JP2001019939A - Near-infrared light-absorbing composition and near- infrared light absorber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in selective absorbability of near-infrared light and selective transmittability of visible light, by including a component comprising a copper ion and specific two kinds of phosphate ester compounds, and/or a component comprising specific two kinds of compounds. SOLUTION: This composition is obtained by including (A) a component comprising (i) a copper ion, (ii) a phosphate ester compound of formula I [X1 is an aryl(alkyl); j is 1 or 2], and (iii) a compound of formula II [X2 is each of formulas III-V (R1 is a 1-20C alkyl; R2 is H or a 1-4C alkyl; R3 is a 1-6C alkylene; m is 1-6) or the like; n is 1 or 2], and/or (B) a component comprising (iv) a phosphate ester copper compound obtained by reacting the component i with the component ii, and (v) a phosphate ester copper compound obtained by reacting the component i with the component iii. The formulating weight ratio of the component ii and/or the component iv to the component iii and/or the component v is pref. (10:90) to (90:10).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a near-infrared light absorbing composition and a near-infrared light absorbing agent having absorption characteristics for light in the near infrared region (near infrared light).

[0002]

2. Description of the Related Art As a conventional near-infrared light absorbing composition, JP-A-6-118228 discloses a composition containing a phosphate ester compound and an ionic metal component containing copper ions as a main component. Is disclosed.

[0003]

The above-mentioned conventional near-infrared light absorbing composition has a property that it absorbs near-infrared light efficiently and has a high visible light transmittance. Depending on the application, the absorbance for light in the near-infrared region in the wavelength region (approximately around 750 nm; hereinafter, referred to as a “boundary wavelength region”) that falls on the boundary between visible light and near-infrared light, and for light in the visible region The transmittance was not always sufficient. Therefore, the present invention has been made in view of such circumstances, and a near-infrared light-absorbing composition and a near-infrared light having sufficiently excellent selective absorption of near-infrared light and selective transmittance of visible light have been provided. It is intended to provide an external light absorber.

[0004]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies on the spectroscopic properties of a compound obtained by reacting a phosphoric acid ester compound with a copper compound. The present inventors have found that a composition containing a phosphate ester compound having the chemical structure described above, and a mixed composition of different phosphate ester compounds are effective in solving the above-mentioned problems, and arrived at the present invention. That is, the near-infrared light absorbing composition of the present invention is characterized by containing the following component (A) and / or the following component (B). Component (A): a component comprising copper ions, a first phosphate compound represented by the following formula (1), and a second phosphate compound represented by the following formula (2): Component (B): A first phosphate ester copper compound obtained by reacting the first phosphate compound with a copper compound,
And a component comprising a second phosphate ester copper compound obtained by reacting the second phosphate ester compound with the copper compound

[0005]

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Wherein X ¹ represents an aryl group or an arylalkyl group, and X ² is represented by the following formula (3), (4), (5), (6) or (7) And j represents a group or an alkyl group, and j and n are each independently 1 or 2. ]

[0007]

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[However, in formulas (3) to (7), R
¹ represents an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³ represents an alkylene group having 1 to 6 carbon atoms, and R ⁴ represents Carbon number is 1
10 represents an alkylene group, R ⁵ represents a hydrogen atom or a methyl group, m is an integer of 1 to 6, and k is 0 to 5
And p is an integer of 2 to 6, and r is an integer of 1 to 5. ]

According to the near-infrared light absorbing composition of the present invention, the phosphate group of the phosphate compound binds to the copper ion through a coordination bond and / or an ionic bond. It is dissolved or dispersed in the composition in a state surrounded by the acid ester, and the near infrared light is selectively absorbed by the electronic transition between the d orbits of the copper ion. At this time,
It was confirmed that when the first phosphoric acid ester compound and the second phosphoric acid ester copper compound were mixed, the absorptivity for near-infrared light on the long wavelength side in the boundary wavelength region was increased. Further, in this case, the transmittance of visible light on the same short wavelength side is increased, and in combination with the improvement of the absorption of near-infrared light,
The absorptivity of visible light with respect to the absorptivity of near infrared light is sufficiently reduced. This is due to the mutual influence of both phosphate ester compounds, such as the fact that the first and second phosphate ester compounds coexist to promote the electron transition of copper ions corresponding to the wavelength of near-infrared light. It seems to be. Therefore, it becomes possible to improve the selective absorption of near-infrared light and the selective permeability of visible light in the near-infrared light absorbing composition.

In addition, as the near-infrared light absorbing composition, a solution (near-infrared light absorbing agent) containing only the first phosphoric acid ester compound and the copper compound or only the first phosphoric acid ester copper compound is prepared. When used as a near infrared light absorbing material,
Immediately after the preparation, it exhibits near-infrared light absorption, but the solution is suspended as time elapses, and eventually there is a tendency that light cannot be transmitted. However, the solution obtained by adding the second phosphate ester compound or the second phosphate ester copper compound to the solution does not cause suspension for a long period of time, and has stable selective absorption of near-infrared light and visible light. It was confirmed that it exhibited selective permeability. Therefore, by containing the first and second phosphoric esters, even in the case of a solution, selective absorption for near-infrared light and selective transmittance for visible light can be maintained for a long period of time. It is extremely excellent in storage stability when the infrared light absorbing composition is used as a solution.

Further, the second phosphate compound is
When the phosphoric acid ester compound has a group represented by any one of the above formulas (3) to (7), the near-infrared light-absorbing composition obtained using such a phosphoric acid ester compound can emit near-infrared light. Is significantly increased. Therefore, it becomes possible to further improve the selective absorption for near-infrared light and the selective transmittance for visible light.

It is preferable that the first phosphate compound has a phenyl group as X ¹ in the above formula (1). In this way, a sufficient absorption effect on near-infrared light can be obtained, and visible light with respect to the absorptivity of near-infrared light can be reduced as compared with the case where X ¹ is an aryl group other than a phenyl group. Has a small ratio of absorptivity and is excellent in solubility in a solvent. Therefore, if X ¹ is a phenyl group,
It becomes possible to further improve the selective absorption of near infrared light and the selective transmittance of visible light in the near infrared light absorbing composition.

Further, the first phosphate compound is
More preferably, j in the above formula (1) is 1. In this case, as compared with the case where j in the above formula (1) has j = 2 (phosphate monoester compound) and / or a copper compound thereof as a component, the ratio of visible light to near-infrared light absorptance is higher. The ratio of absorption is smaller, and
The absorptivity of near-infrared light becomes larger. Therefore, when a compound having a group OX ¹ in which j in the above formula (1) is 1 (phosphate diester compound) is used as the first phosphate compound, the near-infrared light in the near-infrared light-absorbing composition is used. And the selective transmittance of visible light can be further improved.

Further, the first phosphate compound and / or
Alternatively, the content ratio of the first copper phosphate compound and the second copper phosphate compound and / or the second copper phosphate compound is 10:90 to 90:10, preferably 40:90, by weight ratio. 60 to 90:10, particularly preferably 6
The ratio is preferably from 0:40 to 85:15.

When the content of the first phosphoric acid ester compound and / or the first phosphoric acid copper compound is less than 10, the near-infrared light-absorbing composition may contain the first phosphoric acid ester compound and / or Alternatively, the difference in absorbance at wavelengths before and after the boundary wavelength region does not tend to be sufficiently increased compared to the case where the first phosphoric acid ester copper compound is used alone. On the other hand, when the above content ratio exceeds 90, when dissolved in a solvent, the solution tends to be easily suspended after several days to several weeks.

In the second phosphoric acid ester compound, R ⁵ in the above formula (7) is a methyl group, p in the above formula (7) is 2, and It is even more preferable that the compound has a group X ^{2 in} which r is 1, that is, a phosphate compound represented by the following formula (8).

[0017]

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[Where n is 1 or 2] ]

The near-infrared light-absorbing composition obtained by using this phosphate compound as the second phosphate compound further improves near-infrared light absorption. Therefore, by using this phosphate compound as the second phosphate compound, it becomes possible to further enhance the selective absorption for near-infrared light and the selective transmittance for visible light.

Further, the near-infrared light absorber according to the present invention comprises:
The near-infrared light absorbing composition of the present invention is characterized by being dissolved or dispersed in a solvent. By applying such a near-infrared light absorbing agent to, for example, a glass material or a resin material having a property of transmitting visible light, a near-infrared light absorbing material can be obtained extremely easily. This makes it easy to apply the near-infrared light-absorbing composition of the present invention to an arbitrary portion or surface of an article having various sizes and shapes, for example, a large flat display panel or the like. Can also be applied to Moreover, the solvent is a resin (resin monomer)
In this case, a thin-film near-infrared light-absorbing material such as a resin film can be obtained very easily.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The near-infrared ray absorbing composition and near-infrared ray absorbing agent of the present invention will be described in detail below. First, the near-infrared light-absorbing composition of the present invention contains the component (A) and / or the component (B).

