WO2006035756A1

WO2006035756A1 - Near-infrared absorbing material and laminate

Info

Publication number: WO2006035756A1
Application number: PCT/JP2005/017716
Authority: WO
Inventors: Rumi Ueda; Naoki Hayashi; Yutaka Kobayashi; Tomomi Ujiie; Hiroki Katono
Original assignee: Kureha Corporation
Priority date: 2004-09-29
Filing date: 2005-09-27
Publication date: 2006-04-06
Also published as: JP4926712B2; JPWO2006035756A1

Abstract

Disclosed is a near-infrared absorbing material which hardly produces deposits even when irradiated with light for a long time, while having excellent near-infrared absorbing characteristics and light resistance. The near-infrared absorbing material can be applied to interlayers or the like. Also disclosed are a sheet-like molded article and a laminate. A laminate (laminated glass) according to a preferred embodiment of the present invention comprises a pair of light-transmitting substrates (1) and an interlayer (near-infrared absorbing layer) (2) sandwiched between the light-transmitting substrates (1). The interlayer (2) is composed of a near-infrared absorbing material which contains a polyvinyl butyral resin having a polymerization degree of 800-2,300 and copper ions.

Description

Specification

Near infrared light absorbing material and laminate

Technical field

The present invention relates to a near-infrared light absorbing material and a laminate, and particularly to a near-infrared light absorbing material and a laminate that can be applied to a laminated glass having near-infrared light absorption characteristics.

Background art

[0002] As an optical member for use in a window material or the like, a structure having a structure in which an intermediate film having a polyvuracetal resin or an acrylic resin is sandwiched between a pair of translucent substrates having glass or the like is used. Laminated glass is known. Such a laminated glass is frequently used because it has excellent properties such as high strength and high durability.

[0003] In recent years, these laminated glasses have been 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”). If laminated glass having such characteristics is applied to window materials, wall materials, etc., it is possible to suppress, for example, the penetration of light rays having the wavelength in the above-described region in sunlight, that is, heat rays into the room. As a result, it becomes possible to keep the indoor environment comfortable by suppressing the indoor temperature from becoming excessively high, and it is also possible to reduce the cost of power and cooling.

[0004] As a laminated glass capable of blocking near-infrared light, a glass having a property of absorbing near-infrared light (near-infrared light-absorbing layer) as an intermediate film is known. Such an intermediate film can be formed by a composition in which a material having a property of absorbing near infrared light (near infrared light absorbing material) is dispersed in a resin material. For example, in Patent Document 1 below, there is a laminated glass including an interlayer film containing a divalent copper ion and at least one infrared light absorbing component selected from indium oxide and Z or tin oxide, and a rosin component. It is disclosed.

Patent Document 1: Japanese Patent Laid-Open No. 9-211220

Disclosure of the invention

Problems to be solved by the invention

[0005] By the way, in recent years, for laminated glass, the above-described near-infrared light absorption characteristics have been considered and excellent. In other words, it is required to have a high light resistance, i.e., a t-characteristic that has little change in translucency even when irradiated with light. A laminated glass having such properties can maintain a high translucency even when used for a long period of time, and thus has extremely high practicality. The conventional laminated glass has excellent near-infrared light absorption characteristics, but when it is irradiated with light, particularly ultraviolet light for a long time, a black precipitate may be formed in the intermediate film. There was still room for improvement in terms of light resistance.

[0006] Therefore, the present invention has been made in view of such circumstances, and has a near-infrared light absorption characteristic in which precipitates and the like are less likely to occur even when irradiated with light for a long time. An object of the present invention is to provide a near-infrared light-absorbing material applicable to an intermediate film or the like that has both excellent light resistance. Another object of the present invention is to provide a film-like molded article using a powerful near-infrared light absorbing material, and a laminate applicable to laminated glass.

Means for solving the problem

[0007] In order to achieve the above object, the near-infrared light absorbing material of the present invention is characterized by containing polybutyral resin having a polymerization degree of 800 to 2300 and copper ions. Here, the “degree of polymerization” means the average degree of polymerization of the polyvinyl propylal resin (the same applies hereinafter).

According to the study by the present inventors, the black precipitate generated in the conventional laminated glass is caused by products such as copper and copper oxide generated by oxidation or reduction of copper ions contained in the interlayer film. Turned out to be. Such copper and cuprates are presumed to have been generated by acidification or reduction of copper ions by active species derived from the resin components produced in the interlayer film by irradiation with ultraviolet light. The

[0009] On the other hand, the near-infrared light absorbing material of the present invention has a degree of polymerization of 800-2300 as polybulputilal resin (hereinafter abbreviated as "PVB") which is a resin component. Contains. In such a near-infrared light absorbing material, although not necessarily clear, it is considered that each component in the material is extremely stabilized.

[0010] Therefore, even if a long period of light (especially ultraviolet light) is irradiated to a laminated glass including an intermediate film containing such a near-infrared light absorbing material, copper ions are present in the intermediate film. Depending on factors such as difficulty in being oxidized or reduced due to stabilization The generation of can be suppressed. As a result, the generation of black precipitates due to light irradiation is considered to be significantly reduced. In addition, an effect | action is not necessarily limited to these.

[0011] The near-infrared light absorbing material of the present invention includes a phosphinic acid compound, a phosphonic acid compound, a phosphonic acid monoester compound, a phosphoric acid monoester compound, and a phosphoric acid diester compound. It is preferable to further contain at least one selected phosphorus compound. By containing such a phosphorus compound, it is possible to obtain a more excellent near-infrared light absorption characteristic, and to further improve the stability of a layer made of such a material (for example, an intermediate film). Become.

[0012] The near-infrared light absorbing material of the present invention preferably further contains a plasticizer. By containing a plasticizer, the glass transition temperature (Tg) of PVB decreases and becomes softer, making it easier to mix with copper ions, etc., and further improving the solubility of copper ions in PVB. The translucency of the layer containing a strong near-infrared light absorbing material is improved.

[0013] The present invention also provides a sheet-like molded article having the near-infrared light absorbing material power of the present invention. Such a sheet-like molded article has excellent near-infrared light absorption characteristics, and even when it is irradiated with light for a long time, precipitates and the like are rarely generated. Therefore, it can be suitably used as an intermediate film in laminated glass.

