JP2006103069A - Heat barrier multilayer object and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat barrier multilayer object having both of excellent light fastness and light transmissivity. <P>SOLUTION: This laminate is composed of a light pervious substrate and the heat barrier multilayer object provided on the substrate. The heat barrier multilayer object has at least an ultraviolet absorbing layer and a near infrared absorbing layer, and the near infrared absorbing layer is formed from a composition prepared by dispersing a near infrared absorbing material containing copper ions in a resin material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a heat-shielding multilayer body, in particular, a heat-shielding multilayer body suitable as an interlayer film for laminated glass, and a laminate comprising the same.

  As an optical member for use in a window material or the like, a laminated glass having a structure in which an intermediate film made of polyvinyl acetal resin, acrylic resin, or the like is sandwiched between a pair of translucent substrates made of glass or the like is known. Such a laminated glass is frequently used because it has excellent properties such as high strength and high durability.

  These laminated glasses are required to have characteristics capable of blocking infrared rays or light rays having wavelengths in the vicinity thereof (hereinafter referred to as “near infrared light”). When laminated glass having such characteristics is applied to window materials, wall materials, and the like, for example, light having a wavelength in the above-described region in sunlight, that is, entry of heat rays into the room can be suppressed. Thereby, it becomes possible to keep the indoor environment comfortable by suppressing the temperature from becoming excessively high, and it is also possible to reduce the cost for cooling and the like.

  As a laminated glass capable of blocking near-infrared light, one having a structure in which an intermediate film having near-infrared light absorption is sandwiched between a pair of translucent substrates is known. As an intermediate film in this case, a film composed of a composition in which a near-infrared light absorbing material containing metal ions or the like is dispersed in a resin material is known.

  However, a laminated glass having an intermediate film made of such a composition, when irradiated with light, especially ultraviolet light for a long time, discoloration or turbidity occurs in the intermediate film, bubbles occur in the intermediate film, Further, there was a tendency that the light-transmitting properties gradually deteriorated and deteriorated with long-term use, such as colored precipitates formed in the intermediate film. Therefore, in order to put it into practical use as a material such as a window material, further improvement for improving the stability to light (that is, light resistance) is necessary.

Therefore, in recent years, attempts have been made to further add a material (ultraviolet light absorbing material) having a characteristic of absorbing ultraviolet light into the intermediate film in order to improve stability against irradiation of light, particularly ultraviolet light.
JP 2001-264501 A JP 2001-354945 A

  However, even when an ultraviolet light absorbing material is added to an intermediate film containing a near infrared light absorbing material as in the above prior art, the discoloration, turbidity, foaming or precipitation of the intermediate film is sufficiently reduced. However, it was difficult to obtain sufficient light resistance.

  Therefore, the present invention has been made in view of such circumstances, and can be applied to an interlayer film or the like of laminated glass, and can obtain excellent near-infrared light absorbability and also provide sufficient light resistance. An object is to provide a multilayer body. Another object of the present invention is to provide such a heat-shielding multilayer body and to provide a laminate suitable as a laminated glass.

  In order to achieve the above object, a heat shielding multilayer body of the present invention is a heat shielding multilayer body comprising at least an ultraviolet light absorption layer and a near infrared light absorption layer, and the near infrared light absorption layer is made of copper. A near infrared light absorbing material containing ions is dispersed in a resin material.

  Thus, the heat-insulating multilayer body of the present invention includes a layer having an ultraviolet light absorption property in a layer different from the near infrared light absorption layer. Since the heat shielding multilayer body having such a configuration can reduce the irradiation of light in the ultraviolet region to the infrared light absorption layer, it can suppress deterioration of the near infrared light absorption layer due to light (ultraviolet light) irradiation, In addition, such an effect is superior to an intermediate film containing a near-infrared light absorbing material and an ultraviolet light absorbing material in one layer as in the conventional case. Thus, according to the heat shielding multilayer body of the present invention, excellent near-infrared light absorbability can be obtained, and sufficient light resistance can be obtained.

  The near-infrared light absorbing material further contains at least one phosphorus compound selected from the group consisting of phosphinic acid compounds, phosphonic acid compounds, phosphonic acid monoester compounds, phosphoric acid monoester compounds, and phosphoric acid diester compounds. And preferred. If it carries out like this, the near-infrared-light absorption characteristic of a near-infrared-light absorption layer will become further excellent.

  Moreover, the heat-insulating multilayer body of the present invention may further have a light-transmitting layer between the ultraviolet light absorbing layer and the near infrared light absorbing layer. The heat-shielding multilayer body having such a form also provides excellent near-infrared light absorbability and sufficient light resistance.

  Moreover, it is more preferable that the heat-insulating multilayer body of the present invention includes at least two ultraviolet light absorption layers, and the near infrared light absorption layer is disposed between the two ultraviolet light absorption layers. With such a configuration, the light irradiated to the heat shield multilayer body always passes through the ultraviolet light absorption layer and then reaches the near infrared light absorption layer. Therefore, the amount of ultraviolet light reaching the near infrared light absorbing layer is extremely small, and as a result, the deterioration of the near infrared light absorbing layer can be further suppressed.

  The present invention also provides a laminate including a light-transmitting substrate on one surface of the heat shielding multilayer body. Since such a laminate includes the above-described heat-shielding multilayer body of the present invention, it has excellent light resistance such as generation of precipitates and the like even when irradiated with light for a long time. In addition, it has translucency sufficient for practical use as a window material.

  And this invention provides the laminated body which further comprises a translucent board | substrate on the other surface of a thermal-insulation multilayer body. Such a laminate can be applied as a laminated glass having excellent ultraviolet light and near infrared light blocking properties.

  According to the present invention, it can be applied as an intermediate film such as laminated glass, and by including both an ultraviolet light absorbing material and a near infrared light absorbing material, excellent light resistance can be obtained, and excellent translucency can also be obtained. It becomes possible to provide a heat shield multilayer body that can be maintained. Moreover, it is possible to provide a laminated body suitable as a laminated glass, provided with such a heat shielding multilayer body.