<Component (A)> The component (A) is a copper ion,
It comprises a first phosphate compound represented by the above formula (1) and a second phosphate compound represented by the above formula (2). Specific examples of copper salts for supplying copper ions include copper acetate, copper acetate monohydrate, copper formate, copper stearate, copper benzoate, copper ethyl acetoacetate, copper pyrophosphate, copper naphthenate, and citric acid. Copper salt anhydrides and hydrates of organic acids such as copper, and anhydrides and hydrates of copper salts of inorganic acids such as copper hydroxide, copper chloride, copper sulfate, copper nitrate, and basic copper carbonate. . Among these organic acid salts, copper acetate,
Copper acetate monohydrate and copper benzoate are preferably used, and among these inorganic acid copper, copper hydroxide is preferably used. The component (A) may contain metal ions other than copper ions (hereinafter, referred to as “other metal ions”). Examples of the other metal ions include sodium, potassium, calcium, iron, Examples include ions of metals such as manganese, magnesium, and nickel.

The first phosphate compound and the second phosphate compound are produced, for example, by any of the following first method, second method, third method, and the like.

[First Method]: In the first method, a compound represented by the following formula (9) or the following formula (10) is reacted with phosphorus pentoxide without a solvent or in an appropriate organic solvent. It is a way to make it.

[0025]

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Wherein X ¹ represents an aryl group or an arylalkyl group, and X ² is represented by the above formula (3), (4), (5), (6) or (7) Represents a group. ]

When the compound represented by the formula (9) is used,
A phosphoric ester compound of formula (10)
By using the compound represented by the formula, a second phosphate compound can be obtained. The compound represented by the above formula (9) is preferably a specific example in which X ¹ is a phenyl group in that the obtained copper compound of the first phosphate compound has excellent near-infrared light absorption properties. That is, phenol. Further, as the compound represented by the above formula (10), specifically, the following formula (11), formula (12), formula (13), formula (14) or formula (15)
And an alcohol represented by the formula (13) or (14) are preferable, and an alcohol represented by the formula (15) is particularly preferable.

[0028]

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As described above, the compound represented by the formula (9) contains phenol. In the present invention, the compounds represented by the formula (9) or (10) are collectively referred to for convenience. Hereafter, it is referred to as “specific alcohol”. Here, the organic solvent used in the reaction between the specific alcohol and phosphorus pentoxide is an organic solvent that does not react with phosphorus pentoxide, such as hexane, cyclohexane, heptane, octane, benzene, toluene, xylene, and petroleum. Hydrocarbon solvents such as spirit, chloroform, carbon tetrachloride, dichloroethane, halogenated hydrocarbon solvents such as chlorobenzene, diethyl ether, diisopropyl ether,
Examples thereof include ether solvents such as dibutyl ether and tetrahydrofuran, and ketone solvents such as acetone, methyl ethyl ketone, and dibutyl ketone. Of these, toluene and xylene are preferable.

In this [first method], the reaction condition of the specific alcohol with phosphorus pentoxide is such that when the specific alcohol is phenol, the reaction temperature is 0 to 100 ° C., preferably 40 to 80 ° C. The reaction time is from 1 to 96 hours, preferably from 4 to 72 hours. When the specific alcohol is an alcohol represented by the formula (11), the formula (12), the formula (13), the formula (14) or the formula (15), the reaction temperature is 0 to 100 ° C., preferably 40 to 100 ° C. 80 ° C., and the reaction time is 1 to 24 hours, preferably 4 to 9 hours.

In the first method, for example, a specific alcohol and phosphorus pentoxide are mixed at a molar ratio of 3: 1.
By using at a ratio such that the number of hydroxyl groups represented by the above formulas (1) and (2) is 2 (j represented by the formula (1) and n represented by the formula (2) is 2) An ester compound (hereinafter, referred to as “monoester”) and a phosphoric diester compound (hereinafter, “diester”) in which the number of these hydroxyl groups is 1 (j in formula (1) and n in formula (2) are 1) And a ratio of about 1: 1).
Further, by appropriately selecting the ratio between the specific alcohol and phosphorus pentoxide and the reaction conditions, the ratio between the monoester and the diester is adjusted within the range of 99: 1 to 40:60 in molar ratio.

[Second method]: In this second method, a specific alcohol is reacted with phosphorus oxyhalide without solvent or in an appropriate organic solvent, and water is added to the obtained product. This is a method of hydrolysis. As the phosphorus oxyhalide, it is preferable to use phosphorus oxychloride or phosphorus oxybromide, and particularly preferably phosphorus oxychloride.
The organic solvent used in the reaction between the specific alcohol and the phosphorus oxyhalide is an organic solvent that does not react with the phosphorus oxyhalide, for example, hexane,
Hydrocarbon solvents such as cyclohexane, heptane, octane, benzene, toluene, xylene, petroleum spirit,
Chloroform, carbon tetrachloride, dichloroethane, halogenated hydrocarbon solvents such as chlorobenzene, ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether and the like, among these, toluene,
Xylene is preferred. The reaction conditions of the specific alcohol and the phosphorus oxyhalide are as follows.
0 ° C., preferably 40-80 ° C .;
20 hours, preferably 2 to 8 hours. In the second method, for example, a monoester can be obtained by using a specific alcohol and phosphorus oxyhalide in a molar ratio of 1: 1.

When a specific alcohol represented by the formula (12), (13) or (15) is used, the ratio between the specific alcohol and the phosphorus oxyhalide and the reaction conditions are selected. In addition, Lewis acid catalysts such as titanium tetrachloride (TiCl ₄ ), magnesium chloride (MgCl ₂ ), and aluminum chloride (AlCl ₃ ) are used as reaction catalysts, and triethylamine, tributylamine, etc. Amines and pyridine are preferably used. By using these reaction catalysts and the hydrochloric acid catching agent, a mixture of a monoester and a diester is obtained. By appropriately selecting the ratio of the specific alcohol to the phosphorus oxyhalide and the conditions for the reaction including the reaction catalyst, the ratio of the monoester to the diester is 99: 1 to 1: by molar ratio.
It is adjusted within the range of 99.

When a specific alcohol represented by the above formula (11) or (14) is used, the ratio of the specific alcohol to phosphorus oxyhalide and the reaction conditions are selected, and the Lewis acid is used. By using the catalyst and the hydrochloric acid catching agent together, a mixture of a monoester and a diester can be obtained.
It is adjusted within the range of 9: 1 to 1:99. However, when a specific alcohol having a small number m of repeating units of the alkylene oxide group is used, the obtained phosphate ester compound becomes water-soluble, and therefore, when a hydrochloric acid catching agent such as an amine is used, the formation of the phosphate compound becomes difficult. It tends to be difficult to remove the resulting amine hydrochloride by washing with water. In the above, the amount of the reaction catalyst used is 0.005 to 1 mol of phosphorus oxyhalide.
It is 0.2 mol, preferably 0.01 to 0.05 mol.

[Third Method]: In the third method, a phosphonic acid ester compound is synthesized by reacting a specific alcohol with phosphorus trihalide without using a solvent or in an appropriate organic solvent. Thereafter, the resulting phosphonate compound is oxidized. As the phosphorus trihalide, it is preferable to use phosphorus trichloride or phosphorus tribromide, and particularly preferably phosphorus trichloride. The organic solvent used in the reaction between the specific alcohol and phosphorus trihalide is an organic solvent that does not react with phosphorus trihalide, such as hexane, cyclohexane, heptane, octane, benzene, toluene, xylene, Examples include hydrocarbon solvents such as petroleum spirits, halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride, dichloroethane, and chlorobenzene, and ether solvents such as diethyl ether, diisopropyl ether, and dibutyl ether. , Heptane is preferred.
The reaction conditions of the specific alcohol and the phosphorus trihalide are such that the reaction temperature is 0 to 90 ° C, preferably 40 to 75 ° C.
° C, and the reaction time is 1 to 10 hours, preferably 2 to 5 hours.
Time.

As a means for oxidizing the phosphonate ester compound, a phosphorohalolidate compound is synthesized by reacting the phosphonate ester compound with a halogen such as chlorine gas. Can be utilized. Here, the reaction temperature between the phosphonic acid ester compound and the halogen is preferably 0 to 40 ° C., particularly preferably 5 to 40 ° C.
２５25 ° C. Before oxidizing the phosphonate ester compound, the phosphonate ester compound may be purified by distillation. In this third method, for example,
The specific alcohol and phosphorus trihalide in a molar ratio of 3:
By using at a ratio of 1, the diester can be obtained with high purity. Also, by selecting the ratio of the specific alcohol and phosphorus trihalide and the reaction conditions, a mixture of monoester and diester is obtained,
The ratio is adjusted in the range of 99: 1 to 1:99 in molar ratio.