Furthermore, the present invention is a laminate comprising a translucent substrate and a near-infrared light absorbing layer that is provided on the translucent substrate and is a near-infrared light-absorbing material of the present invention. Provide the body. Such a laminate includes a near-infrared light absorbing layer composed of the near-infrared light-absorbing composition of the present invention, and therefore has excellent near-infrared light absorption characteristics, and also by light irradiation. It also has excellent light resistance with very few precipitates. Further, when the laminate is configured such that the near-infrared light absorbing layer is sandwiched between a pair of translucent substrates, a laminated glass excellent in both near-infrared light absorption characteristics and light resistance is provided. be able to.

The invention's effect

[0015] According to the present invention, an intermediate film or the like excellent in both near-infrared light absorption characteristics and light resistance, which generates little precipitates even when irradiated with light for a long time. An applicable near-infrared light absorbing material can be provided. Also provided are a film-like molded article using a powerful near-infrared light absorbing material and a laminate applicable to laminated glass. It becomes possible.

Brief Description of Drawings

FIG. 1 is a diagram schematically showing an example of a cross-sectional structure of a laminated glass of an embodiment.

FIG. 2 is a diagram schematically showing an example of a cross-sectional structure of a laminated glass having a reflective layer.

FIG. 3 is a diagram schematically showing an example of a cross-sectional structure of a laminated glass having a reflective layer between a plurality of layers provided between translucent substrates.

FIG. 4 is a view showing a micrograph of the laminated glass of Example 2.

FIG. 5 is a view showing a micrograph of a laminated glass of Comparative Example 4.

Explanation of symbols

[0017] 1 ... translucent substrate, 2 ... intermediate film, 10 ... laminated glass, 20 ... laminated glass, 21 ... translucent substrate, 22 ... near infrared light absorbing layer, 23 ... reflective layer, 30 ··· Laminated glass, 31 ··· Translucent substrate, 32 ··· Near-infrared light absorbing layer, 33 ··· Reflecting layer, 34 ··· Grease layer.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary.

[Near-infrared absorbing material]

[0019] The near-infrared light absorbing material according to the embodiment contains at least polyvinyl butyral resin (PVB) having a polymerization degree of 800 to 2300 and copper ions.

[0020] (PVB)

First, PVB contained in the near infrared light absorbing material will be described. PVB has a degree of polymerization of 800-2300. Here, the degree of polymerization means the number of basic units constituting one molecule of PVB, and a value measured based on the method defined in JISK 6728 (2001 edition) can be adopted.

[0021] PVB having such a degree of polymerization is, for example, a polybulal alcohol (PVA) having a degree of polymerization (or molecular weight) sufficient to satisfy the degree of polymerization of PVB as described above as a precursor of PVB. Prepared by reacting butyraldehyde with it. Specifically, as the PVB having a degree of polymerization of 800 to 2300, for example, the following are commercially available. That is, for example, ESREC BM-5 (degree of polymerization 850), BH-3 (degree of polymerization 1700, manufactured by Sekisui Chemical Co., Ltd.) and the like.

[0022] (Copper ion)

Next, copper ions will be described. Copper ions are divalent copper ions. This copper ion can be supplied into the near-infrared light absorbing material in the form of a copper salt. Specific examples of the copper salt include copper acetate anhydrides of organic acids such as copper acetate, copper formate, copper stearate, copper benzoate, copper ethylacetoacetate, copper pyrophosphate, copper naphthenate, copper citrate, Hydrates or hydrates, or anhydrides, hydrates or hydrates of copper salts of inorganic acids such as copper oxide, copper chloride, copper sulfate, copper nitrate, basic copper carbonate, or copper hydroxide Can be mentioned. Of these, copper acetate, copper acetate monohydrate, copper benzoate, copper hydroxide, and basic copper carbonate are preferably used. These copper salts as the copper ion source may be used alone or in combination.

[0023] (phosphorus compound)

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

[Chemical 1]

0 0

R ³ — P— OH to (1C) RP— OH (1 D)

I

OH OR ⁴²

In the above formula, n is 1 or 2, R ¹ , R ²¹ , R ²² ,

R ⁴¹ and R ⁴² each independently represents an alkyl group, a cycloalkyl group, an alkyl group, an alkyl group, an aryl group, or an aryl group. A group, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxyaryl group, a (meth) atallyloyloxyalkyl group or a (meth) atallyloylpolyoxyalkyl group, each of which has a carbon number of 1 to 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) attaroyl group, a (meth) attaroyloxyalkyl group, a (meth) attaloyl polyoxyalkyl group or an ester group. In addition, as a phosphorus compound, you may use in combination of multiple types which may use only 1 type among the compounds represented by said formula (1A)-(: LD). In addition, for each of the above (1A) to (ID) phosphorus compounds, those having the above various functional groups may be used alone V, or two or more kinds may be used in combination! ,.

In particular, the phosphoric acid compound is preferably a phosphoric acid ester compound (monoester and Z or diester) represented by the above general formula (1A)! In the phosphoric acid ester compound represented by the general formula (1A), examples of the group represented by R ¹ include an alkyl group, an alkenyl group, and a polymerizable functional group represented by the following general formula (2). It is done. 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.

[Chemical 2]

X 0

I II

H ₂ C = _C -C "(0C _p H _2p ) ^… (

Among the functional groups represented by R ¹ described above, the alkyl group is more preferably an alkyl group having 1 to 18 carbon atoms, which is preferably an alkyl group having 1 to 30 carbon atoms. Examples of such an alkyl group include n-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group and the like. Ethylhexyl group is preferred. The alkenyl group is preferably an oleyl group.

[0027] When the near-infrared light absorbing material of the embodiment contains a phosphorus compound as described above, in the near-infrared light absorbing material, the copper ion and the phosphorus compound may be present merely as a mixture. In addition, copper ions react with phosphorus compounds to form phosphorus-containing copper compounds. May be present.

[0028] In the latter case, the phosphorus-containing copper compound is formed by an ionic bond and a Z or coordinate bond between a phosphorus-containing group in a phosphorus compound (for example, a phosphate group in a phosphate ester) and a copper ion. A phosphorus-containing copper complex is preferable. Such a phosphorus-containing copper compound can be prepared, for example, by mixing a raw material of copper ions and a phosphorus compound and reacting them.

[0029] The near-infrared light-absorbing material containing PVB, copper ions and phosphorus compounds can be prepared, for example, by adding and mixing copper ion raw materials and phosphorus compounds in PVB. it can. More specifically, PVB, a copper ion raw material and a phosphorus compound are heated and melted and kneaded, or PVB is dissolved and Z or dispersed in a solvent to form a solution, and the copper ion raw material and phosphorus are added to this solution. The method of removing a solvent after adding and mixing a compound etc. can be illustrated.