Hereinafter, preferred embodiments of the present invention will be described with reference to the raw surfaces. In addition, the same code | symbol is attached | subjected to the same element and the overlapping description is abbreviate | omitted.
[Heat insulation multilayer]

  First, a thermal barrier multilayer according to a preferred embodiment will be described. The thermal barrier multilayer body of the embodiment includes an ultraviolet light absorption layer and a near infrared light absorption layer. In addition, this heat insulation multilayer body should just contain an ultraviolet light absorption layer and a near-infrared light absorption layer at least one layer each, and the number of layers is not specifically limited. Moreover, other layers (resin layer, glass, etc.) which have translucency may be included between the ultraviolet light absorption layer and the near infrared light absorption layer.

(Ultraviolet light absorption layer)
First, the ultraviolet light absorbing layer will be described. The ultraviolet light absorbing layer is a layer in which an ultraviolet light absorbing material is dispersed in a base material constituting the layer. As a base material, if it consists of a material which has the characteristic which permeate | transmits visible light at least, such as a resin material and glass, it can apply without a restriction | limiting especially. In consideration of dispersion of the ultraviolet light absorbing material, thinning of the intermediate film, and the like, the base material is preferably a resin material whose viscosity, thickness, etc. are relatively easy to adjust. In addition, as long as this ultraviolet light absorption layer has the characteristic which mainly absorbs ultraviolet light, it may further contain the material which can provide other characteristics, such as a near infrared light absorption material. In this case, it is preferable to use a material having excellent light resistance as the near infrared light absorbing material.

  Examples of the ultraviolet light absorbing material dispersed in the substrate include benzoate compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, oxalic acid anilide compounds, triazine compounds, and the like. .

  More specifically, as the benzoate compound, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate (Viosorb-80, manufactured by Kyodo Yakuhin Co., Ltd.) Examples of salicylate compounds include phenyl salicylate and pt-butylphenyl salicylate (Viosorb-90, manufactured by Kyodo Yakuhin Co., Ltd.).

  Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone (Viosorb-110, manufactured by Kyodo Yakuhin), 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2- Hydroxy-4-n-octyloxybenzophenone (Viosorb-130, manufactured by Kyodo Yakuhin Co., Ltd.), 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2 ′, 4,4′-tetrahydrobenzophenone, bis (5-benzoyl) -4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-sodium disulfonate 2,2'-dihydroxy-5-methoxy Benzophenone, 2-hydroxy-4-methacryloyloxyethyl benzophenone, 4-benzoyloxy-2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxy benzophenone.

  Examples of benzotriazole compounds include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole (Tinvin-P, manufactured by Ciba Geigy), 2- (2′-hydroxy-3′-t-butyl-5 ′). -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5-t-butylphenyl) benzotriazole, 2 -[2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] Nzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole (Tinuvin-328, manufactured by Ciba Geigy), 2- (2′-hydroxy-5-t-octyl) Phenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethoxybenzoyl) phenyl] benzotriazole (Tinvin-234, manufactured by Ciba Geigy), 2,2′-methylenebis [4 -(1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzo Triazole, 2- (2′-hydroxy-3′-dodecyl-5′-methylphenyl) benzotriazole, methyl- - condensates of [3-t-butyl-5-(2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol.

  Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenyl acrylate (Viosorb-910, manufactured by Kyodo Yakuhin Co., Ltd.) and octyl-2-cyano-3,3-diphenyl acrylate. Examples of the compound include 2-ethoxy-2′-ethyloxalic acid bisanilide (Tinuvin-312, manufactured by Ciba Geigy) and 2-ethoxy-5-t-butyl-2′-ethyloxalic acid bisanilide. Examples of the triazine-based compound include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol.

  The ultraviolet light absorption layer containing the above-described components can be formed, for example, by the following method. That is, for example, when the base material is made of a resin material, the ultraviolet light absorbing material is mixed in a melted state of the resin material, or after the ultraviolet light absorbing material is mixed in the monomer solution that is a precursor of the resin material A method for causing a polymerization reaction is mentioned. Moreover, when a base material consists of glass, the method of mixing various metal compounds, such as cerium, titanium, and iron, as an ultraviolet light absorption material in the state which fuse | melted glass is mentioned.

(Near infrared light absorption layer)
Next, the near-infrared light absorbing layer according to a preferred embodiment will be described. The near infrared light absorbing layer is made of a composition containing a resin material and a near infrared light absorbing material containing copper ions. In addition, if this near-infrared light absorption layer has the characteristic which mainly absorbs near-infrared light, it will contain further the material which can provide other characteristics, such as an ultraviolet light absorption material as mentioned above, for example. You may do it.

  As the resin material, a material that is excellent in dispersibility of the near-infrared light absorbing material described later and has a property of transmitting visible light can be used. Examples of such resin materials include polyvinyl acetal resin, ethylene-vinyl acetate copolymer (EVA), (meth) acrylic resin, polyester resin, polyurethane resin, vinyl chloride resin, polyolefin resin, polycarbonate resin, norbornene resin, and the like. Is mentioned.

  Among these, polyvinyl acetal resin is preferable, and polyvinyl butyral (PVB) is particularly preferable. Polyvinyl butyral resin has a characteristic that it is flexible and easily deforms depending on temperature. For this reason, by using such a resin material, it becomes easy to form and process the laminated body. Moreover, the polyvinyl acetal resin also has a characteristic that the near-infrared light absorbing material is easily dissolved and / or dispersed. Therefore, according to the combination of the near-infrared light absorbing material and the polyvinyl acetal resin, a laminate (laminated glass) having excellent translucency and light resistance can be obtained.

  The near infrared light absorbing material contains a divalent copper ion. The copper ions can be supplied into the near infrared light absorbing material in the form of a copper salt. Specific examples of copper salts include copper acetate anhydrides, hydrates of organic acids such as copper acetate, copper formate, copper stearate, copper benzoate, copper ethylacetoacetate, copper pyrophosphate, copper naphthenate, and copper citrate. Alternatively, a hydrate, an anhydride, a hydrate or a hydrate of a copper salt of an inorganic acid such as copper oxide, copper chloride, copper sulfate, copper nitrate, basic copper carbonate, or copper hydroxide can be used. Among these, copper acetate, copper acetate monohydrate, copper benzoate, copper hydroxide, and basic copper carbonate are preferably used. In addition, these copper salts which are copper ion sources may be used independently, and may be used in multiple combination.