Preferred specific examples of the first phosphate compound obtained by the above first to third methods include compounds represented by the following formulas (16) -a and (16) -b: Is mentioned. These phosphoric acid ester compounds can be used alone or in combination of two or more as the first phosphoric acid ester compound, and from the viewpoint of near-infrared light absorption properties of those copper compounds, the formula (I) is a diester. 16) It is preferable to use a phosphate compound represented by -b.

[0038]

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Preferred specific examples of the second phosphate compound obtained by the above first to third methods include the following formulas (17) to ax and the following formulas (18) to a:
x, compounds represented by the following formulas (19) -at. These phosphate compounds can be used alone or in combination of two or more as the first phosphate compound. From the viewpoint of near-infrared light absorption properties of the copper compounds, the compounds represented by the formula (18)- Phosphate compounds represented by a to x and formulas (19) to at are preferred, and phosphate compounds represented by formulas (19) to st are particularly preferred.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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<Component (B)> The component (B) is composed of a first phosphate ester copper compound and a second phosphate ester compound obtained by reacting the first phosphate ester compound with the copper compound. It consists of a second copper phosphate ester compound obtained by reaction with a copper compound. As the copper compound, the above-mentioned copper salts can be used, and the reaction between the first or second phosphate ester compound (hereinafter, referred to as “specific phosphate ester compound”) and the copper salt is carried out under an appropriate condition. This is performed by bringing the two into contact with each other. In particular,
The following methods (a), (b), and (c) can be used. (A) A method in which a specific phosphate compound and a copper salt are mixed and reacted. (B) A method of reacting a specific phosphate compound with a copper salt in an appropriate organic solvent. (C) contacting an organic solvent layer containing a specific phosphate compound in an organic solvent with an aqueous layer in which a copper salt is dissolved or dispersed to form a specific phosphate compound and a copper salt; How to react with.

The reaction conditions of the specific phosphate compound and the copper salt are such that the reaction temperature is 0 to 150 ° C., preferably 20 to 120 ° C., and the reaction time is 0.5 to 15 hours, preferably It is 1 to 10 hours, preferably 1 to 7 hours.

The organic solvent used in the method (b) is not particularly limited as long as it can dissolve or disperse the specific phosphate compound used.
For example, benzene, toluene, aromatic compounds such as xylene, methyl alcohol, ethyl alcohol, alcohols such as isopropyl alcohol, methyl cellosolve, glycol ethers such as ethyl cellosolve, diethyl ether, diisopropyl ether, ethers such as dibutyl ether, Examples include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, hexane, kerosene, petroleum ether and the like. Also, a polymerizable organic solvent such as a (meth) acrylate such as (meth) acrylate, an aromatic vinyl compound such as styrene and α-methylstyrene, and the like are used.

On the other hand, the organic solvent used in the above method (c) is not particularly limited as long as it is insoluble or hardly soluble in water and can dissolve or disperse the specific phosphate compound used. However, for example, among those exemplified as the organic solvent used in the method (b), aromatic compounds, ethers, esters, hexane, kerosene, (meth) acrylates, aromatic vinyl compounds and the like can be mentioned. Can be

In the reaction between a specific phosphate compound and a copper salt, an acid component as an anion is released from the copper salt. Such an acid component, when a resin composition obtained by dissolving or dispersing the near-infrared light-absorbing composition of the present invention as described below in a resin, reduces the moisture resistance and thermal stability of the resin composition. It is preferable to remove it as necessary because it may cause a reduction. When the phosphate copper compound is produced by the above method (a) or (b), a specific phosphoric ester compound is reacted with a copper salt, and then the produced acid component ((b)) In the above, the generated acid component and organic solvent) can be removed by distillation. Further, in the case of producing the phosphoric acid ester copper compound by the method (c), as a preferable method for removing the acid component, a specific phosphoric acid ester compound is contained in an organic solvent which is insoluble or hardly soluble in water. After the organic solvent layer is neutralized by adding an alkali, by contacting the organic solvent layer with an aqueous layer in which the copper salt is dissolved or dispersed, a specific phosphate compound and a copper salt are converted. After the reaction, there is a method of separating an organic solvent layer and an aqueous layer. Here, examples of the alkali include sodium hydroxide, potassium hydroxide, ammonia and the like, but are not limited thereto. According to this method, a water-soluble salt is formed by the acid component and the alkali released from the copper salt, and the salt migrates to the aqueous layer, and the specific phosphoric acid ester copper compound is formed in the organic solvent layer. The acid component is removed by separating the aqueous layer and the organic solvent layer.

Further, the number m of repeating units of the alkylene oxide group in the phosphate compound represented by the above formulas (3), (4) and (5) is an integer of 1 to 6, preferably 1 to 3. It is. When the value of m exceeds 6, the hardness when the near-infrared light-absorbing composition is contained in, for example, a resin to form a resin composition is significantly reduced.
On the other hand, when the value of m is 0, that is, when the alkylene oxide group is not bonded, when the resin composition is used,
Copper ions are difficult to disperse in the resin. Further, the number k of repeating units of the alkylene oxide group in the above formula (6) is an integer of 0 to 5, preferably 0 to 2. If the value of k exceeds 5, the hardness of the resin composition tends to decrease.

Further, from the viewpoint of thermal stability and environmental resistance of the phosphate ester compound and the phosphate ester copper compound, the number of repeating units of the alkylene oxide group is m.
Is particularly preferably 1. The copper salt of a phosphate ester compound having an alkylene oxide group in which m is 1 and the copper phosphate compound have a higher thermal decomposition temperature than those having an alkylene oxide group in which m is an integer of 2 or more. Therefore, when a composition containing a copper salt of a phosphate ester compound having an alkylene oxide group and m is 1 and a composition containing a phosphate ester copper compound are thermoformed, the molding temperature can be increased. Therefore, molding is facilitated, and molding workability can be further improved.
Further, the copper salt of a phosphate ester compound having an alkylene oxide group in which m is 1 and a copper phosphate ester compound are superior in environmental resistance to those having an alkylene oxide group in which m is an integer of 2 or more. Has the property. Specifically, the copper salt of a phosphate ester compound having an alkylene oxide group in which m is 1 and the copper phosphate compound hardly deteriorate with time in the light transmittance in the visible region under a high-temperature and high-humidity environment. In contrast, those having an alkylene oxide group in which m is an integer of 2 or more tend to deteriorate with time.

As described above, as the specific phosphate ester compound, a monoester or a diester is used. In the above formula (1) or the above formula (2), the triester having no hydroxyl group is Since it does not have a hydroxyl group capable of coordinating and / or ionic bonding with copper ions, it is difficult to disperse copper ions in the resin when forming a resin composition described later.

Further, R ¹ in the formulas (3) to (6) is an alkyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 4, and particularly preferably 1 to 2 carbon atoms. is there. When the phosphate compound having more than 20 carbon atoms in the alkyl group R ¹ is used as a resin composition, the compatibility with the resin may be reduced, and it is difficult to disperse copper ions in the resin. Further, R in formulas (3) and (4)
² is an alkyl group having 1 to 4 carbon atoms. That is,
Examples of the alkylene oxide group in the formulas (3) and (4) include a propylene oxide group and a butylene oxide group, and a propylene oxide group is particularly preferable. When the carbon number of R ² exceeds 4, it is difficult to disperse the near-infrared light absorbing composition in a solvent or a resin at a high ratio. Further, R ³ in the formulas (5) and (6) is an alkylene group having 1 to 6, preferably 1 to 4, more preferably 3 to 4, and particularly preferably 3 carbon atoms. That is, examples of the alkylene oxide group (OR ³ ) include a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, a pentyleneoxy group, and a hexyleneoxy group, and particularly, a propyleneoxy group and a butyleneoxy group. Is preferred. This R ³
When the number of carbon atoms exceeds 6, it is difficult to disperse the near-infrared light absorbing composition in a solvent or a resin at a high ratio. Furthermore, R ⁴ in the above formula (6) has 1 to 10, preferably 3 to 6, more preferably 3 to 6 carbon atoms.
4, especially preferably 3 alkylene groups.

The ratio of the first and second phosphate compounds to the copper ions is such that the hydroxyl groups or the oxygen atoms derived from the hydroxyl groups in the first and second phosphate compounds are relative to 1 mole of the copper ions. 0.5 to 10 mol, especially 1.5
It is preferably from 5 to 5 mol. When this ratio is less than 0.5 mol, it tends to be difficult to disperse copper ions in the resin when forming a resin composition. If this proportion exceeds 10 mol, the proportion of hydroxyl groups not involved in coordination bonds and / or ionic bonds with copper ions becomes excessive, so that the near-infrared light-absorbing composition has a relatively large hygroscopic property. Tend to be. Therefore, this ratio should be 0.5 to
When the molar ratio is 10 mol, when a resin composition is used, copper ions can be dispersed well in the resin to improve the near-infrared light absorption property, and the near-infrared light absorption property excellent in moisture absorption resistance It is possible to obtain a composition and a near-infrared light absorbing material containing the composition.