[0030] (Amount of each component)

When the near-infrared light-absorbing material contains the PVB, copper ion, and phosphorus compound described above, and the phosphorus-containing copper compound is formed by the copper ion and the phosphorus-containing compound, these components are It is preferable that they are blended at the composition ratio shown below. That is, the content of the phosphorus-containing copper compound with respect to 100 parts by mass of PVB is 0.1 to: LOOO parts by mass, preferably 1 to 500 parts by mass, and 2 to 300 parts by mass. And more preferred. When the content of the phosphorus-containing copper compound relative to PVB is less than 0.1 parts by mass, the near-infrared light absorption characteristics tend to be remarkably lowered. On the other hand, when it exceeds 1000 parts by mass, the compatibility of the copper ion and the phosphorus compound is lowered, and the translucency tends to be deteriorated.

[0031] In particular, when the near-infrared light absorbing material is a sheet-like molded product used for an interlayer film of laminated glass applied to a window material or the like, the phosphorus-containing copper compound content is 100 parts by mass of PVB. On the other hand, it is preferably 0.5 to 45% by weight, more preferably 1 to 40% by weight, and even more preferably 1 to 35% by weight.

[0032] Further, in such a near-infrared light absorbing material, the content of copper ions and the content of phosphorus compounds are such that these phosphorus compounds have hydroxyl groups or oxygen atoms derived from hydroxyl groups. (Total amount of hydroxyl groups or oxygen atoms) Z (copper ion content) is preferably 1 to 6, more preferably 1 to 4, more preferably 1.5 to 5 in terms of molar ratio. 2. Satisfies relationship 5 And preferred. When this ratio is less than 1, the near-infrared light absorbability and visible light transmittance tend to decrease. 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.

[0033] (Plasticizer)

In addition, the near-infrared light absorbing material of the embodiment may further include other components for adjusting various characteristics in addition to the above-described components. Examples of other components include a plasticizer. When the near-infrared light absorbing material contains a plasticizer, the solubility and Z or dispersibility of copper ions in PVB tend to be further improved, and the near-infrared light absorbability and visible light transmittance are further improved. be able to.

[0034] 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-ethylbutyrate (3GH), dihexyl adipate (DHA), tetraethylene glycol diheptanoate (4G7), tetraethylene Examples include glycol diethyl hexanoate (4GO) and triethylene glycol diheptanoate (3G7).

[0035] When the plasticizer described above is contained in the near-infrared light absorbing material, the content of the plasticizer is preferably 1 to 120 parts by mass with respect to 100 parts by mass of PVB. More preferably, it is 2-80 parts by mass. If the content of the plasticizer is less than 1 part by mass with respect to 100 parts by mass of PV B, the solubility of the copper ion-phosphorus compound may be reduced and the translucency may be insufficient. On the other hand, when it exceeds 100 parts by mass, PVB becomes too flexible, and for example, it tends to be difficult to use as an interlayer film in laminated glass.

[0036] (Ultraviolet light absorber)

Further, in order to further improve the stability against ultraviolet light, an ultraviolet light absorber can be contained. Examples of the ultraviolet light absorber include benzoate compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, oxalate-amide compounds, and triazine compounds.

[0037] More specifically, as the benzoate-based compound, 2,4-di-tert-butylphenol 3 ', 5, -di-tert-butyl-4, -hydroxybenzoate is exemplified, and salicylate-based compounds include phenyl salicylate and p-t-butylphenol salicylate.

[0038] Examples of the benzophenone compounds include 2, 4 dihydroxybenzophenone, 2 hydroxy 4 methoxybenzophenone, 2-hydroxy-4 methoxybenzophenone 5 sulphonoic acid, 2 hydroxy 1 4-n-o. Ctyloxybenzophenone, 2-hydroxy-1,4-n-dodecyloxybenzophenone, 2, 2 ', 4, 4, monotetrahydrobenzophenone, bis (5-benzoyl-4-hydroxy-1,2-methoxyphenol) methane 2,2,1-dihydroxy-1,4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 1,5,5, sodium monodisulfonate, 2,2'-dihydroxy 1-Methoxybenzophenone, 2-hydroxy-4-methacryloyloxychetylbenzophenone, 4-benzoyloxy-2-hydroxybenzophenone, 2, 2 ', 4 , 4'-tetrahydroxybenzophenone and the like.

[0039] Examples of the benzotriazole compounds include 2- (2,1hydroxy-1,5, methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'methylphenol) 5 Oral benzotriazole, 2— (2,1hydroxy-1,3,5,1 tert-butylphenol) 5 Chronobenzozoazole, 2— (2,1 hydroxy1,3,5,1 Butylphenol) -benzotriazole, 2- (2,1-hydroxyl 5-tert-octylphenol) benzotriazole, 2- (2, -hydroxy-5 t-butylphenol) benzotriazole, 2- [2,1- Hydroxy-1,3,1 (3,4,5 ", 6, monotetrahydrophthalimidomethyl) 5, monomethyl] benzotriazole, 2- (2, monohydroxy-1,3,5, Tert-amyl benzyl) benzotriazole, 2- (2, 1-hydroxy-1-5-octylphenol) benzotriazole, 2- [2,1-hydroxy-1,3,5,1-bis (α, a-dimethoxybenzoyl) phenol] benzotriazole, 2, 2 , Monomethylenebis [4- (1, 1, 3, 3-tetramethylbutyl) —6— (2N-benzotriazole 2-yl) phenol], 2- (2, monohydroxy-1,5-methacryloyloxyche (Tilphenyl) 2H-benzotriazole, 2- (2'-hydroxy-3, dodecyl-5, monomethylphenol) benzotriazole, methyl-3- [3-t-butyl 5- (2H benzotriazole 2-yl ) 4 Hydroxyphenol] propi Examples include condensates of ionate and polyethylene glycol.

[0040] Examples of the cyanoacrylate compound include ethyl 2 cyano 3, 3 diphenyl acrylate, octal 2 cyano 3, 3 diphenyl acrylate, and oxalate-lide compound includes 2-ethoxy. 2'-Ethyloxalic acid bis-arylide 2-ethoxy 5-tert-butyl- 2'-Ethyloxalic acid bis-aryl. Examples of triazine compounds include 2- (4,6 diphenyl-1,3,5 triazine-2-yl) 5-[(hexyl) oxy] phenol.