The near-infrared light absorbing material preferably contains a phosphorus-containing compound in addition to copper ions. Examples of the phosphorus-containing compound include a phosphoric acid ester compound represented by the following general formula (1A), a phosphinic acid compound represented by the following general formula (1B), a phosphonic acid compound represented by the following general formula (1C), and And at least one phosphorus compound selected from the group consisting of phosphonic acid monoester compounds represented by the following general formula (1D).

In the above formula, n is 1 or 2, and R ¹ , R ²¹ , R ²² , R ³ , R ⁴¹ and R ⁴² each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group or an aryl group. , An allyl group, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxyaryl group, a (meth) acryloyloxyalkyl group or a (meth) acryloylpolyoxyalkyl group, and the carbon number of these groups is 1-30. In these groups, at least one hydrogen atom in the group is a halogen atom, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxyaryl group, an acyl group, an aldehyde group, a carboxyl group, a hydroxyl group, It may be substituted with a (meth) acryloyl group, a (meth) acryloyloxyalkyl group, a (meth) acryloyl polyoxyalkyl group or an ester group. In addition, as a phosphorus compound, only 1 type of the compounds represented by said formula (1A)-(1D) may be used, and you may use in combination of multiple types. Moreover, about each of said phosphorus compound of (1A)-(1D), what has the said various functional groups may be used independently, and 2 or more types may be used in combination.

Especially, as a phosphorus compound, the phosphate ester compound (monoester and / or diester) represented by the said general formula (1A) is preferable. In the phosphate compound represented by the general formula (1A), the group represented by R ¹ includes an alkyl group, an alkenyl group, a polymerizable functional group represented by the following general formula (2), or oxy Alkyl groups containing groups are preferred. In the following general formula (2), X represents a hydrogen atom or a methyl group, p is an integer of 2 to 6, and m is an integer of 0 to 5.

Among the functional groups represented by R ¹ described above, the alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 18 carbon atoms. Examples of such an alkyl group include an n-butyl group, an n-hexyl group, an n-octyl group, a 2-ethylhexyl group, an n-decyl group, and an n-dodecyl group. Among them, a 2-ethylhexyl group is preferable. preferable. Moreover, as an alkenyl group, an oleyl group is preferable. Furthermore, among the groups represented by R ¹ , the polymerizable functional group represented by the general formula (2) includes acryloyloxyethyl in which X = H, p = 2, and m = 1. Groups are preferred.

Furthermore, among the groups represented by R ¹ , examples of the alkyl group containing an oxy group include groups represented by the following chemical formulas (3A) to (3N), and in particular, a methoxyisopropyl group (the following chemical formula (3C )), An ethoxydiethylene glycol group (the following chemical formula (3K)) or a butoxytriethylene glycol group (the following chemical formula (3N)) is preferable.

  When the near-infrared light-absorbing material contains such a phosphorus-containing compound, the copper ion and the phosphorus-containing compound may exist as a mixture, but exist in the state of a copper complex in which they have reacted. It is more preferable. Such a copper complex is formed by an ionic bond and / or a coordinate bond between a phosphorus-containing group in a phosphorus compound (for example, a phosphate group in a phosphate ester) and a copper ion.

  When a phosphate ester is included as the phosphorus-containing compound, it is particularly preferable that the above-described copper complex (hereinafter referred to as “phosphate ester copper complex”) is formed. Examples of such a phosphate ester copper complex include a copper complex of 2-ethylhexyl phosphate (hereinafter, such a copper complex is abbreviated as “2-EHP-C”, the same shall apply hereinafter), a copper complex of oleyl phosphate ( OLP-C), acryloyloxyethyl phosphate copper complex (P2M-C), phosphoric acid (methoxyisopropyl) copper complex (MPP-C), phosphoric acid (ethoxydiethylene glycol) copper complex (EDEP-C), phosphorus A copper complex of acid (butoxytriethylene glycol) (BTEP-C) is preferred.

  Such a complex of phosphorus-containing compound and copper ion may be formed by adding and mixing these directly into the resin material, or mixing the phosphorus-containing compound and copper complex in a predetermined solvent. The complex may be prepared in advance and added to the resin material. In the latter case, the copper complex tends to be more reliably formed.

  And when the composition which comprises a near-infrared-light absorption layer contains a resin material and the said copper complex, content of this copper complex is 0.5-45 with respect to 100 mass parts of resin materials. It is preferable that it is mass%, it is more preferable that it is 1-40 mass%, and it is still more preferable that it is 1-35 mass%.

  The compounding amount of the copper ion and the phosphorus-containing compound is, when the phosphorus-containing compound has a hydroxyl group or an oxygen atom derived from a hydroxyl group, (total amount of hydroxyl group or oxygen atom) / (content of copper ion), The molar ratio is preferably adjusted so as to satisfy the relationship of 1 to 6, more preferably 1 to 4, and still more preferably 1.5 to 2.5. If this ratio is less than 1, the near-infrared light absorbability and visible light transmittance tend to be reduced. On the other hand, if it exceeds 6, the amount of hydroxyl groups that do not participate in coordination bonds or ionic bonds with copper ions becomes excessive, and the hygroscopicity tends to be excessive.

  In addition, the composition which comprises a near-infrared-light absorption layer may further contain the other component for adjusting a various characteristic other than each component mentioned above. As other components, first, a plasticizer may be mentioned. When the plasticizer is contained in this manner, the solubility and / or dispersibility of copper ions in the resin material tends to be further improved, and the near-infrared light absorbability and visible light transmittance can be further improved. .

  Examples of the plasticizer include phosphate ester plasticizers, phthalic acid plasticizers, fatty acid plasticizers, glycol plasticizers, and the like. More specifically, triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2 ethyl butyrate (3GH), dihexyl adipate (DHA), tetraethylene glycol diheptanoate (4G7) , Tetraethylene glycol di-2-ethylhexanoate (4GO), triethylene glycol diheptanoate (3G7) and the like.

  The plasticizer content in the composition is preferably 1 to 120 parts by mass, more preferably 1 to 100 parts by mass, and 2 to 80 parts by mass with respect to 100 parts by mass of the resin material. Is more preferable. When the content of the plasticizer is less than 1 part by mass with respect to 100 parts by mass of the resin material, the solubility of the copper ions and the phosphorus-containing compound may be reduced, and the translucency may be insufficient. On the other hand, when it exceeds 100 parts by mass, the resin material as the base material becomes too flexible, and for example, it tends to be difficult to use as an interlayer film in laminated glass.