Further, when the near-infrared light absorbing composition of the present invention is used as a resin composition as described later, the content of copper ions is 0.1 to 60% by weight of the whole resin composition.
Preferably 0.1-20% by weight, more preferably 0.3%
To 15% by weight, more preferably 0.5 to 5% by weight. When this ratio is less than 0.1% by weight, the near-infrared light absorption characteristics tend not to be enhanced. On the other hand, when this ratio exceeds 60% by weight, it is extremely difficult to disperse copper ions in the resin. It tends to be difficult.

The use ratio of the above-mentioned metal ions is preferably 50% by weight or less, more preferably 30% by weight or less, further preferably 20% by weight or less based on the total metal ions including copper ions. If this proportion exceeds 50% by weight, the bond coordination between the copper ion and the phosphate compound is affected by other metal ions,
It tends to be difficult to obtain a near-infrared light absorbing composition having a sufficiently high near-infrared light absorption rate.

According to such a near-infrared light absorbing composition of the present invention, the phosphate groups of the first and second phosphate compounds are bonded to copper ions by coordination bonds and / or ionic bonds. The copper ions are dissolved or dispersed in the composition in a state of being surrounded by the phosphate ester, and near infrared light is selectively absorbed by electronic transition between d orbitals of the copper ions. At this time, if the first and second phosphoric acid ester copper compounds are mixed, the absorptivity to near-infrared light on the long wavelength side in the boundary wavelength region is increased. In addition, the transmittance of visible light on the same short wavelength side is increased, and together with the improvement of the absorption of near-infrared light, the absorption of visible light with respect to the absorption of near-infrared light is sufficiently reduced. . This is due to the mutual influence of both phosphate ester compounds, such as the fact that the first and second phosphate ester compounds coexist to promote the electron transition of copper ions corresponding to the wavelength of near-infrared light. It seems to be. Therefore, it becomes possible to improve the selective absorption of near-infrared light and the selective permeability of visible light in the near-infrared light absorbing composition.

Since the first and second phosphate compounds are mixed, suspension such as a solution containing only the first phosphate compound or the first phosphate copper compound is unlikely to occur. . Therefore, stable selective absorption of near-infrared light and selective transmission of visible light are exhibited, and even when a solution in which the near-infrared light absorbing composition is dissolved is used, the selective absorption for near-infrared light is also achieved. In addition, it can maintain selective transmittance to visible light for a long period of time, and is extremely excellent in storage stability when a near-infrared light absorbing composition is used as a solution.

Further, as the second phosphate compound, X ² in the above formula (2) is represented by the above formula (3), (4), (5), (6) or (7). Since it is a phosphate compound having a group to be formed, the near-infrared light-absorbing composition obtained using the compound has a very high absorption rate for near-infrared light. Therefore, it becomes possible to further improve the selective absorption for near-infrared light and the selective transmittance for visible light.

When the first phosphate compound is a phosphate compound having a phenyl group as X ¹ in the above formula (1), a sufficient absorption effect for near infrared light is obtained. In addition, the ratio of the absorptivity of visible light to the absorptivity of near-infrared light is smaller than that in the case where X ¹ is an aryl group other than a phenyl group, and the solubility in a solvent is excellent. Therefore, when X ¹ is a phenyl group, it becomes possible to further improve the selective absorption of near-infrared light and the selective transmittance of visible light in the near-infrared light absorbing composition.

Further, the first phosphate compound is
When j in the above formula (1) is 1, a near-monophosphate compound and / or a copper compound thereof in which j in the above formula (1) is 2 is contained as a component. The ratio of the absorptivity of visible light to the absorptivity of infrared light becomes smaller, and the absorptivity of near infrared light becomes larger. As a result, the near-infrared light absorbing composition and the near-infrared light selective absorptivity and visible light selective transmissivity can be further improved.

Further, the first phosphate compound and / or
Alternatively, the content ratio of the first copper phosphate compound and the second copper phosphate compound and / or the second copper phosphate compound is 10:90 to 90:10, preferably 40:90, by weight ratio. 60 to 90:10, particularly preferably 6
The ratio is preferably from 0:40 to 85:15.

When the content ratio of the first phosphate ester compound and / or the first phosphate ester copper compound is less than 10, the near-infrared light-absorbing composition becomes less than the first phosphate ester compound and / or the first phosphate ester compound. Alternatively, the difference in absorbance at wavelengths before and after the boundary wavelength region tends not to be sufficiently increased as compared with the case where the first phosphoric acid ester copper compound is used alone. On the other hand, when the above content ratio exceeds 90, when dissolved in a solvent, the solution tends to be easily suspended after several days to several weeks.

Further, in the second phosphate compound, R ⁵ in the above formula (7) is a methyl group, p in the above formula (7) is 2, and A phosphate compound having a group X ^{2 in} which r is 1, that is, a phosphate compound represented by the above formula (19) -s to t (a phosphate compound represented by formula (8)) Then, the absorptivity for near-infrared light in the near-infrared light absorbing composition is further improved. Therefore, in this case, it is possible to further enhance the selective absorption for near-infrared light and the selective transmittance for visible light.

<Near-infrared light absorber (liquid composition)>
The near-infrared light absorbing agent of the present invention is a liquid composition obtained by dissolving or dispersing the near-infrared light absorbing composition according to the present invention in a solvent, and a thin film formed by evaporating the solvent is optically If it is transparent, the near-infrared light absorber itself may be transparent, translucent, or opaque. As the solvent, water or an organic solvent can be used, and as the organic solvent, methyl alcohol, ethyl alcohol,
Alcohols such as isopropyl alcohol and butyl alcohol, glycol ethers such as methyl cellosolve and ethyl cellosolve, ethers such as diethyl ether and diisopropyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethyl acetate, Isopropyl acetate, butyl acetate,
Esters such as butyl acetate cellosolve, aromatic compounds such as benzene, toluene and xylene, hexane, kerosene, petroleum ether and the like are used. Further, as other solvents, resins (resin monomers) as described in the resin composition described later, for example, (meth) acrylates such as (meth) acrylate, and aromatics such as styrene and α-methylstyrene An organic solvent having a polymerizability such as an aromatic vinyl compound can also be used.

The content of the near-infrared light-absorbing composition of the present invention in the near-infrared light-absorbing agent varies depending on the type of the solvent used, and the use or purpose of the near-infrared light-absorbing agent. However, from the viewpoint of the viscosity after preparation, the solvent is usually 100
The amount is adjusted within the range of 0.1 to 1900 parts by mass, preferably 1 to 900 parts by mass, particularly preferably 5 to 400 parts by mass with respect to parts by mass.

Such a near-infrared light absorbing agent (liquid composition)
Is applied to, for example, a glass material or a resin material having a property of transmitting visible light, whereby a near-infrared light-absorbing material can be obtained extremely easily. This makes it easy to apply the near-infrared light-absorbing composition of the present invention to an arbitrary portion or surface of an article having various sizes and shapes, for example, a large flat display panel or the like. Can also be applied to Moreover, when the solvent is a resin (resin monomer), a thin-film near-infrared light-absorbing material such as a resin film can be obtained very easily.

<Resin Composition> The near-infrared light absorbing composition of the present invention has excellent compatibility with the resin and, as described above, since the copper ions are well dispersed in the resin. And a resin composition having excellent near-infrared light absorption properties. The resin composition may be a monomer composition or a polymer composition obtained by polymerizing the monomer composition. The resin monomer constituting such a resin composition is not particularly limited as long as it is a resin excellent in dispersibility of the near-infrared light absorbing composition of the present invention or a copper compound thereof, for example, Acrylic resin shown below,
Alternatively, a resin monomer other than the acrylic resin can be preferably used.

As the acrylic resin, a polymer obtained from a (meth) acrylate monomer is preferably used. Specific examples of (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, Alkyl (meth) acrylates such as tertiary butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Modified (meth) acrylates such as hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isobornyl (meth) acrylate, methoxypolyethylene (meth) acrylate, and phenoxy (meth) acrylate; ethylene glycol di (meth) acrylate ) Acrylate,
Diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy-1,3
-Di (meth) acrylate, 2,2-bis [4- (meth) acryloxyethoxyphenyl] propane, 2-hydroxy-1- (meth) acryloxy-3- (meth) acryloxypropane, trimethylolpropanetri ( Examples include polyfunctional (meth) acrylates such as (meth) acrylate, pentaerythrit tri (meth) acrylate, and pentaerythrite tetra (meth) acrylate.