[0041] (Light stabilizer)

Further, the near-infrared light absorbing material can also contain a light stabilizer for further improving the stability to light. In particular, when the ultraviolet light absorber described above and this light stabilizer are used in combination, the stability to light tends to be very good. As the light stabilizer, a hindered amine light stabilizer (HALS) or a Ni compound can be used.

More specifically, as HALS, bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, bis (1, 2, 2, 6, 6 pentamethyl-4-piperidyl) sebacade, 1 [ 2

[3— (3,5-tert-butyl-4-hydroxyphenyl) propio-loxy] ethyl] 4 [3 -— (3,5-di-tert-butyl-4-hydroxyphenyl) propio-loxy] —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 1,4 dione, bis (1, 2, 2, 6, 6 pentamethyl 1 4-piperidyl)-2- (3,5-di-t-butyl-4-hydroxybenzyl) -2 — N-Butyl malonate, 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 Pen Tamethyl 1 4 Piperidyl / Tridecyl) 1 1, 2, 3, 4 Butanetetracarboxylate, Mixed {1, 2, 2, 6, 6 Pentamethinole 4 Piberidinore Z j8, β, β ', j8, 1 Tetramethyl 3, 9 — [2, 4, 8, 10-Tetraoxaspiro (5, 5) undecane] jetyl} 1

, 2, 3, 4 Butanetetracarboxylate, (Mixed 2, 2, 6, 6-tetramethyl— 4-piperidyl Z-tridecyl) 1, 2, 3, 4 Butanetetracarboxylate, Mixed {2, 2 , 6, 6-Tetramethinole 4 Piberidinore Z j8, β, β ', j8, One tetramethinole 3, 9- [2, 4, 8, 10-Tetraoxaspiro (5,5) undecane] jetyl} 1, 2, 3 , 4 Butantetolacarboxylate, 2, 2, 6, 6—Teramethyl— 4 Piperidyl methacrylate, 1, 2, 2, 6, 6 Pentamethyl mono-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-1-4-piberyl) iminol], dimethyl succinate polymer with— 4 hydroxy 2, 2, 6, 6-tetramethinole 1-piperidine ethanol, N, Ν ', Ν ", Ν'" — Tetrakis (4, 6 bis (butyl- (ー -methyl-2,2,6,6-tetramethylpiperidine-4-yl) amino) Riadin—2-yl) —4,7 diazadecane— 1,10 diamine, dibutylamine— 1, 3, 5 triazine 1 Ν, Ν, 1 bis (2, 2, 6, 6-tetramethyl 1 4 piperidyl 1 1, 6 Polycondensate of monohexamethylenediamine and Ν— (2, 2, 6, 6-tetramethylpiperidyl) butyramine, bis (2, 2, 6, 6-tetramethyl-1)-(octyloxy) ) — 4—Piberidyl) ester and the like.

[0043] Ni-based light stabilizers include [2, 2, 1-thiobis (4-t-otatino refenolate)] 1-2-ethylhexylamine-nickel (II), nickel dibutyldi And thiocarbonate, [2,2, -thiobis (4-tert-octylphenolate)]-butylamine mononickel (Π) and the like.

[0044] (Other ingredients)

In addition to the components for stabilizing the near-infrared light absorbing material, an antioxidant, a heat stabilizer and the like can be contained. Moreover, you may add dye, a pigment, a metal compound, etc. as a component for adjusting a color tone. Furthermore, when applied to laminated glass, Silane compounds, alkali metal salts, alkaline earth metal salts, and the like can be added as components for adjusting the adhesion to a light-transmitting substrate such as glass. . Furthermore, as a resin component, in addition to the above PVB, do not deteriorate the properties of the near-infrared light absorbing material! / In combination with ethylene acetate butyl copolymer or acrylic resin in the range of ヽ. Well, okay.

[Optical member]

[0045] By using the above-described near-infrared light-absorbing material, it has excellent properties for blocking near-infrared light. Various optical members can be obtained. Examples of such an optical member include the following first and second forms.

1st form: The sheet-like molding obtained by processing a near-infrared light absorptive composition.

Second embodiment: A laminate having a light-transmitting substrate and a near-infrared light absorbing layer provided adjacent to the light-transmitting substrate.

[0046] (First form)

First, the first embodiment will be described. The optical member of the first form is a sheet-like molded product made of the above-described near-infrared light absorbing material, and specifically includes a sheet and a film. Here, the sheet is a thin plate having a thickness exceeding 250 / zm. The film is a thin film having a thickness of 5 to 250 / ζ πι. These sheets or films can be produced using a known sheet or film forming 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.

[0047] (Second form)

Next, the second embodiment will be described. The optical member of the second form is a laminate having a light-transmitting substrate and a near-infrared light absorbing layer made of a near-infrared light-absorbing material provided adjacent to the light-transmitting substrate. .

[0048] The material constituting the translucent substrate is not particularly limited as long as it is a translucent material having visible light transmissivity, and can be appropriately selected according to the use of the optical member. From the viewpoint of obtaining good hardness, heat resistance, chemical resistance, durability, etc., glass and plastic are preferably used. Examples of the glass include inorganic glass and organic glass. Depending on the purpose, specific glass such as colored glass, UV-cut glass having a wavelength dependency on transmittance, or glass having a heat shielding function such as green glass is specified. It is also possible to use glass having the following functions. Examples of the plastic include polycarbonate, acrylonitrile-styrene copolymer, polymethyl methacrylate, vinyl chloride resin, polystyrene, polyester, polyolefin, norbornene resin, and these are also specific to glass. Those having functions may be appropriately selected and used. When there are a plurality of translucent substrates, each substrate may be composed of the same material or different materials. Yes.

[0049] Such a laminated body is manufactured, for example, by forming a sheet or film similar to the optical member of the first embodiment described above, and then bonding the sheet or the like to the light-transmitting substrate. Can do. Examples of a method for bonding them together include 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. .

[0050] Further, as a method for producing a laminate, in addition to a method of pasting sheets formed in advance, a near-infrared light absorbing layer is directly formed on a light-transmitting substrate without using the above-mentioned sheet-like molded product. This method can also be applied. As such a method, for example, a near-infrared light absorbing material is dissolved and Z or dispersed in an appropriate solvent to form a coating agent, and this solution is applied to a light-transmitting substrate, and then the solvent is evaporated, Examples thereof include a method of forming a thin film, a covering, or a thin layer having a near infrared light absorbing material force on a translucent substrate. The thin film formed in this way is called coating. When a near-infrared light absorbing layer is formed using such a method, solubilizing agents such as various surfactants such as a leveling agent and an antifoaming agent are added for the purpose of improving the flatness of the layer. It can be added to the coating agent mentioned above.