  Further, as described above, the composition may contain an ultraviolet light absorbing material, and may contain a light stabilizer for further improving the stability to light. As the latter light stabilizer, a hindered amine light stabilizer (HALS) or a Ni compound can be applied.

  More specifically, HALS includes bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1 -[2- [3- (3,5-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy ] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl- 1,3,8-triazaspiro [4,5] decane-2,4-dione, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t -Butyl-4-hydroxybe Diyl) -2-n-butylmalonate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6) , 6-Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, (Mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3 , 4-Butanetetracarboxylate, Mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2,4,8, 10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, (Mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, Mixed {2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2 , 4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1 , 2,2,6,6-pentamethyl-4-piperidyl methacrylate, poly [(6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl) ] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) iminol], dimethyl succinate polymer-with-4 - Droxy-2,2,6,6-tetramethyl-1-piperidineethanol, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2 , 2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-triazine-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethylpiperidyl) butylamine polycondensate, decane And diacid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester.

  Ni-based light stabilizers include [2,2′-thio-bis (4-t-octylphenolate)]-2-ethylhexylamine-nickel (II), nickel dibutyldithiocarbonate, [2,2 '-Thio-bis (4-t-octylphenolate)]-butylamine-nickel (II) and the like.

  In addition, an antioxidant, a heat stabilizer, etc. can be contained in the composition. Moreover, you may add dye, a pigment, a metal compound, etc. as a component for adjusting a color tone. Furthermore, a silane compound, an alkali metal salt, an alkaline earth metal salt, or the like may be added in order to adjust the adhesion to a light-transmitting substrate such as glass when used as an intermediate film.

(Preferable combination of ultraviolet light absorbing material and copper complex)
The heat-insulating multilayer body according to the embodiment includes at least one layer of the ultraviolet light absorption layer and the near infrared light absorption layer described above. In such a thermal barrier multilayer body, the ultraviolet light absorbing material in the ultraviolet light absorbing layer and the near infrared light absorbing material (copper complex) in the near infrared light absorbing layer are shown in Tables 1 to 3 below. No. When used in a combination of 1 to 54, the ultraviolet light absorption characteristics and the near infrared light absorption characteristics tend to be particularly excellent. In addition, when the heat-insulating multilayer body has a plurality of ultraviolet light absorption layers and / or near infrared light absorption layers, a plurality of combinations can be considered, but in this case, each combination may be the same. , May be different.

［積層体］

[Laminate]

  Next, the laminated body which concerns on suitable embodiment is demonstrated. The laminate according to the embodiment includes a light-transmitting substrate and the above-described heat-shielding multilayer body on the light-transmitting substrate.

(First form)
FIG. 1 is a diagram schematically showing a cross-sectional structure of the laminate according to the first embodiment.

  As shown in the figure, the laminate 10 has a structure in which a thermal barrier multilayer 18 is formed on a substrate 12, and the thermal barrier multilayer 18 is formed from the substrate 12 side by the near infrared light absorption layer 14 and The ultraviolet light absorption layer 16 is laminated in this order.

  Here, the substrate 12 is a light-transmitting substrate made of a light-transmitting material, and can transmit visible light from the viewpoint of obtaining good hardness, heat resistance, chemical resistance, durability, and the like. Those made of glass or plastic are preferred. Examples of the glass include inorganic glass, organic glass, and the like. Depending on the purpose, the glass has a specific function such as colored glass, UV-cut glass having a wavelength dependency on transmittance, or glass having a heat shielding function such as green glass. The glass which has can also be used. Examples of the plastic include polycarbonate, acrylonitrile-styrene copolymer, polymethyl methacrylate, vinyl chloride resin, polystyrene, polyester, polyolefin, norbornene resin, and the like, which also have a specific function like glass. May be appropriately selected and used.

  The laminate 10 having such a configuration is prepared, for example, by a sheet or film made of a constituent material of an ultraviolet light absorbing layer, and a sheet or film made of a constituent material (composition) of a near infrared light absorbing layer, These can be manufactured by bonding them to the substrate 12. Examples of a method for bonding them together include a means for bonding by pressurization or pressure reduction such as a press method, a multi-roll method, and a pressure reduction method, a means for bonding by heating with an autoclave, or a combination of these.

  Here, the sheet | seat or film mentioned above is producible using a well-known sheet | seat or film formation method. Specific examples include a melt extrusion molding method, a stretch molding method, a calendar molding method, a press molding method, and a solution casting method. The sheet is a thin plate having a thickness exceeding 250 μm, and the film is defined as a thin film having a thickness of 5 to 250 μm.

  Moreover, as a manufacturing method of the laminated body 10, the method of forming the near-infrared light absorption layer 14 and the ultraviolet light absorption layer 16 directly on the board | substrate 12 without using the said sheet-like molded object is also applicable. Specifically, first, a coating agent is prepared by dissolving and / or dispersing a constituent material of the near-infrared light absorbing layer 14 or the ultraviolet light absorbing layer 16 in an appropriate solvent. Next, a coating agent for forming the near-infrared light absorbing layer 14 is applied on the substrate 12, and then the solvent is evaporated to form a thin film, a covering, or a thin layer. Subsequently, a thin film, a covering, or a thin layer is further formed on the thin film or the like using a coating agent for forming the ultraviolet light absorption layer 16 to obtain the laminate 10. The thin film formed in this way is called a coating. When the laminate 10 is formed by such a method, various surfactants such as a leveling agent and an antifoaming agent are used for the purpose of improving the flatness of the near-infrared light absorbing layer 14 and the ultraviolet light absorbing layer 16. You may add a solubilizing agent in the coating agent mentioned above.

(Second form: Laminated glass)
FIG. 2 is a diagram schematically showing a cross-sectional structure of the multilayer body according to the second embodiment.

  The laminated body 20 is a laminated glass having a structure in which a heat shielding multilayer body 28 is sandwiched between a pair of substrates 22 and having the composite film 28 as an intermediate film. The thermal barrier multilayer 18 is formed by laminating a near-infrared light absorbing layer 24 and an ultraviolet light absorbing layer 26 in this order from the one substrate 22 side. As the substrate 22, the near-infrared light absorption layer 24, and the ultraviolet light absorption layer 26, those made of the same material as the above-described stacked body 10 can be applied. The pair of substrates 22 may be made of the same material or different materials.

