid and mixed by stirring to obtain an infrared shielding body liquid.

(3) Production of Glass with Infrared Shielding Film The obtained infrared shielding body fluid was applied onto a 3 mm thick soda lime glass substrate using a bar coater so that the cured film had a thickness of 3 μm. After drying at 50 ° C. for 1 minute, the temperature was raised to 200 ° C. and held for 10 minutes to obtain a glass with an infrared shielding film (cured film).

(4) Evaluation of glass with infrared shielding film The transmittance of glass with infrared shielding film is measured using a spectrophotometer UV-3600 (manufactured by Hitachi, Ltd.), and the visible light transmittance and shielding coefficient are calculated according to JIS R3106. did.
The visible light transmittance was 71% and the shielding coefficient was 0.67.

Example 4
(1) Production of solution X 3.75 g of 1-methoxy-2-propanol was charged into a sample tube with a volume of 50 ml and stirred at 500 rpm, while 3.18 g of water, 1.50 g of acetic acid, M silicate 51 (Tama Chemical Co., Ltd.) 1.20 g of a “tetraalkoxysilane partial condensate (average 3-5 mer)”, 4.53 g of methyltrimethoxysilane, dimethoxy-3-glycidoxypropylmethylsilane 65 g and 20% by mass of p-toluenesulfonic acid methanol solution 0.15 g were added dropwise over 1 minute each. Subsequently, after stirring at room temperature and 500 rpm for 60 minutes, the mixture was allowed to stand for one day, which was designated as X1b solution.
A sample tube with a volume of 20 ml was charged with 3.30 g of 3-isocyanatopropyltriethoxysilane and 1.05 g of 2-butanone oxime (isocyanate group blocking agent), stirred at room temperature at 500 rpm for 10 minutes, and then allowed to stand for one day. This was designated as X2b solution. The blocking of the isocyanate group was confirmed by the disappearance of the isocyanate group signal by ¹³ C-NMR. The total amount of 3-isocyanatopropyltriethoxysilane and 2-butanone oxime was taken as the amount of blocked isocyanatosilane compound: (A-4) component.

Into a 200 ml three-necked flask equipped with a condenser tube, the X1b solution and a stirrer were placed, and while stirring at 500 rpm, IPA-ST-L (manufactured by Nissan Chemical Industries, Ltd. (colloidal silica, isopropanol dispersion, colloidal silica concentration 30 mass) %, Average particle size 40-50 nm (manufacturer's published value) 19.50 g was added dropwise over 5 minutes and stirred at room temperature for 60 minutes, followed by heating at 600 rpm and 80 ° C. for 3 hours under a nitrogen stream. , X2b solution was added, and the mixture was stirred at 80 ° C. for 4 hours under the same conditions, and then allowed to stand overnight at room temperature.
Further, 1.20 g of 3-aminopropyltrimethoxysilane was added dropwise thereto over 2 minutes. After stirring at room temperature for 10 minutes, the mixture was further heated at 700 rpm and 80 ° C. for 3 hours under a nitrogen stream.
Subsequently, the solution was allowed to stand for 1 week to obtain a solution X.

(2) Production of Y liquid Cesium tungsten complex oxide dispersion YMS-01A-2 (manufactured by Sumitomo Metal Mining, cesium tungsten complex oxide (Cs _0.33 WO ₃ ) and dispersant (polyalkylene glycol dispersant) Containing, solid content concentration 40%, cesium tungsten composite oxide: dispersant = 100: 60) was heated to 100 ° C. to evaporate the solvent, and concentrated to 2.7 g. 1-methoxy-2-propanol was added there until it became 6g, and it stirred and mixed until it became uniform using the sand grinder (Imex Co., Ltd. BSG-01 type | mold), and Y liquid was obtained.

  4 g of Y liquid and 2 g of 1-methoxy-2-butanol were added to 2 g of X liquid and mixed by stirring to obtain an infrared shielding body liquid.

(3) Production of Glass with Infrared Shielding Film The obtained infrared shielding body fluid was applied onto a 3 mm thick soda lime glass substrate using a bar coater so that the cured film had a thickness of 3 μm. After drying at 50 ° C. for 1 minute, the temperature was raised to 250 ° C. and held for 10 minutes to obtain a glass with an infrared shielding film (cured film).

(4) Evaluation of glass with infrared shielding film The transmittance of glass with infrared shielding film is measured using a spectrophotometer UV-3600 (manufactured by Hitachi, Ltd.), and the visible light transmittance and shielding coefficient are calculated according to JIS R3106. did.
The visible light transmittance was 73% and the shielding coefficient was 0.69.

  The composition for forming an infrared shielding body of the present invention can be used for window materials, electronic devices, and the like used in the construction field, transportation equipment field, and the like.