[0051] (Laminated glass)

The optical member of the second form, that is, the laminate is not limited to one having the above-described light-transmitting substrate and the near-infrared light absorbing layer, but may have a plurality of these layers. Good. Specifically, a substrate including a pair of light-transmitting substrates and an intermediate film (near-infrared light absorbing layer) made of the near-infrared light-absorbing material disposed between the light-transmitting substrates can be given. Such a laminate is called a so-called laminated glass and can be suitably used as a window material or the like.

[0052] Here, a laminated glass of a preferred embodiment will be described with reference to FIG.

FIG. 1 is a diagram schematically showing an example of a cross-sectional structure of the laminated glass of the embodiment. A laminated glass 10 shown in FIG. 1 includes a pair of translucent substrates 1 and an intermediate film 2 (near infrared light absorption layer) sandwiched between the pair of translucent substrates 1. The intermediate film 2 also has the near-infrared light absorbing material force of the above-described embodiment, and the light-transmitting substrate 1 can be the same as the above-described laminate. [0054] The laminated glass 10 having a powerful structure is obtained by, for example, sandwiching a sheet-like molded product made of the above-described near-infrared light absorbing composition between a pair of light-transmitting substrates 1, and preliminarily using this. It can be manufactured by a method in which air remaining between the respective layers is removed by pressure bonding, and then these are pressure bonded to bring them into close contact.

[0055] Note that, when the laminated glass 10 is manufactured by such a manufacturing method, the sheet-like molded product to be the intermediate film 2 is formed into a lump when the sheets are bonded together during storage. It is important that the blocking phenomenon does not occur and that the degassing property in the pre-bonding is good. When these requirements are satisfied, the workability when superimposing the translucent substrate 1 and the sheet is improved, and the translucency due to bubbles generated due to insufficient deaeration, for example. Decline can be prevented.

[0056] From the viewpoint of application to window materials and the like, the laminated glass 10 is also required to have not only the property of blocking near infrared light but also the property of transmitting visible light, that is, the property of transmitting light in the visible light region. It is done. In order to obtain excellent visible light transmittance, it is preferable that bubbles remain between the translucent substrate 1 and the intermediate film 2 as much as possible.

As one means for reducing the bubbles, a method using an intermediate film 2 having a large number of minute concaves and convexes called emboss on the surface is known. According to the embossed intermediate film 2, the degassing property in the above-described pre-compression bonding process and the like becomes good, and the remaining bubbles become extremely small and are easily taken into the intermediate film 2. As a result, the laminated glass 10 is less deteriorated in translucency due to bubbles.

[0058] As the form of embossing, for example, various concave and convex patterns composed of a large number of convex portions and a large number of concave portions corresponding to these convex portions, and various types of embossed strips 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 uneven patterns, roughness, arrangement, size, etc.

[0059] Examples of these embosses include those described in JP-A-6-198809, in which the size of the protrusions is changed and the size and arrangement thereof are defined, and in JP-A-9-40444. The surface roughness is 20-50 / ζ πι, the one described in Japanese Patent Application Laid-Open No. 9-295839, the ridges arranged so as to intersect, or the Japanese Patent Application Laid-Open No. 2003-48762. No. 1, and a smaller convex part formed on the main convex part. [0060] In addition, as another characteristic recently required for the laminated glass 10, sound insulation is cited. According to the laminated glass having excellent sound insulation, for example, when used for a window material, it is possible to reduce the influence of ambient noise and the like, and further improve the indoor environment. In general, sound insulation performance is shown as transmission loss amount according to frequency change, and the transmission loss amount is specified by JISA 4 708 at a constant value depending on the sound insulation grade, over 500Hz!ヽ.

However, the sound insulation performance of a glass plate generally used as a light-transmitting substrate in laminated glass tends to be significantly reduced 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 the 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.

[0062] In this regard, it is known from the equal loudness curve that human auditory sensation exhibits a very good sensitivity in the range of 1000 to 6000 Hz compared to other frequency regions. Therefore, it is important to improve the soundproofing performance to eliminate the drop in the soundproofing performance due to the coincidence effect described above. From this point of view, in order to improve the sound insulation performance of the laminated glass 10, 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 the coincidence effect from being lowered.

[0063] Here, as a method of imparting sound insulation to the laminated glass 10, there are a method of increasing the mass of the laminated glass 10, a method of compounding the glass to be the translucent substrate 1, and subdividing this glass area. And a method for improving the glass plate supporting means. In addition, the sound insulation performance depends on the dynamic viscoelasticity of the interlayer film 2, and is particularly affected by the loss tangent, which is the ratio between the storage elastic modulus and the loss elastic modulus. Therefore, the sound insulation performance of the laminated glass 10 can be improved.

[0064] As a means for controlling the value of the loss tangent of the interlayer film 2, for example, a method using a resin film having a specific degree of polymerization, a resin as described in JP-A-4-2317443 A method for defining the structure of the resin, and a plasticizer in the resin as described in JP-A-2001-220183 Examples include a method for defining the amount. It is also known that the sound insulation performance of the laminated glass 10 can be enhanced over a wide temperature range by forming an intermediate film by combining two or more different types of resin. For example, a method of blending a plurality of types of resin described in JP-A-2001-206742, and a method of blending a plurality of types of resin described in JP-A-2001-206741 and JP-A-2001-226152. Examples thereof include a method of laminating, a method described in Japanese Patent Application Laid-Open No. 2001-192243, and a method of imparting a deflection to the amount of plasticizer in the intermediate film. A resin material that should form the intermediate film 2 by adopting these technologies and implementing appropriate combinations of means such as modification of the resin structure, addition of a plasticizer, and a combination of two or more kinds of resin. It is possible to control the value of the loss tangent of and to obtain the desired sound insulation.

[0065] Further, it is preferable that the laminated glass 10 can further exhibit heat shielding properties other than blocking near infrared light. As a method for improving the heat shielding property of the laminated glass 10, there can be mentioned a method in which the intermediate film 2 further contains oxide fine particles having a heat shielding function. As such a method, for example, methods described in JP-A-2001-206743, JP-A-2001-261383, JP-A-2001-302289, etc. can be applied.