  In the laminate 20 having such a structure, for example, the above-described sheet or film for forming the near-infrared light absorbing layer 24 and the ultraviolet light absorbing layer 26 is sandwiched between a pair of substrates 22, respectively. It can be manufactured by a method in which air remaining between the respective layers is removed by pre-compression and then subjected to main-compression to bring them into close contact.

(Third form: Laminated glass)
FIG. 3 is a diagram schematically showing a cross-sectional structure of the laminate according to the third embodiment.

  The laminated body 30 has a structure in which a heat shielding multilayer body 38 is sandwiched between a pair of substrates 32, and the heat shielding multilayer body 38 has a near infrared light between two ultraviolet light absorption layers 36. It has a two-layer structure in which the absorption layer 34 is disposed. As the board | substrate 32, the near-infrared light absorption layer 34, and the ultraviolet light absorption layer 36, what consists of a material similar to the laminated body 10 grade | etc., Mentioned above is applicable.

  Similarly to the laminate 20, the laminate 30 having such a configuration also has a predetermined sheet or film for forming the near infrared light absorbing layer 24 and the ultraviolet light absorbing layer 26 between the pair of substrates 32. These are pre-pressed to remove the air remaining between the respective layers, and then subjected to main pressure bonding so that they are brought into close contact with each other.

  In this laminated body 30, the ultraviolet light absorbing layer 36 is formed on both sides of the near infrared light absorbing layer 34, so that the light irradiated to the laminated body 30 must pass through the ultraviolet light absorbing layer 36 before being near. The infrared light absorption layer 34 is reached. For this reason, the near-infrared light absorbing layer 34 is irradiated with light from which the wavelength in the ultraviolet region has been sufficiently removed. As a result, the generation of colored precipitates by irradiation with ultraviolet light, which has been easy to occur in an intermediate film containing metal ions or the like, is extremely reduced. Thus, the laminate 30 has a very low light resistance even when irradiated with light for a long time, and has extremely excellent light resistance.

(Fourth form: Laminated glass)
FIG. 4 is a diagram schematically showing a cross-sectional structure of the laminated body according to the fourth embodiment.

  The laminated body 40 is a laminated glass having a structure in which a heat shielding multilayer body 48 is sandwiched between a pair of substrates 42. In this heat shield multilayer body 48, a near infrared light absorbing layer 44 is disposed between two ultraviolet light absorbing layers 46, and further, between the near infrared light absorbing layer 44 and the ultraviolet light absorbing layer 46. Is provided with an intermediate layer 47. As described above, in the thermal barrier multilayer 48, the near infrared light absorption layer 44 and the ultraviolet light absorption layer 46 are bonded via the intermediate layer 47.

  Here, as each constituent material of the board | substrate 42, the near-infrared light absorption layer 44, and the ultraviolet light absorption layer 46, the thing similar to each in the laminated body 10 mentioned above is applicable, respectively. In addition, the constituent material of the intermediate layer 47 can be applied without particular limitation as long as it is a material having excellent translucency, and examples thereof include glass, resin materials such as polyethylene terephthalate and polycarbonate. The intermediate layer 47 may have specific functions such as heat ray absorption, ultraviolet light absorption, and the like.

  The laminated body 40 having such a configuration can be formed in the same manner as each laminated glass described above. That is, sheets and films for constituting each layer are arranged in a predetermined order between the pair of substrates 42, and after these are pre-crimped to remove air remaining between the respective layers, this is crimped. Can be produced by bringing them into close contact.

  Moreover, the laminated body 40 can also be formed as follows, for example. That is, first, the substrate 42 and the intermediate layer 47 are arranged at a predetermined interval in the order shown in FIG. Next, a monomer material for forming the near-infrared light absorbing layer 44 and the ultraviolet light absorbing layer 46 is injected into a predetermined position between them in a state of a solution or the like. Thereafter, these monomer materials are polymerized and cured to form the near-infrared light absorbing layer 44 and the ultraviolet light absorbing layer 46 to obtain the laminate 40.

(Fifth form: laminated glass)
FIG. 5 is a diagram schematically showing a cross-sectional structure of the multilayer body according to the fifth embodiment.
The laminated body 50 is obtained by laminating a near-infrared light absorbing layer 54, a translucent material layer 57, and an ultraviolet light absorbing layer 56 in this order on a substrate 52. In this laminated body 50, a heat shielding multilayer body 58 is constituted by the near-infrared light absorbing layer 54, the translucent material layer 57 and the ultraviolet light absorbing layer 56.

  Here, as the translucent material layer 57, a layer made of a translucent resin material such as glass, polyethylene terephthalate, or polycarbonate can be used. The light-transmitting material layer 57 can also be viewed as the other substrate facing the substrate 52, that is, the laminated body 50 has one of the laminated glasses having an intermediate film between the pair of light-transmitting substrates. It can be said that the laminated glass has a structure in which an ultraviolet light absorption layer is provided on the outside of the substrate.

  In the laminate 50 having such a configuration, for example, a sheet or a film for forming the near-infrared light absorbing layer 54 is disposed between the substrate 52 and the translucent material layer 57, and these are reserved. After the pressure bonding, the pressure bonding is performed to form a laminated glass, and then a sheet for forming the ultraviolet light absorption layer 56 is pressure bonded to the outside of the light transmitting material layer 57, or the ultraviolet light absorption layer 56 is formed. It can form by performing the coating mentioned above using the material to form.

(Preferred form of laminated glass)
The laminated body of the 2nd-4th form mentioned above corresponds to what is called a laminated glass which has an intermediate film between a pair of board | substrates. And in the laminated glass having such a configuration, it is preferable that bubbles do not remain as much as possible between the substrate and the heat shielding multilayer body in order to ensure excellent translucency and the like.

  As one means for reducing the bubbles, there is known a method of forming a large number of minute irregularities called embosses on the surface of the heat shielding multilayer body. According to the heat-insulating multilayer body to which embossing has been applied, the deaeration property in the above-described precompression bonding process and the like becomes good, and the remaining bubbles become extremely small and are easily taken into the heat-shielding multilayer body. As a result, the laminated glass has extremely little decrease in translucency due to bubbles.