As another acrylic resin, other (meth) acrylate monomers and other copolymerizable copolymerizable with this (meth) acrylate monomer can be used. Copolymers with monomers are also used. Specific examples of such a copolymerizable monomer include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid,
Unsaturated carboxylic acids such as 2- (meth) acryloyloxyethylphthalic acid, acrylamides such as N, N-dimethylacrylamide, styrene, α-methylstyrene, chlorostyrene, dibromostyrene, methoxystyrene,
Aromatic vinyl compounds such as vinylbenzoic acid and hydroxymethylstyrene are exemplified. Other resins other than the acrylic resin include polyethylene terephthalate (PET), polyethylene, polypropylene, polyvinyl chloride, polycarbonate, styrene, α-methylstyrene, chlorostyrene, dibromostyrene, methoxystyrene, and vinyl benzoate. Examples thereof include polymers such as acids and aromatic vinyl compounds such as hydroxymethylstyrene. The above resin monomers can be used alone or in combination of two or more.

When only a monofunctional resin monomer is used, a thermoplastic resin is obtained. When a polyfunctional resin is used as a part or all of the monomer, a thermoplastic resin is obtained. Since a thermosetting resin is obtained, it is possible to obtain a near-infrared light-absorbing composition according to the purpose of use, application, processing method and the like by appropriately selecting these resin compositions. Of these, if you use a thermoplastic,
Since the remolding after the polymerization and curing is facilitated, the moldability of the near-infrared light absorbing composition is improved.

The resin composition containing the near-infrared light-absorbing composition of the present invention is prepared by incorporating the component (A) and / or the component (B) into the resin. The content ratio of the component (A) and / or the component (B)
Depending on the use or purpose of use of the obtained near-infrared light-absorbing material, from the viewpoint of moldability (or moldability),
0.1 to 400 parts by mass, preferably 0.3 to 200 parts by mass, particularly preferably 1 to 1 part by mass with respect to 100 parts by mass of the resin.
It is adjusted within the range of 00 parts by mass. The proportion of copper ions in the resin composition is preferably, for example, 0.1 to 20% by weight of the entire resin composition.
It is possible to reliably obtain a resin composition having excellent visible light transmittance. Although a specific method for preparing the resin composition is not particularly limited, it is preferable to use the following two methods.

[First Method]: In the first method, the component (A) (here, a mixture of the first and second phosphate compounds and a copper salt) in a resin monomer is used. And / or a component (B) is added to prepare a monomer composition, and the monomer composition is subjected to a radical polymerization treatment. In this method, the specific method of the radical polymerization treatment of the monomer composition is not particularly limited, and a radical polymerization method using a usual radical polymerization initiator, for example,
Known methods such as a bulk (cast) polymerization method, a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method can be used.

[Second Method] The second method is a method in which the component (A) and / or the component (B) are added to the resin and mixed. This method is used when a thermoplastic resin is used as the resin. Specifically, a method of adding the component (A) and / or the component (B) to the molten resin and kneading the resin, dissolving, dispersing, or swelling the resin in an appropriate organic solvent, and adding (A) After adding and mixing the component (B) and / or the component (B), there is a method of removing the organic solvent from the solution.

In the above method, as a means for kneading the resin and the component (A) and / or the component (B), means generally used as a melt kneading method for a thermoplastic resin, for example, a mixing roll is used. A kneading means, a means for pre-mixing with a Henschel mixer or the like, and a means for melt-kneading with an extruder may be used. On the other hand, the organic solvent used in the above method is not particularly limited as long as it can dissolve, disperse, or swell the resin, and specific examples thereof include methyl alcohol, ethyl alcohol, and isopropyl alcohol. Alcohols such as acetone, ketones such as methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene and xylene, chlorinated hydrocarbons such as methylene chloride, and amide compounds such as dimethylacrylamide and dimethylformamide. .

In the preparation of the above resin composition, (A)
When a component is used and a copper salt of an organic acid or an inorganic acid is used as the copper salt, a specific phosphate compound reacts with the copper salt, so that an acid component as an anion is released from the copper salt. Such an acid component is preferably removed as necessary. As a method therefor, (a) a method of extracting an acid component by immersing the resin composition in an appropriate organic solvent, and (b) a method of subjecting the monomer composition to polymerization before performing the polymerization treatment of the monomer composition An example is a method in which the composition is subjected to a cooling treatment to precipitate and separate an acid component.

The organic solvent used in the above method (a) can dissolve an acid component to be liberated, and has an appropriate affinity for the resin used (the resin does not dissolve, It is not particularly limited as long as it has an affinity for permeation. Specific examples of such solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, lower aliphatic alcohols such as isopropyl alcohol, acetone, methyl ethyl ketone, ketones such as methyl isobutyl ketone,
Ethers such as diethyl ether and petroleum ether, n-
Examples include aliphatic hydrocarbons such as pentane, n-hexane, n-heptane, chloroform, methylene chloride, and carbon tetrachloride, and halides thereof, and aromatic hydrocarbons such as benzene, toluene, and xylene. on the other hand,
In the above method (b), as the copper salt constituting the component (A), a copper salt other than an organic acid or an inorganic acid salt, in which a liberated acid component is hardly soluble in a monomer, may be used. Preferred and specific examples thereof include copper salts of carboxylic acids having an aromatic ring such as benzoic acid and copper hydroxide.

<Polyvinyl butyral resin composition, composition containing ethylene-vinyl acetate copolymer, composition containing partially saponified product of the copolymer> Among the compositions containing resins other than acrylic resin, Polyvinyl butyral-based resin, ethylene-vinyl acetate copolymer, or a composition containing a partially saponified copolymer thereof has excellent adhesion to a substrate made of a glass material or a plastic material, and
It has flexibility in itself, and has a characteristic that its temperature dependency is small. Therefore, when such a resin composition containing a near-infrared light-absorbing composition is used, adhesion to a substrate is ensured without using an adhesive, and therefore, near-infrared light having excellent moldability. A molded article having absorptivity can be easily obtained, and the resistance of the molded article to a temperature change can be improved.

In addition to the above-mentioned acrylic resins, a resin composition obtained by adding a near-infrared light-absorbing composition to these resins includes, as other components, various plasticizers having compatibility with the resin. Can be contained, whereby the dispersibility of the copper ion used as the near-infrared light absorbing component in the resin component can be increased. Specific examples of such plasticizers include phosphate plasticizers such as tricresyl phosphate and triphenyl phosphate, phthalic plasticizers such as dioctyl phthalate and dibutyl phthalate, dibutyl sebacate, butyl ricinolate, and methyl. Fatty acid plasticizers such as acetyl ricinoleate and butyl succinate;
Butylphthalylbutyl glycolate, triethylene glycol dibutyrate, triethylene glycol di-2-
Examples include glycol-based plasticizers such as ethyl butyrate and polyethylene glycol. Further, it may further contain a benzotriazole-based, benzophenone-based or salicylic acid-based ultraviolet absorber, other antioxidants, stabilizers, and the like.

<Display Front Plate> A front plate of an electronic display such as a plasma display panel (hereinafter simply referred to as a PDP) using the near infrared light absorbing composition or the near infrared light absorbing agent according to the present invention. It is very suitable to apply to a so-called display front panel. Some of the illuminants included in these electronic displays include
Some devices generate near-infrared light having a wavelength of 800 nm to 1100 nm. Near-infrared light emitted from the front of an electronic display is used for a near-infrared light remote control system such as a TV used around the electronic display (infrared remote control). ) May cause a malfunction. In particular,
In a PDP, discharge excitation of a rare gas (Xe, Ne) sealed between light-emitting electrodes is used, and near-infrared light having a higher intensity than other electronic displays is emitted. Under such circumstances, a display front panel excellent in near-infrared light absorption characteristics and visible light transmittance has been desired.

Thus, for example, a display front plate is made of the above resin composition containing the near-infrared light absorbing composition of the present invention, or the surface of the display front plate is coated with the near-infrared light absorbing composition of the present invention. Or by applying the near-infrared light absorber (liquid composition) of the present invention to the front panel of the display, it is extremely excellent in selective absorption of near-infrared light and selective transmittance of visible light. A display front panel can be obtained. Hereinafter, a display front plate using the near infrared light absorbing composition or near infrared light absorbing agent of the present invention will be described.

FIG. 1 is a structural view showing an example of a display front plate using the near-infrared light absorbing composition of the present invention. FIG. 1 (a) is a sectional view and FIG. 1 (b). FIG. 2 is an exploded perspective view showing a laminated structure. The display front plate 1 shown in FIG. 1 is an optically transparent plate attached to the front surface of a PDP, has a substantially flat plate shape, and has a near-infrared light composed of the near-infrared light absorbing composition of the present invention. On one surface of the transparent member 11 having an absorbing layer, a shield mesh 13 in which a thin wire having conductivity is braided vertically and horizontally to form a mesh is covered with a transparent film 14 made of resin, for example, polyethylene terephthalate (PET). It is affixed so that it can be seen.
Further, the entire surface of the other surface of the transparent member 11 is provided with a reflection reducing film 12.
Are formed. Further, an antireflection film 15 is formed on a surface of the transparent film 14 which is not in contact with the shield mesh 13.