[0066] Examples of the oxide fine particles that can improve the heat-shielding property include tin-doped indium oxide (ITO), antimony monophosphate-tin (ATO), aluminum-doped oxide-zinc (AZO), and the like. In addition, since the intermediate film 2 containing 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), A method of improving dispersibility and maintaining good translucency may be applied. As a method for enhancing the dispersibility of the oxide fine particles as in the latter case, a known fine particle dispersion technique such as mechanically dispersing the fine particles or using a dispersant can be applied.

[0067] As a method of improving 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 an organic dye having a heat shielding function, or a light transmitting property having a heat shielding property A method using a conductive substrate is also included. Examples of the former method of incorporating a dye having an organic heat shielding function include the methods described in JP-A-7-157344 and JP-A-319271. In addition, as a translucent substrate having a heat-shielding performance applicable to the latter method, for example, an Fe-containing substrate described in JP-A-2001-151539 Examples thereof include glass (for example, green glass), a glass plate in which a metal and a metal oxide described in JP-A-2001-261384 and JP-A-2001-226148 are laminated.

As described above, the laminated glass 10 according to the above-described embodiment has the near-infrared light that is a heat ray when the near-infrared light absorbing material included in the intermediate film 2 absorbs light in the near-infrared light region. However, the laminated glass 10 has a near-infrared absorption intermediate film 2 (near-infrared light absorbing layer) for the purpose of further improving the near-infrared light blocking characteristics. ) And a layer having a property of reflecting near infrared light (near infrared light reflecting layer)!

FIG. 2 is a diagram schematically showing an example of a cross-sectional structure of a laminated glass having a reflective layer. The laminated glass 20 has a structure including a translucent substrate 21, a near infrared light absorbing layer 22, a near infrared light reflecting layer 23, and a translucent substrate 21 in this order. As the light-transmitting substrate 21 and the near-infrared light absorbing layer 22, the same materials as the light-transmitting substrate 1 and the intermediate film 2 in the laminated glass 10 described above can be applied.

[0070] Examples of the near-infrared light reflection layer 23 include layers composed of metals and metal oxides. Specifically, for example, gold, silver, copper, tin, aluminum, nickel, noradium, keys, and the like. Examples include simple metals such as elemental, chromium, titanium, indium, and antimony, alloys, mixtures, and oxides.

[0071] The laminated glass 20 having such a near-infrared light reflection layer 23 can be manufactured, for example, as follows. That is, first, the near-infrared light reflection layer 23 is formed on one surface of the translucent substrate 21 by, for example, depositing a metal or a metal oxide. Next, a sheet-like molded product to be the near-infrared light absorbing layer 22 is prepared, and the translucent substrate 21 having the near-infrared light reflecting layer 23 formed on one surface thereof is attached to the reflecting layer 23. Arrange them so that they touch each other. Further, the translucent substrate 21 is overlaid on the other surface of the sheet-like molded product. The laminated glass 20 is obtained by, for example, pressing the laminate thus obtained.

Here, when the near-infrared light reflecting layer 23 is formed between the translucent substrate 21 and the near-infrared light absorbing layer 22 like the laminated glass 20, the reflecting layer 23 and the near-infrared Adhesiveness with the light absorption layer 22 may be reduced. In this case, for example, when the laminated glass 20 is broken, the translucent substrate 21 is easily peeled and scattered, which causes a problem in terms of safety. Therefore, in order to avoid such a decrease in adhesion, the near-infrared light absorbing layer 22 and the near-infrared light reflecting layer 23 It is preferable to further provide a layer capable of improving the adhesive strength between the two.

[0073] As a means for improving the adhesive strength in this way, for example, a higher acetal degree than the near infrared light absorbing layer 22 is provided between the near infrared light absorbing layer 22 and the near infrared light reflecting layer 23. A method of providing a layer having a polyvinylacetal force (Japanese Patent Laid-Open No. 7-187726, Japanese Patent Laid-Open No. 8-337446), a layer made of PVB having a predetermined ratio of acetoxy groups (Japanese Patent Laid-Open No. 8-33 7445) Or a method of providing a layer having a predetermined silicone oil force (Japanese Laid-Open Patent Publication No. 7-314609).

[0074] In the laminated glass, the near-infrared light reflecting layer is not necessarily provided between the translucent substrate and the near-infrared light absorbing layer as described above. In the case where a plurality of layers of resin are formed between them, a form provided between these layers may be used.

FIG. 3 is a diagram schematically showing an example of a cross-sectional structure of a laminated glass having a reflective layer between a plurality of layers provided between translucent substrates. Laminated glass 30 includes a light-transmitting substrate 31, a near-infrared light absorbing layer 32, a near-infrared light reflecting layer 33, a resin layer 34, a near-infrared light absorbing layer 32, and a light-transmitting substrate 31 in this order. It has a structure. In the strong laminated glass 30, the translucent substrate 31, the near-infrared light absorbing layer 32, and the near-infrared light reflecting layer 33 are the same as described above. As a constituent material of the resin layer 34, a known resin material having excellent translucency can be applied, and examples thereof include polyethylene terephthalate and polycarbonate. In the laminated glass 30, if at least one near infrared light absorption layer 32 is provided, sufficient near infrared light absorption characteristics can be obtained. One of the layers 32 may be a layer made of a resin material that does not have near infrared light absorption characteristics.

[0076] In this manner, by adding a near-infrared light absorbing layer (intermediate film) and further providing a reflective layer, the near-infrared light blocking characteristics of laminated glass can be further improved due to the effects of both layers. It can be granted. Moreover, if the method for improving the adhesion between the near-infrared light reflecting layer and the near-infrared light absorbing layer as described above is adopted, in addition to the near-infrared light blocking property, a higher strength can be obtained. It is also possible to obtain existing laminated glass.

[0077] When a light containing a heat ray component such as sunlight is incident on a laminated body such as laminated glass having the above-described configuration, the near-infrared light that the near-infrared light absorbing layer that is an intermediate film appears. Absorption characteristics Depending on the nature, heat rays in the near-infrared light region (wavelength 700 to 1200 nm) are blocked. In general, the 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 such near infrared light. Since it is blocked, 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.