  As the form of this embossing, for example, various uneven patterns composed of a large number of convex portions and a large number of concave portions corresponding to these convex portions, and various uneven patterns composed of a large number of convex strips and a large number of concave grooves corresponding to these convex strips. There are embossed shapes with various values for various shape factors such as roughness, arrangement, size, etc.

  As these embossments, for example, those described in Japanese Patent Laid-Open No. 6-198809, the size of the convex portion is changed, and the size and arrangement thereof are defined, and those described in Japanese Patent Laid-Open No. 9-40444 are disclosed. Surface roughness of 20-50 μm, described in JP-A-9-295839, arranged so that the ridges intersect, or described in JP-A-2003-48762, The thing which formed the smaller convex part on the main convex part is mentioned.

  In recent years, laminated glass has been required to have sound insulation. According to the laminated glass having excellent sound insulation, for example, when used for a window material, the influence of ambient noise and the like can be reduced, and the indoor environment can be further improved. In general, the sound insulation performance is shown as a transmission loss amount corresponding to a change in frequency, and the transmission loss amount is defined by JISA 4708 at a constant value according to the sound insulation grade at 500 Hz or more.

  However, the sound insulation performance of a glass plate generally used as a translucent substrate in laminated glass tends to be remarkably lowered due to the coincidence effect in a frequency region centered on 2000 Hz. Here, the coincidence effect means that when a sound wave is incident on a glass plate, the transverse wave propagates through the glass plate due to the rigidity and inertia of the glass plate, and the transverse wave and the incident sound resonate. This is a phenomenon that occurs. Therefore, in general laminated glass, it is difficult to avoid a decrease in sound insulation performance in a frequency region centered on 2000 Hz, and improvement of this point is demanded.

  In this regard, it is known from the equal loudness curve that human hearing exhibits a very good sensitivity in the range of 1000 to 6000 Hz compared to other frequency regions. Accordingly, it is important to eliminate the drop in the sound insulation performance due to the coincidence effect described above in order to improve the sound insulation performance. From this point of view, in order to improve the sound insulation performance of the laminated glass, it is necessary to alleviate the decrease in the sound insulation performance due to the coincidence effect and to prevent the minimum portion of the transmission loss due to this coincidence effect.

  Here, as a method of imparting sound insulation to the laminated glass, the method of increasing the mass of the laminated glass, the method of compounding the glass to be the substrate, the method of subdividing the glass area, and the glass plate support means are improved. There are ways to do it. In addition, the sound insulation performance depends on the dynamic viscoelasticity of the heat insulation multilayer body, and is particularly affected by the loss tangent, which is the ratio between the storage elastic modulus and the loss elastic modulus. The sound insulation performance of the laminated glass can also be improved.

  As a means for controlling the loss tangent value of the heat shielding multilayer body, for example, a method of using a resin film having a specific degree of polymerization in a base material of a near infrared light absorption layer and / or an ultraviolet light absorption layer; Examples thereof include a method for defining the resin structure as described in JP-A-4-2317443, a method for defining the amount of plasticizer in the resin as described in JP-A-2001-220183, and the like. It is also known that the sound insulation performance of laminated glass can be enhanced over a wide temperature range by combining two or more different resins to form a base material. For example, a method of blending a plurality of types of resins described in JP-A-2001-206742, and a method of laminating a plurality of types of resins described in JP-A-2001-206741 and JP-A-2001-226152. And a method described in Japanese Patent Application Laid-Open No. 2001-192243 for imparting a deflection to the amount of plasticizer in each layer.

  Adopting these techniques, the loss tangent value of the resin material that is the base material of the heat-shielding multilayer body by appropriately combining means such as modification of the resin structure, addition of plasticizer, combination of two or more resins, etc. Can be controlled, and a desired sound insulation property can be obtained.

  Furthermore, it is more preferable that the laminated glass can further exhibit heat shielding properties other than blocking near infrared light. Examples of the method include a method of further containing oxide fine particles having a heat shielding function in any layer constituting the heat shielding multilayer body. As such a method, for example, methods described in JP 2001-206743 A, JP 2001-261383 A, JP 2001-302289 A, and the like can be applied.

  Examples of the oxide fine particles that can improve the heat shielding property include tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), and aluminum-doped zinc oxide (AZO). In addition, since the intermediate film 2 containing the oxide fine particles tends to have low translucency, the particle size of the oxide fine particles can be reduced (Japanese Patent Laid-Open No. 2002-293583) or the dispersibility can be reduced. For example, a method for improving the light transmissivity may be applied. As a method for enhancing the dispersibility of oxide fine particles as in the latter case, known fine particle dispersion techniques such as mechanically dispersing the fine particles or using a dispersant can be applied.

  As a method for enhancing the heat shielding property of the laminated glass, in addition to the method of containing the oxide fine particles described above, for example, a method of containing a dye having an organic heat shielding function, or a translucent substrate having a heat shielding performance The method used is also mentioned. Examples of the former method of incorporating a dye having an organic heat-shielding function include methods described in JP-A-7-157344 and JP-A-319271. Moreover, as a translucent board | substrate which has the thermal insulation performance applicable to the latter method, Fe containing glass (for example, green glass etc.) described in Unexamined-Japanese-Patent No. 2001-151539, for example, Unexamined-Japanese-Patent No. 2001-261384 is mentioned. The glass plate which laminated | stacked the metal and metal oxide which were described in gazette and Unexamined-Japanese-Patent No. 2001-226148 is mentioned.

  Laminated glass is not only a near-infrared light absorbing layer in a heat-shielding multilayer body, but also a layer having a property of reflecting near-infrared light (near-infrared light) for the purpose of further improving near-infrared light blocking characteristics. A light reflection layer) may be further provided. Such a near-infrared light reflection layer can be introduced into an arbitrary position of the laminated structure constituting the laminated glass. For example, the near-infrared light reflecting layer may be introduced into the layer structure constituting the heat shielding multilayer body.

  As the near-infrared light reflection layer, a transparent layer composed of a metal or a metal oxide can be applied. Specifically, for example, gold, silver, copper, tin, aluminum, nickel, palladium, silicon, chromium, Examples thereof include a layer made of a simple metal such as titanium, indium and antimony, an alloy, a mixture or an oxide. Such a near-infrared light reflection layer can be formed by vapor-depositing a metal or a metal oxide on a layer on which the layer is to be formed.