Claims (12)

The composition for infrared shielding body containing the following (A)-(E) component.
(A) Hydrolysis condensate of a silane compound having an alkoxy group of the following components (A-1) to (A-4) (A-1) An alkoxysilane compound represented by the following formula (1), or the alkoxysilane Polyalkoxysilane compound in which compounds are connected by a siloxane bond (Si—O bond) (R ¹ ) _m Si (OR ² ) _4-m (1)
(In the formula, R ¹ may be the same or different, an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group, or a methacryloxy alkyl group having 1 to 3 carbon atoms which is substituted with a group .R ² Is an alkyl group having 1 to 4 carbon atoms, and m is 0, 1 or 2.)
(A-2) Aminosilane compound represented by the following formula (2) (R ¹¹ ) _n Si (OR ¹² ) _4-n (2)
(In the formula, R ¹¹ may be the same or different and substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group, or a methacryloxy group and an amino group. an alkyl group having 1 to 3 carbon atoms, at least one of R ¹¹ is an alkyl group having 1 to 3 carbon atoms substituted with an amino group. the amino group may have a substituent. R ¹² is an alkyl group having 1 to 4 carbon atoms, and n is 1 or 2.)
(A-3) Epoxysilane compound represented by the following formula (3) (R ²¹ ) _k Si (OR ²² ) _4-k (3)
(In the formula, R ²¹ may be the same or different and is selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group, or a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. An alkyl group having 1 to 3 carbon atoms substituted with one or more groups, and at least one of R ²¹ is an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group; R ²² is an alkyl group having 1 to 4 carbon atoms, and k is 1 or 2.)
(A-4) Blocked isocyanatosilane compound having an alkoxy group (B) Curing catalyst (C) Dispersion medium (D) Formula M _x W _y O _z (where M is a hydrogen atom, an alkali metal, an alkaline earth) Metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge , Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I 1 More than one kind of element or ammonium group, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1.1, and 2.2 ≦ z / y ≦ 3.0. ) Composite tungsten oxide represented by (E) (D) component dispersion Agent   The composition for forming an infrared shielding body according to claim 1, further comprising (F) organic polymer fine particles comprising a copolymer containing a monomer unit having an ultraviolet absorbing group.   The organic polymer fine particles include an acrylic monomer having a skeleton selected from a benzophenone skeleton, a benzotriazole skeleton, and a triazine skeleton in a side chain, acrylic acid, acrylic acid derivative, methacrylic acid, methacrylic acid derivative, styrene, and vinyl acetate. The composition for forming an infrared shielding body according to claim 2, which is a copolymer with an ethylenically unsaturated compound selected and has a weight average molecular weight of more than 10,000.   Furthermore, the composition for infrared shielding body formation in any one of Claims 1-3 containing (G) colloidal silica. After mixing the components (D) to (E) and the component (C), an external force is applied to disperse the component (D) to form a Y liquid,
The manufacturing method of the composition for infrared shielding body formation which forms the composition for infrared shielding body formation by mixing X liquid containing the following (A)-(C) component, and the said Y liquid.
(A) Hydrolysis condensate of a silane compound having an alkoxy group of the following components (A-1) to (A-4) (A-1) An alkoxysilane compound represented by the following formula (1), or the alkoxysilane Polyalkoxysilane compound in which compounds are connected by a siloxane bond (Si—O bond) (R ¹ ) _m Si (OR ² ) _4-m (1)
(In the formula, R ¹ may be the same or different, an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group, or a methacryloxy alkyl group having 1 to 3 carbon atoms which is substituted with a group .R ² Is an alkyl group having 1 to 4 carbon atoms, and m is 0, 1 or 2.)
(A-2) Aminosilane compound represented by the following formula (2) (R ¹¹ ) _n Si (OR ¹² ) _4-n (2)
(In the formula, R ¹¹ may be the same or different and substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group, or a methacryloxy group and an amino group. an alkyl group having 1 to 3 carbon atoms, at least one of R ¹¹ is an alkyl group having 1 to 3 carbon atoms substituted with an amino group. the amino group may have a substituent. R ¹² is an alkyl group having 1 to 4 carbon atoms, and n is 1 or 2.)
(A-3) Epoxysilane compound represented by the following formula (3) (R ²¹ ) _k Si (OR ²² ) _4-k (3)
(In the formula, R ²¹ may be the same or different and is selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group, or a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. An alkyl group having 1 to 3 carbon atoms substituted with one or more groups, and at least one of R ²¹ is an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group; R ²² is an alkyl group having 1 to 4 carbon atoms, and k is 1 or 2.)
(A-4) Blocked isocyanatosilane compound having an alkoxy group (B) Curing catalyst (C) Dispersion medium (D) Formula M _x W _y O _z (where M is a hydrogen atom, an alkali metal, an alkaline earth) Metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge , Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I 1 More than one kind of element or ammonium group, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1.1, and 2.2 ≦ z / y ≦ 3.0. ) Composite tungsten oxide represented by (E) (D) component dispersion Agent   6. The method for producing an infrared shielding composition according to claim 5, wherein the liquid X further comprises (F) organic polymer fine particles comprising a copolymer containing a monomer unit having an ultraviolet absorbing group.   The method for producing a composition for forming an infrared shielding body according to claim 5 or 6, wherein the liquid X further contains (G) colloidal silica.   In the mixing of the components (D) to (E) and the component (C), the component (D) is dispersed using the component (E) and the ester solvent, and then the solution containing the ester solvent is heated to obtain a solvent. The method for producing an infrared shielding body forming composition according to claim 5, wherein the component (C) is added thereto and the component (C) is added thereto.   The cured film formed by hardening | curing the composition manufactured by the method of any one of Claims 1-4, or the method of Claims 5-8. A substrate;
The cured film according to claim 9 formed on the substrate,
A laminate having   The laminate according to claim 10, wherein the substrate is a film.   The laminate according to claim 10, wherein the substrate is glass.