[0078] Further, since the near-infrared light absorbing layer in the laminate is not easily oxidized or oxidized by copper ions even when irradiated with long-time light (particularly ultraviolet light), Generation of black precipitates such as copper and copper oxide is extremely small. For this reason, a decrease in translucency due to the formation of strong precipitates hardly occurs. Therefore, the laminate (laminated glass) of the present invention has excellent reliability as a window material or the like in which the decrease in translucency due to long-term use is extremely small.

[0079] Thus, since the laminate (laminated glass) of the present invention has excellent near-infrared light blocking performance, it is a building material for incorporating natural light such as sunlight and other external light (architecture). Not limited to material parts), for example, car, ship, aircraft or train (railway) vehicle window materials, canopy materials for passages such as arcades, curtains, carport and garage canopies, solarium windows or wall materials Window materials for show windows and showcases, tents or window materials, blinds, roofing materials for fixed and temporary housing, skylights, other window materials, covering materials for painted surfaces such as road signs, sunshades such as parasols, etc. It can be suitably used for various materials that need to be shielded from materials and other heat rays.

Example

[0080] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[Preparation of Copper Phosphate Ester Complex]

[0081] (Preparation of 2-ethylhexyl copper phosphate complex)

As the phosphorus compound, 2-ethylhexyl phosphate (an equimolar mixture of monoester and diester, manufactured by Tokyo Chemical Industry Co., Ltd.) was used, and 5 g thereof was dissolved in 15 g of toluene. To the obtained solution, 2.37 g of copper acetate monohydrate was added, and acetic acid was removed while refluxing this solution. Then, toluene was distilled off from the reaction solution to obtain 6.04 g of 2-ethylhexyl phosphate copper complex (hereinafter referred to as “2EHPC”! /). [0082] (Preparation of oleyl phosphate complex)

As a phosphorus compound, oleyl phosphate (an equimolar mixture of monoester and diester, manufactured by Tokyo Chemical Industry Co., Ltd.) was used, and 63.lg thereof was dissolved in 180 g of toluene. Copper acetate monohydrate (20 Og) was added to the resulting solution, and acetic acid was removed while the solution was refluxed. Thereafter, toluene was distilled off from the reaction solution to obtain 80.4 g of a copper oleyl phosphate complex (hereinafter referred to as “OLPC”).

[0083] (Preparation of 2-ethylhexyl phosphate ester / oleyl phosphate ester mixed copper complex) As a phosphorus compound, 2-ethyl hexyl phosphate (an equimolar mixture of monoester and diester, manufactured by Tokyo Chemical Industry Co., Ltd.) 15. 8 g and oleyl phosphate (equal molar mixture of monoester and diester, manufactured by Tokyo Chemical Industry Co., Ltd.) 8. 89 g were dissolved in 80 g of toluene. Copper acetate monohydrate (10 Og) was added to the resulting solution, and acetic acid was removed while the solution was refluxed. Thereafter, toluene was distilled off from the reaction solution to obtain 28.8 g of 2-ethylhexylphosphate ester / oleylphosphate mixed copper complex (2EHPC + OLPC).

[Production of laminated glass]

(Examples 1 to 4, Comparative Examples 1 to 4)

Each phosphate ester copper complex obtained in the above-mentioned preparation examples 1. Og is dissolved in the plasticizer triethylene glycol-2-hexanate 2. Og, and this is PVB7 having various degrees of polymerization. After mixing with Og, press several times at 85 ° C with a press machine (WF-50, manufactured by Shindo Metal Industry Co., Ltd.), press several times at 120 ° C and knead to form a sheet of lmm thickness A molded product was produced. Table 1 shows the types of phosphate ester copper complexes and the degree of polymerization of PVB used in the preparation of each sheet-like molded product.

[0085] Next, the obtained sheet-like molded product was sandwiched between two slide glasses having a length of 26 mm, a width of 76 mm, and a thickness of 1 mm, and a temperature of 130 ° was applied to the laminate by autoclave. C, pressure bonding of 1.2 Mpa was performed for 30 minutes, and laminated glasses of Examples 1 to 4 and Comparative Examples 1 to 3 were obtained.

[Characteristic evaluation]

[0086] (Evaluation of blackening)

First, for each laminated glass of Examples 1-4 and Comparative Examples 1-4, xenon weathering 100 hours of ultraviolet light (UV) irradiation using 1 ter (Atlas C135, manufactured by Toyo Seiki Seisakusho; light source: xenon lamp, automatic irradiation intensity: 0.87 W / m ² , black panel temperature: 63 ° C) went.

[0087] Next, each laminated glass after UV irradiation was observed with a microscope, and the degree of occurrence of black precipitates was evaluated. The results obtained are shown in Table 1. In Table 1, A indicates that almost no black precipitates are observed, and B indicates that a large amount of black precipitates are generated. As an example, micrographs obtained by observing the laminated glass of Example 2 and the laminated glass of Comparative Example 4 are shown in FIGS. 4 and 5, respectively.

[0088] (Measurement of visible light transmittance)

For each laminated glass of Examples 1 to 4 and Comparative Examples 1 to 4, a spectrophotometer (U) immediately after production and in each state after UV irradiation similar to the above “evaluation of blackening” was performed. -4000, manufactured by Hitachi, Ltd.). Based on these results, the visible light transmittance (Tvis (Oh)) in the laminated glass immediately after fabrication and the visible light transmittance (Tvis (100h)) in the laminated glass after UV irradiation are determined according to the method according to J ISR 3106. Calculated. The change in visible light transmittance (ATvis) was calculated by subtracting the value of Tvis (Oh) from the value of Tvis (100h). The results obtained are shown in Table 1.

[table 1]

Phosphoric ester PVB polymerization Blackening Tvis (Oh) Tvis (IOOh) ATvis Copper complex Degree

Example 1 2EHPC 850 A 83.95 82.85 -1.1 Example 2 2EHPC 1700 A 83.94 83.52 -0.42 Example 3 OLPC 1700 A 85.84 81.95 -3.89 Example 4 2EHPC + 0LPC 1700 A 85.19 83.06 -2.13 Comparative Example 1 2EHPC 300 B 77.27 49.16 -28.11 Comparative Example 2 2EHPC 650 B 84.72 76.08 -7.24 Comparative Example 3 OLPC 650 B 86.56 81.64 -4.92 Comparative Example 4 2EHPC 2400 B 82.9 51.56 -31.34

[0089] From Table 1, the combined glass of Examples 1 to 4 using PVB having a polymerization degree within the range of the present invention is the same as that of Comparative Examples 1 to 4 in which the polymerization degree of PVB is outside the range of the present invention. It was found that the generation of black precipitates was very small compared to the laminated glass. This is because, in FIG. 4 (laminated glass of Example 2), black precipitates are hardly seen, whereas in FIG. 5 (combined glass of Comparative Example 4), a large amount of black and precipitates are generated. It can also be confirmed from what is seen in Furthermore, from Table 1, it was found that the laminated glasses of Examples 1 to 4 had a smaller change in visible light transmittance than the laminated glasses of Comparative Examples 1 to 4. From the above, the laminated glass obtained using the near-infrared light-absorbing material of the present invention has little deterioration in translucency even when used for a long time, and has excellent characteristics as a window material or the like. It was confirmed that he would speak.