  By the way, when the near-infrared light reflection layer described above is introduced into the laminated glass, the adhesiveness between the near-infrared light absorption layer and the layer adjacent thereto is lowered, and these are likely to be peeled off. In this case, for example, when a near-infrared light reflecting layer is formed between the substrate and the heat-shielding multilayer body, the laminated glass is likely to be peeled off and scattered when the laminated glass is broken. Will cause problems. Therefore, in order to avoid such a decrease in adhesiveness, it is preferable to appropriately employ means for improving the adhesive force between the near-infrared light reflection layer and the layer adjacent to the reflection layer.

  Examples of means for improving the adhesive force as described above include the following. That is, when the near-infrared light reflection layer and the near-infrared light absorption layer in the heat-shielding multilayer body are adjacent to each other, between the two layers, polyvinyl acetal having a higher acetal degree than the near-infrared light absorption layer. The method of providing the layer (Unexamined-Japanese-Patent No. 7-187726, Unexamined-Japanese-Patent No. 8-337446) is mentioned. In addition, a method of providing a layer made of PVB having a predetermined ratio of an acetoxy group (Japanese Patent Laid-Open No. 8-337445) between the near-infrared light reflecting layer and a layer adjacent thereto, or from a predetermined silicon oil And a method of providing a layer (Japanese Patent Laid-Open No. 7-314609).

  Thus, in laminated glass, by providing a near-infrared light reflecting layer in addition to a near-infrared light-absorbing layer, the near-infrared light blocking property is further improved with respect to laminated glass due to the effects of both layers. Can be granted. Moreover, if the method for improving the adhesiveness with the near-infrared light absorbing layer as described above is employed, it is possible to obtain a laminated glass having even better strength.

  As described above, in the laminated body such as laminated glass of the present embodiment, when light including a heat ray component such as sunlight is incident, the near infrared light absorbing layer in the heat shielding multilayer body is expressed. The heat absorption in the near-infrared light region (wavelength 700 to 1200 nm) is blocked by the light absorption characteristics. In general, light in this wavelength range tends to feel the irritating and exciting heat that burns the skin, but the light transmitted through the above-mentioned laminate is blocked by such near-infrared light. Therefore, it is mainly visible light. Therefore, if such a laminated body is used for a window material or the like, it is possible to suppress an increase in indoor or indoor temperature while efficiently capturing visible light.

  Moreover, in the laminated body of this embodiment, the heat insulation multilayer body has not only a near-infrared light absorption layer but an ultraviolet light absorption layer. For this reason, the irradiation of ultraviolet light to the near-infrared light absorbing layer is extremely reduced, and thereby the occurrence of turbidity in the near-infrared light absorbing layer due to light irradiation is sufficiently reduced.

  Thus, since the laminated body (laminated glass) of the present invention has excellent near-infrared light blocking performance, it is a building material (a building member) for taking in natural light such as sunlight or other external light. For example, window materials for automobiles, ships, aircraft or train (railway) vehicles, canopy materials for passages such as arcades, curtains, canopies for carports and garages, solarium windows or wall materials, show windows, Showcase window materials, tents or window materials, blinds, roofing materials such as stationary and temporary housing, skylights and other window materials, coating materials for painted surfaces such as road signs, sunshade materials such as parasols, and other heat shielding Can be suitably used for various members that require the above.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.
[Preparation of near-infrared light absorbing sheet]

(Preparation of copper complex)
After dissolving 30 g of 2-ethylhexyl phosphate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 52 g of oleyl phosphate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 233 g of toluene, 33 g of copper acetate monohydrate was added. While this solution was refluxed, acetic acid and water were removed. Thereafter, toluene was distilled off from the resulting solution to obtain 94 g of a 2-ethyl phosphate ester / oleyl phosphate mixed copper complex (2-EHP-C + OLP-C).

(Near infrared light absorbing sheet)
12 g of 2-EHP-C + OLP-C was dissolved in 24 g of triethylene glycol-di-2-ethylhexanate (3GO) as a plasticizer, and further 84 g of PVB resin (S-LEC BH-3, manufactured by Sekisui Chemical Co., Ltd.) And then mixed several times with a press machine (WF-50, manufactured by Kondo Metal Industry Co., Ltd.) several times at 85 ° C. and further several times at 120 ° C., and uniform with a thickness of 1 mm. A near infrared light absorbing sheet having a smooth surface was obtained.
[Preparation of UV light absorbing sheet]

(Ultraviolet light absorbing sheet A)
1 g of Biosorb 90 (manufactured by Kyodo Yakuhin Co., Ltd.), an ultraviolet light absorbing material, is dissolved in 30 g of triethylene glycol-di-2-ethylhexanate (3GO) as a plasticizer, and further PVB resin (S-Rec BH-3, Sekisui). And then mixed several times with a press machine (WF-50, manufactured by Shindo Metal Industry Co., Ltd.) at 85 ° C. and several times at 120 ° C. An ultraviolet light absorbing sheet A having a uniform surface with a thickness of 1 mm was obtained.

(Ultraviolet light absorbing sheet B)
Tinuvin-234 (2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethoxybenzoyl) phenyl] benzotriazole) with respect to 100 parts by mass of a copolymer of methyl methacrylate and butyl acrylate Was molded to contain an ultraviolet light absorbing sheet B having a thickness of 50 μm.
[Preparation of infrared and ultraviolet light absorbing sheets]

(Infrared and ultraviolet light absorbing sheet)
24 g of 2-EHP-C + OLP-C and 1.2 g of Viosorb 130 (manufactured by Kyodo Pharmaceutical Co., Ltd.), an ultraviolet light absorbing material, are added to 12 g of triethylene glycol-di-2-ethylhexanate (3GO) as a plasticizer. After dissolving and further mixing with 84 g of PVB resin (S-Rec BH-3, manufactured by Sekisui Chemical Co., Ltd.), it was pressed several times at 85 ° C. with a press machine (WF-50, manufactured by Kondo Metal Industry Co., Ltd.). Kneading was performed by pressing several times at 0 ° C. to obtain an infrared and ultraviolet light absorbing sheet having a uniform surface with a thickness of 1 mm.
[Production of laminate]

Example 1
Glass slide, architectural interlayer (made by Solusia, thickness 0.36 mm, film containing PVB / 3GO / Tinuvin 328 (compounding ratio 81/19 / 0.25)), near infrared light absorbing sheet, same as above The intermediate film and the slide glass were stacked in this order, and prepress-bonded by performing a vacuum press while maintaining this at 90 ° C. for 30 minutes. This was pressure-bonded for 30 minutes in an autoclave under conditions of 130 ° C. and a pressure of 1.5 MPa to obtain a laminate as a laminated glass.