Further, as the transparent member 11, the following three types are suitable. [First Embodiment]: A resin composition containing the near-infrared light-absorbing composition of the present invention, or a resin composition bonded to a transparent substrate made of glass or a transparent resin plate. [Second embodiment]: A structure in which a near-infrared light absorbing film 16 as a near-infrared light absorbing layer made of the near-infrared light absorbing composition of the present invention is formed on the transparent substrate. [Third embodiment]: One formed of the near-infrared light absorbing composition of the present invention, or one in which the near-infrared light absorbing composition of the present invention is bonded to the transparent substrate.

The resin used in the resin composition used in the first embodiment is preferably an acrylic resin, a polycarbonate resin, a styrene resin, a polyester resin, or a cellulose resin, and has visible light transmittance and weather resistance. From the viewpoints of moldability and the like, acrylic resins are particularly preferred. When a resin composition composed of an acrylic resin is used, an image displayed on a display can be easily viewed without being darkened, and the display front panel 1 which is excellent in durability and has few restrictions on a processing shape can be obtained. .

In the second embodiment, for example, the near-infrared light-absorbing agent of the present invention is applied to the transparent substrate surface and the solvent is evaporated, so that the near-infrared light-absorbing agent is formed on the transparent member 11. A film 16 is formed. Alternatively, on the transparent substrate surface,
The component (B) itself or a powder containing the component (B) may be applied by spraying with a powder spray or the like, or the powder may be attached via an adhesive substance such as an adhesive. On the other hand, the transparent member 11 according to the third embodiment is manufactured as a film-shaped or plate-shaped molded product by, for example, press-molding only the near-infrared light-absorbing composition of the present invention. When the transparent member 11 according to the third embodiment is used, it is possible to excel in near-infrared light absorption characteristics and to eliminate a slight absorption of visible light by a resin or the like.

Here, in the display front plate 1 provided with the transparent member 11 of each of the above forms, the wavelength of 800 nm
Display front plate 1 in wavelength region of 1000 nm
Near infrared light transmittance of 20% or less, preferably 1
Kind and concentration of component (A) and / or component (B) in the near-infrared light-absorbing composition or near-infrared light absorbing agent of the present invention so as to be 5% or less, more preferably 10% or less. The layer thickness (the thickness of the layer when applied or laminated, or the thickness of the resin layer when dispersed in a resin) is adjusted. In this way, for example, near-infrared light having a wavelength of around 950 nm, which is mainly used in infrared communication and the like, is sufficiently attenuated. Less is.

Further, the shield mesh 13 is, for example,
When knitted with a plastic fiber coated with a transition metal such as copper or nickel, electromagnetic waves in a frequency range of several MHz to several hundred MHz can be effectively and reliably shielded. The reflection reducing film 12 and the antireflection film 15 are formed by alternately laminating a thin film made of a low refractive index material such as silicon dioxide or aluminum oxide and a thin film made of a high refractive index material such as titanium dioxide or yttrium oxide. In particular.

FIG. 2 shows the display front panel 1 shown in FIG.
It is a perspective view which shows the use condition of. As shown in FIG. 2, the display front panel 1 is arranged so as to cover the panel surface 21 of the PDP 2 with the surface on which the antireflection film 15 is formed facing forward. The near-infrared light emitted from the panel surface 21 of the PDP 2 is absorbed by the near-infrared light absorbing layer, and the intensity is reduced to 20% or less, preferably 15% or less, more preferably 10% or less. On the other hand, panel surface 2 of PDP2
The visible light emitted simultaneously with the near-infrared light from No. 1 is hardly absorbed by the near-infrared light absorbing composition contained in the display front plate 1. Therefore, even if devices that operate with near-infrared light are placed around the PDP 2 shown in FIG. 2, the near-infrared light emitted from the panel surface 21 of the PDP 2 may cause the devices to malfunction. This can be effectively prevented, and an image or the like projected on the panel surface 21 can be watched without any trouble.

Electromagnetic waves are emitted from the panel surface 21 of the PDP 2, and such electromagnetic waves are effectively shielded by the shield mesh 13 shown in FIG.
There is no exposure to such electromagnetic waves while watching the PDP 2. Further, since the shield mesh 13 has the same conductivity as that of metal, static electricity is hardly charged on the display front panel 1 and dust and the like are prevented from adhering to the display front panel 1 due to the static electricity. Further, when the shield mesh 13 is mainly composed of plastic fibers, the weight of the display front panel 1 can be reduced. Moreover, since the shield mesh 13 is rich in flexibility, there is an advantage that the shield mesh 13 can be easily bonded even when the display front plate 1 has an uneven shape.

External light (mainly natural light or light from an electric light) entering the panel surface 21 from the display front plate 1 side.
When the light is incident on the antireflection film 15 of the display front panel 1, reflection is prevented by the action of the multilayers having different refractive indices forming the antireflection film 15, so that even if the surroundings of the PDP 2 are bright, external light This prevents the image and the like on the panel surface 21 from becoming difficult to see due to the reflection. At this time, a very small part of the external light passes through the anti-reflection film 15, and the reflection of the transmitted light is reduced by the reflection reducing film 12. The difficulty of seeing is further prevented.

<Heat Absorbing Coating Agent> Near-infrared light and infrared light are heat rays, and the near-infrared light-absorbing composition or near-infrared light absorbing agent of the present invention is required to have heat-ray absorbing properties. It is also suitable for application to members. Hereinafter, as an example of such an application,
The heat ray absorbing coating agent, the heat ray absorbing composite, the heat ray absorbing pressure-sensitive adhesive and the like will be described. As the heat-ray-absorbing coating agent, one obtained by dissolving or dispersing the near-infrared light absorbing composition of the present invention in an appropriate solvent, that is, the above-mentioned near-infrared light absorbing agent (liquid composition) is useful. If the thin film formed by evaporating the solvent is optically transparent, the heat ray absorbing coating agent itself may be transparent, translucent or opaque.

Further, in order to increase the solubility or dispersibility of the near-infrared light absorbing composition of the present invention in a solvent, or to improve the flatness or the like of a surface coated with a heat ray absorbing coating agent, A solubilizer or the like may be added to the near-infrared light absorber as an additive. As such additives, for example, various surfactants as a leveling agent and an antifoaming agent are preferably used. The content ratio of the component (A) and / or the component (B) in the heat-ray-absorbing coating agent varies depending on the type of the liquid medium used and the use or purpose of the heat-ray-absorbing coating agent.
From the viewpoint of the viscosity after preparation, usually 0.1 to 1900 parts by mass, preferably 1 to 9 parts by mass, per 100 parts by mass of the liquid medium.
The amount is preferably adjusted to be 00 parts by mass, particularly preferably 5 to 400 parts by mass.

<Heat Absorbing Composite> As the heat absorbing composite, a near-infrared light-absorbing composition using the near-infrared light-absorbing composition of the present invention on one surface of a light-transmitting substrate is used. A layer provided with a layer is useful, and another substrate having a light-transmitting property may be bonded to one surface of the near-infrared light absorbing layer. The material constituting the substrate is not particularly limited as long as it has visible light transmittance, and is appropriately selected according to the use of the heat ray absorbing composite. From the viewpoint of chemical properties, durability, etc., glass materials such as inorganic glass or organic glass, or, for example, a plastic material such as polycarbonate, acrylonitrile-styrene copolymer, polymethyl methacrylate, vinyl chloride resin, polystyrene, polyester, etc. It is preferred to use. Further, the substrates may be made of the same type of material, or may be made of different materials. Further, it is preferable that the surface of the base material that is not in contact with the near-infrared light absorbing layer is cured, from the viewpoint of preventing damage to the surface and durability. Further, the substrate may be further provided with a layer made of another translucent material.

As the near-infrared light absorbing layer, the above-mentioned heat ray absorbing coating agent is applied to one or both surfaces of a light-transmitting film or sheet material or a light-transmitting plate material, and a solvent is applied. Is preferably used. Here, as the light-transmitting film-shaped or sheet-shaped material or the light-transmitting plate used, a glass or plastic material that forms the base material can be used. Further, as the near-infrared light absorbing layer, the above-mentioned resin composition containing the near-infrared light absorbing composition of the present invention is preferably used. As the resin in this case, a resin having excellent translucency is preferable, and specifically, a vinyl chloride resin, an acrylic resin, a polycarbonate resin, a polyester resin, a polyurethane resin, a polyvinyl butyral resin, ethylene -Vinyl acetate copolymers and partially saponified products thereof. These resins are used alone or in combination of two or more, from the viewpoint of adhesion to glass and plastic materials,
Polyvinyl butyral, an ethylene-vinyl acetate copolymer or a partially saponified product of the copolymer is particularly preferred. In addition, an acrylic resin is preferable from the viewpoints of visible light transmittance and moldability.