[Preparation of copper phosphonate complex]

[0090] (Preparation of ethylphosphonic acid copper complex)

Ethylphosphonic acid was used as the phosphorus compound, and 0.55 g (5.OOmmol) thereof was dissolved in 10 mL of THF. To the resulting solution was added copper acetate monohydrate 1.OOg (5. Olmmol), and the mixture was heated to reflux with heating. The solid formed in the solution after the reaction was separated by filtration, A copper fonate complex was obtained.

[Production of laminated glass]

(Example 5 and Comparative Example 5)

Various phosphoric acid ester copper complexes 1. Laminated glasses were produced in the same manner as in Examples 1 to 4 and Comparative Examples 1 to 4 except that 0.14 g of an ethyl phosphonate complex was used instead of Og. As PVB, those having a polymerization degree of 1700 and 650 were used, respectively. The case of using PVB with a polymerization degree of 1700 corresponds to Example 5, and the case of using PVB with a polymerization degree of 650 corresponds to Comparative Example 5.

[Characteristic evaluation]

[0092] (Evaluation of blackening)

For the laminated glass of Example 5 and Comparative Example 5, except that the UV irradiation intensity was set to 0.75 WZm ² and the UV irradiation time was set to 50 hours, the above-mentioned Examples 1 to 4 and Comparative Examples 1 to 4 were combined. Black candy was evaluated in the same manner as glass. As a result, it was confirmed that the laminated glass of Example 5 was less likely to generate black spots with much less black precipitates than the laminated glass of Comparative Example 5.

[0093] (Measurement of visible light transmittance)

The laminated glass of Example 5 and Comparative Example 5 was subjected to spectroscopic measurement in the same manner as the laminated glass of Examples 1 to 4 and Comparative Examples 1 to 4, and the visible light transmittance (Tvis ( 0 h)), and the visible light transmittance (Tvis (50h)) after UV irradiation similar to the above-mentioned “evaluation of black candy” was calculated. Also, the value of Tvis (50h) was calculated by subtracting the value of Tvis (Oh) from the change in visible light transmittance (ΔTvis). Table 2 shows the results obtained.

[Table 2] Polymerization of copper phosphonate complex PVB Tvis (Oh) Tvis (50h) △ Tvis

J Example 5 Ethylphosphonic acid copper complex 1 700 62.8 5 56. 6 5-6.2 Comparative Example 5 Ethylphosphonic acid copper complex 650 67.44 5 7.6 3-9.8 1 [0094] From Table 2, it was confirmed that the laminated glass of Example 5 had a smaller change in visible light transmittance than that of Comparative Example 5, and it was difficult to cause a decrease in translucency.

[Preparation of copper phosphinate complex]

[0095] (Preparation of copper dimethylphosphinate complex)

Dimethylphosphinic acid was used as a phosphorus compound, and 0.47 g (5. Ommol) thereof was dissolved in 10 mL of toluene. To the resulting solution, 0.50 g (2.5 mmol) of copper acetate monohydrate was added and heated to reflux. The solid produced in the solution after the reaction was separated by filtration to obtain a copper dimethylphosphinate complex.

[Production of laminated glass]

[0096] (Example 6 and Comparative Example 6)

Various phosphate ester copper complexes 1. Laminated glasses were prepared in the same manner as in Examples 1 to 4 and Comparative Examples 1 to 4 except that 0.14 g of a dimethylphosphinic acid copper complex was used instead of Og. As PVB, those having a polymerization degree of 1700 and 650 were used, respectively. The case where PVB having a polymerization degree of 1700 is used corresponds to Example 6, and the case where PVB having a polymerization degree of 650 is used corresponds to Comparative Example 6.

[Characteristic evaluation]

[0097] (Evaluation of blackening)

For the laminated glass of Example 6 and Comparative Example 6, the UV irradiation intensity was set to 0.75 WZm ² and the UV irradiation time was set to 50 hours, and the above-mentioned Examples 1 to 4 and Comparative Examples 1 to 4 were combined. Black candy was evaluated in the same manner as glass. As a result, in the laminated glass of Example 6, the generation of black precipitates was strong, whereas in the laminated glass of Comparative Example 6, a small amount of black and precipitates were observed.

[0098] (Measurement of visible light transmittance)

The laminated glass of Example 6 and Comparative Example 6 was subjected to spectroscopic measurement in the same manner as the laminated glass of Examples 1 to 4 and Comparative Examples 1 to 4, and the visible light transmittance (Tvis ( 0 h)), and the visible light transmittance (Tvis (50h)) after UV irradiation similar to the above-mentioned “evaluation of black candy” was calculated. Also, the value of Tvis (50h) was calculated by subtracting the value of Tvis (Oh) from the change in visible light transmittance (ΔTvis). The results obtained are shown in Table 3. [Table 3]

From Table 3, it was confirmed that the laminated glass of Example 6 had a smaller change in visible light transmittance than that of Comparative Example 6, and it was found that the translucency was hardly lowered.

Claims

The scope of the claims

[1] A near-infrared light-absorbing material characterized by containing polybutyral resin having a degree of polymerization of 800 to 2300 and copper ions.

[2] A phosphinic acid compound, a phosphonic acid compound, a phosphonic acid monoester compound, a phosphoric acid monoester compound, and a phosphoric acid diester compound, further comprising at least one phosphorous compound selected from the group consisting of: The near infrared light absorbing material according to claim 1

[3] The near-infrared light absorbing material according to [1] or [2], further comprising a plasticizer.

[4] A sheet-like molded article having the near-infrared light absorbing material force according to any one of claims 1 to 3.

[5] a translucent substrate;

A near-infrared light absorbing layer made of the near-infrared light absorbing material according to any one of claims 1 to 3, provided on the translucent substrate,

The laminated body characterized by including.