(Example 2)
Except for using an interlayer film for automobiles (Saflex, manufactured by Solusia, thickness 0.76 mm, a film containing PVB / 3GO / Tinvin 328 (mixing ratio 73/27 / 0.25)) instead of the interlayer film for construction In the same manner as in Example 1, a laminate was obtained.

(Example 3)
A green glass (manufactured by Asahi Glass Co., Ltd., cool veil (trade name), thickness 2 mm), a near infrared light absorbing sheet, and a slide glass are stacked in this order, and this is processed in the same manner as in Example 1 to obtain a laminate. It was. In this laminate, the green glass was the upper side. In addition, it is estimated that the ultraviolet light absorptivity of green glass originates in the iron compound in the said glass.

Example 4
A slide glass, an ultraviolet light absorbing sheet A, a near infrared light absorbing sheet, and a slide glass were stacked in this order, and this was processed in the same manner as in Example 1 to obtain a laminate. In addition, in this laminated body, the slide glass near the ultraviolet light absorbing sheet A was set as the upper side.

(Example 5)
A laminated body was obtained in the same manner as in Example 4 except that an interlayer film for automobile (Saflex, manufactured by Solusia Inc., thickness 0.76 mm) was used instead of the ultraviolet absorbing sheet A. In addition, in this laminated body, the slide glass on the side close to the interlayer film for automobiles was set as the upper side.

(Example 6)
Using a slide glass instead of the green glass, the laminate obtained in the same manner as in Example 3, and further, an ultraviolet light absorbing sheet B was attached on the outer surface of one slide glass, and the laminate Got. In addition, in this laminated body, the formation surface of the ultraviolet light absorption sheet B was set to the upper side.

(Comparative Example 1)
The near-infrared light absorbing sheet was sandwiched between slide glasses from both sides, and prepress-bonded by vacuum pressing while maintaining this at 90 ° C. for 30 minutes. This was pressure-bonded for 30 minutes in an autoclave under conditions of 130 ° C. and a pressure of 1.5 MPa to obtain a laminate as a laminated glass.

(Comparative Example 2)
A laminate was obtained in the same manner as in Comparative Example 1 except that infrared and ultraviolet light absorbing sheets were used in place of the near infrared light absorbing sheet.
[Evaluation of laminate]

About the laminated body of Examples 1-6 and Comparative Examples 1-2, the cloudiness of the laminated body immediately after preparation was confirmed visually. Table 4 shows the case where no coloring or turbidity occurred, and the case where the coloring or turbidity occurred as x. Moreover, about each laminated body immediately after preparation, the value of haze was measured in accordance with the method based on JISK7136. The obtained values are shown in Table 4.
[Evaluation of laminate after light resistance test]

For the laminates of Examples 1 to 6 and Comparative Examples 1 and 2, a UV tester (Iwasaki Electric Co., Ltd., Eye Super UV Tester) was used to irradiate light from the upper side of the laminate, and a light resistance test was performed. . The light irradiation conditions were as follows: irradiation intensity: 83 mW / cm ² , irradiation time: 62 h, black panel temperature: 63 ° C.

  For each laminate after the light resistance test, the presence or absence of coloring of the intermediate film is confirmed visually, the generation of bubbles between the substrate and the sheet adjacent to the substrate, and the black precipitates in the near-infrared light absorbing sheet Occurrence was confirmed visually. In Table 4, those in which bubbles or black precipitates were not generated are indicated by ○, and those in which bubbles were generated are indicated by ×. Further, the haze was measured in the same manner as described above. Table 4 shows the obtained results.

  From Table 4, the laminated body (Examples 1-6) provided with the thermal-insulation multilayer body which provided the ultraviolet-light absorption layer separately in addition to the infrared-light absorption layer which consists of an infrared-light absorption sheet has an ultraviolet-light absorption layer. Compared to the laminates of Comparative Examples 1 and 2 that do not have, it was confirmed that the generation of bubbles and precipitates after the light resistance test was small and the haze was small. From this, it was confirmed that the laminated body of Examples 1-6 has the outstanding light resistance compared with the thing of a comparative example.

It is a figure which shows typically the cross-section of the laminated body which concerns on a 1st form. It is a figure which shows typically the cross-section of the laminated body which concerns on a 2nd form. It is a figure which shows typically the cross-section of the laminated body which concerns on a 3rd form. It is a figure which shows typically the cross-section of the laminated body which concerns on a 4th form. It is a figure which shows typically the cross-section of the laminated body which concerns on a 5th form.

Explanation of symbols

  10, 20, 30, 40, 50 ... laminate, 12, 22, 32, 42, 52 ... substrate, 14, 24, 34, 44, 54 ... near infrared light absorbing layer, 16, 26, 36, 46, 56 ... ultraviolet light absorbing layer, 18, 28, 38, 48, 58 ... heat shield multilayer, 47, 57 ... intermediate layer.

Claims (6)

A thermal barrier multilayer body comprising at least an ultraviolet light absorbing layer and a near infrared light absorbing layer,
The near-infrared light absorbing layer is a heat shielding multilayer body in which a near-infrared light absorbing material containing copper ions is dispersed in a resin material.   The near-infrared light absorbing material further contains at least one phosphorus compound selected from the group consisting of a phosphinic acid compound, a phosphonic acid compound, a phosphonic acid monoester compound, a phosphoric acid monoester compound, and a phosphoric acid diester compound. The heat-insulating multilayer body according to claim 1, characterized in that:   The heat-insulating multilayer body according to claim 1, further comprising a light-transmitting layer between the ultraviolet light absorbing layer and the near infrared light absorbing layer.   The at least two ultraviolet light absorbing layers are provided, and the near infrared light absorbing layer is disposed between the two ultraviolet light absorbing layers. The heat-insulating multilayer body described in 1.   The laminated body provided with a translucent board | substrate on the one surface of the thermal-insulation multilayer body as described in any one of Claims 1-4. The laminate according to claim 5, further comprising a translucent substrate on the other surface of the heat shielding multilayer body.

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