The near-infrared light absorbing layer made of a resin composition containing these resins includes, as other components, various plasticizers having compatibility with the resin component, and benzotriazole-based, benzophenone-based or salicylic acid-based ultraviolet rays. An absorbent, other antioxidants, stabilizers and the like may be contained. Means for mixing and preparing the components for forming the near-infrared light absorbing layer include a method of mixing with a mixer such as a Henschel mixer, a method of kneading and mixing with a roll kneader, or a kneading extruder. Can be used. Further, means for dispersing each component in an appropriate organic solvent and removing the organic solvent from the dispersion can be used. Further, as a means for producing a resin molded body for the near infrared light absorbing layer, a melt extrusion molding method, a calendar molding method, a press molding method, or the like, which is a molding method of a thermoplastic resin, can be used. Further, as means for bonding the near-infrared light absorbing layer to the substrate,
A method of bonding by pressurization or decompression, such as a press method, a multi-roll method, or a decompression method, a method of bonding by heating using an autoclave or the like, or a combination thereof can be used. When the above-mentioned polyvinyl butyral, ethylene-vinyl acetate copolymer or a partially saponified product thereof is used as the resin, the heat-ray-absorbing composite in which the near-infrared light absorbing layer and the base material are bonded with sufficient strength is obtained. can get.

The near-infrared light absorbing layer thus formed has a thickness of 0.1 to 10 mm, particularly 0.3 to 5 mm.
It is preferable that The thickness of the near infrared light absorbing layer is 0.1
If it is less than mm, it tends to be difficult to obtain a near-infrared light-absorbing layer having sufficiently high near-infrared light absorption, and the heat-ray absorbing composite obtained has insufficient heat-ray absorption. Tend to be. On the other hand, if the thickness of the near-infrared light absorbing layer exceeds 10 mm, it tends to be difficult to obtain a near-infrared light absorbing layer having high visible light transmittance, Visible light transmittance tends to be low. Note that a reflection reducing layer or an antireflection layer may be provided on at least one surface of the substrate of the heat ray absorbing composite and the near infrared light absorbing layer. As this reflection reduction layer or antireflection layer,
It can be formed by various known methods such as vacuum deposition, ion plating, and sputtering using a known material such as an inorganic oxide and an inorganic halide. Also, if necessary, a visible light absorber that absorbs visible light of a specific wavelength, for example, a wavelength of 500 nm to 600 n
A metal ion-containing component including a cobalt ion that selectively absorbs m and other additives may be mixed in the resin composition.

<Heat-ray-absorbing pressure-sensitive adhesive> As the heat-ray-absorbing pressure-sensitive adhesive, those containing a resin having tackiness and the near-infrared light-absorbing composition of the present invention are useful. As the resin having adhesiveness, an acrylic resin having adhesiveness can be preferably used, and this is obtained by polymerizing a monomer composition containing an acrylic resin monomer constituting an adhesive component. can get. As such an acrylic resin monomer, the alkyl group has 4 to 12 carbon atoms, and the glass transition point of the homopolymer is −70 ° C. to −30 ° C.
Can be suitably used, and specific examples thereof include n-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, and decyl acrylate.

[0103] In addition to the acrylic resin monomer used as the above-mentioned adhesive component, a monomer constituting an aggregating component and a monomer for obtaining an acrylic resin having adhesiveness may be used. It is desirable to include a monomer constituting the modifying component. As a monomer having this aggregation component,
What can be copolymerized with an acrylic resin monomer used as an adhesive component, and has an effect of increasing the glass transition point of the obtained copolymer is used, specifically,
Examples thereof include alkyl acrylates having lower alkyl groups having 1 to 3 carbon atoms, alkyl methacrylates, vinyl acetate, vinylidene chloride, acrylonitrile, and styrene. Further, as the monomer used as the modifying component, a monomer that can be copolymerized with the acrylic resin monomer used as the adhesive component and has a functional group is used. Carboxyl group-containing compounds such as acid, methacrylic acid, maleic acid and maleic acid monoester, hydroxyl group-containing compounds such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, acrylamide, methacrylamide, Nt
acid amide compounds such as tert-butylacrylamide, N-octylacrylamide, glycidyl acrylate,
Examples include glycidyl group-containing monomers such as glycidyl methacrylate.

The proportion of each monomer used in the above-mentioned monomer composition varies depending on the kind of the monomer used, the purpose of use of the obtained acrylic resin composition, and the like. 30-9 resin monomer
5% by mass, 5 to 50 monomers used as an aggregating component
% By mass, the monomer used as the modifying component is 0.1 to 1
0% by mass. As a method for polymerizing the monomer composition, a solution polymerization method and an emulsion polymerization method can be used. Examples of the catalyst used in these polymerization treatments include peroxides such as benzoyl peroxide, azobisisobutylnitrile, ammonium persulfate, and potassium persulfate. When performing the polymerization treatment of the monomer resin composition by a solution polymerization method, various organic solvents can be used as a polymerization solvent, for example, esters such as ethyl acetate, aromatic hydrocarbons, ketones and the like. Is mentioned. When the monomer composition is polymerized by an emulsion polymerization method, various known emulsifiers used in ordinary emulsion polymerization can be used.

By subjecting the monomer composition to a polymerization treatment as described above, an acrylic resin having tackiness can be obtained in the form of a polymer solution or latex. The heat-ray-absorbing pressure-sensitive adhesive can be obtained by mixing the near-infrared light-absorbing composition of the present invention with the polymer solution or latex thus obtained, and, if necessary, a visible light having a specific wavelength. Visible light absorber which absorbs light, for example, wavelength 50
You may mix the metal ion containing component containing a cobalt ion which selectively absorbs 0 nm-600 nm, etc., and other additives. Here, the content ratio of the component (A) and / or the component (B) in the heat ray-absorbing pressure-sensitive adhesive is preferably as large as possible within a range that does not impair the translucency and the tackiness of the acrylic resin having tackiness. Desirably, 0.1 to 4 parts by mass per 100 parts by mass of the acrylic resin having tackiness.
It is suitably adjusted to be in the range of 00 parts by mass, preferably 0.3 to 200 parts by mass, more preferably 1 to 100 parts by mass.

The heat ray-absorbing coating agent, heat ray-absorbing composite and heat ray-absorbing pressure-sensitive adhesive described above are preferably applied to a light-transmitting member or the like that requires shielding of heat rays. It is suitable to be applied to members for obtaining lighting and a view, such as window materials of houses and other buildings, windows of vehicles such as automobiles and trains, and windows of vehicles such as aircraft and ships. The window material to which the heat ray-absorbing coating agent, the heat ray-absorbing composite and the heat ray-absorbing pressure-sensitive adhesive of the present invention are applied, as compared with the case where a light-shielding member that absorbs visible light to obtain heat ray-shielding properties is used. Since it has excellent visible light transmittance while having the same or better heat ray absorption, it tends to be excellent in visibility of the scenery outside the window and easy to obtain a sense of openness. In addition, it is possible to obtain a translucent member which is excellent in thermal and chemical stability and environmental resistance and hardly deteriorates.

As another application, there is an agricultural covering material for constructing a greenhouse facility for covering a plant cultivation atmosphere. Although the purpose of the greenhouse facility is to keep the inside warm, there is a possibility that the inside temperature may rise more than necessary due to heat rays from the outside in summer. According to the coating material to which the heat ray absorbing coating agent, the heat ray absorbing composite and the heat ray absorbing pressure-sensitive adhesive of the present invention are applied, such an excessive rise in temperature is effectively suppressed, and the period of use of the greenhouse facility is extended. It is possible to improve the operation rate. In addition, since it has excellent visible light transmittance, the visibility of the inside from the outside of the greenhouse is also improved.
Further, it is possible to obtain a coating material which is excellent in thermal and chemical stability and environmental resistance and is hardly deteriorated.

[0108]

EXAMPLES Hereinafter, specific examples according to the present invention will be described, but the present invention is not limited thereto.

<Example 1> (1) Production of phosphonate compound: A stirrer, a thermometer, a condenser connected with a water scrubber and a dropping funnel were attached to a four-necked flask. 275 g (2.0 mol) of phosphorus trichloride and 200 g of hexane as a solvent were charged and heated to 50 ° C. Next, 1-methoxy-2-propanol 5 was added to this solution.
40 g (6.0 mol) were added to the solution at a temperature of 50-70.
It was added over a period of 2 hours while maintaining the temperature. In the above,
Hydrogen chloride generated when 1-methoxy-2-propanol was added was introduced into a water scrubber and collected. 1-
After the addition of methoxy-2-propanol was completed, the inside of the four-necked flask was heated at 60 ° C. under a reduced pressure of 500 mmHg for 1 hour.
The remaining hydrogen chloride was removed by suction for a period of time. Then, after replacing the condenser attached to the four-necked flask with a distillation apparatus, hexane in the reaction solution and 1-methoxy-2-chloropropane as a reaction by-product were removed by the distillation apparatus, and further, distillation under reduced pressure was performed. Then, by collecting the fraction at 119.0 to 125.0 ° C. at 3 mmHg, 398 g of a liquid material was obtained. The liquid was analyzed by gas chromatography to find that bis (2-methoxy-1-methylethyl)
The purity of the hydrogen phosphonate (calculated area ratio of the chart) was 96.3%.

(2) Production of phosphate compound: A four-necked flask was equipped with a stirrer, a thermometer, a condenser connected to a 5% aqueous sodium hydroxide scrubber, and a dip tube for introducing chlorine gas. In a flask, 226 g of the obtained liquid substance (bis (2-methoxy-
(1.0 mol as 1-methylethyl) hydrogenphosphonate) and cooled to 10 ° C. Then
Chlorine gas was blown into the bis (2-methoxy-1-methylethyl) hydrogen phosphonate while maintaining the temperature at 10 to 20 ° C., until the solution turned slightly yellow. Then, the inside of the four-necked flask is 15 mmHg
By performing suction treatment at 25 ° C. under reduced pressure to remove excess chlorine gas and hydrogen chloride as a reaction by-product,
263 g of a liquid was obtained. When this liquid was analyzed by gas chromatography, bis (2-methoxy-1
The purity of (-methylethyl) phosphorochloridate (calculated area ratio of the chart) was 92.4%. In addition, the chlorine concentration of the liquid material was measured according to the “analytical chemistry experiment method” (published by Kagaku Dojin Co., Ltd.) according to the “method for quantifying chloride ions using a silver nitrate standard solution”. %Met. 90 g of water in the obtained liquid
(5.0 mol), the temperature of the solution was gradually increased, and bis (2-methoxy-1) was added at 40 ° C. for 2 hours.
-Methylethyl) phosphorochloridate was hydrolyzed. Then, after replacing the condenser attached to the four-necked flask with a distillation apparatus, water was removed from the reaction solution by the distillation apparatus to obtain 234 g of a reaction product.

The obtained reaction product was subjected to spectroscopic analysis by infrared absorption spectrum.
m and the phosphate compound represented by the formula (17) -n (the second phosphate compound). In addition, about the obtained reaction product, an autotitrator COMTITE-101 manufactured by Hiranuma Sangyo Co., Ltd.
The neutralization titration of the reaction product is carried out by using the above. From the obtained titration amounts at the first inflection point and the second inflection point, the phosphoric acid represented by the formulas (17) -m and (17) -n When the content ratio of the ester compound was calculated, it was 3.8% by weight and 9% by weight, respectively.
It was 1.6% by weight (hereinafter, this mixture of phosphate ester compounds is referred to as "MPP").

(3) Preparation of liquid composition: MPP obtained in the above (2) and diphenyl phosphate represented by the formula (16) -b as the first phosphate compound (Tokyo Kasei Kogyo Co., Ltd. 0.20 g of a mixture thereof with methyl ethyl ketone (hereinafter referred to as “MEHP”).
K ") and an equivalent amount of copper acetate monohydrate (an amount in which the hydroxyl group of the phosphate compound is 2 mol per mol of copper). I got

(4) Measurement of Absorbance: In the above (3), DIPHP with respect to the total amount of MPP and DIPHP
About the liquid composition obtained by changing the content ratio of variously,
Immediately after the preparation of the liquid composition and after 6 days, the spectral absorbance was measured using a U-4000 spectrophotometer manufactured by Hitachi, Ltd. From the obtained spectral absorption curve, a wavelength of 700 nm
And the absorbance for light having a wavelength of 800 nm. FIG.
Is a graph showing the value of the ratio of (absorbance at a wavelength of 700 nm) / (absorbance at a wavelength of 800 nm) with respect to the content (% by weight) of DIPHP (here, only results after 6 days have been shown). In FIG. 3, the smaller the value on the vertical axis, the better the selective absorption of near-infrared light and the selective transmittance of visible light in the boundary wavelength region. FIG. 10 shows that the content (% by weight) of DIPHP is
(Absorbance at a wavelength of 800 nm-Absorbance at a wavelength of 700 nm)
4 shows a graph representing the change in the. FIG. 10 shows that the larger the value on the vertical axis, the better the selective absorption of near-infrared light and the selective transmittance of visible light in the boundary wavelength region.

FIG. 3 shows that as the content ratio of DIPHP increases, the ratio value on the vertical axis gradually decreases, and
Was contained at about 75% by weight, the value of the ratio showed the minimum value and was about 55%. In addition, the content of DIPHP is 9
If it exceeds 0%, suspension will occur in the liquid composition after 6 days, making it difficult to measure the absorbance, and the value of the ratio on the vertical axis will be almost 100% (neither near infrared light nor visible light is transmitted. Is gone.) Immediately before suspension occurs (DIPHP
(Content of about 90%), the value of the ratio on the vertical axis was smaller than when DIPHP was not contained. From this result, the liquid composition of the near-infrared light-absorbing composition containing DIPHP (first phosphate ester compound) and MPP (second phosphate ester compound) shows a selective absorption of near-infrared light. In particular, it has excellent properties, selective transmittance of visible light, and storage stability. In particular, when the content ratio of DIPHP and MPP is 10:90 to 90:10 by weight, more excellent effects are exhibited. It will be understood that This tendency was almost the same in FIG.

<Example 2> Instead of MPP, a second phosphate compound represented by the formula (19) -s and the formula (19)
-T phosphate compound (JP-A-6-11)
No. 8228; hereinafter, referred to as “PMOE”), to obtain a pale blue transparent liquid composition in the same manner as in Example 1 above. In addition, when the content ratio of the phosphate compound represented by Formula (19) -s and Formula (19) -t in PMOE used here was analyzed in the same manner as in Example 1, each was 37.5% by weight. % And 62.5% by weight. The spectral absorbance of this liquid composition was measured in the same manner as in Example 1 above. The results are shown in FIGS.

FIG. 4 shows that as the content ratio of DIPHP increases, the ratio value on the vertical axis gradually decreases, and
Was contained at about 80% by weight, the value of the ratio showed the minimum value and was about 53%. In addition, the content of DIPHP is 9
When it exceeds 0%, similar to the liquid composition of Example 1 described above,
After 6 days, the liquid composition became suspended.
From these results, the liquid composition of the near-infrared light-absorbing composition containing DIPHP (first phosphate ester compound) and PMOE (second phosphate ester compound) showed a selective absorption of near-infrared light. Excellent permeability and selective permeability of visible light,
In particular, it is understood that when the content ratio of DIPHP and PMOE is 10:90 to 88:12 by weight, more excellent effects are achieved. This tendency was almost the same in FIG.

Example 3 (1) Preparation of acetyloxyalkyl (C3) alcohol: 120 g of acetic acid and 8.2 g of anhydrous sodium acetate
The mixture was heated and maintained at 850 ° C., and 118 g of propylene oxide was added dropwise to the mixture over 3.5 hours. Thereafter, the mixture was kept at a temperature of 85 ° C. for 7 hours to react acetic acid and anhydrous sodium acetate with propylene oxide. After cooling the obtained reaction product,
The precipitated sodium acetate was separated by filtration, and the obtained filtrate was subjected to decompression distillation to obtain an acetyloxyalkyl (carbon number 3) alcohol 1 as a fraction at 5 mmHg and 68 to 70 ° C.
95 g were obtained.

(2) Preparation of acetyloxyalkyl (C3) phosphate: mixture of acetyloxyalkyl (C3) alcohol 14 obtained in (1) above
To a solution of 0 g in 250 ml of dimethoxyethane, 52.2 g of phosphorus pentoxide was added over 1 hour. Then
By stirring this solution at 60 ° C. for 5 hours, an acetyloxyalkyl (C3) alcohol was reacted with phosphorus pentoxide. Thereafter, dimethoxyethane in the obtained reaction product liquid was decompressed and distilled off to obtain 173 g of a colorless viscous liquid as a reaction product. As a result of the above reaction, mono [1- (acetyloxymethyl) ethyl] phosphate represented by the formula (18) -a and bis [1- (acetyloxymethyl) ethyl] represented by the formula (18) -b
Phosphate, mono [2- represented by formula (18) -c
(Acetyloxy) propyl] phosphate, of the formula (1
8) bis [2- (acetyloxy) propyl] phosphate represented by -d and [1] represented by the formula (18) -e
-(Acetyloxymethyl) ethyl] [2- (acetyloxy) propyl] phosphate mixture (hereinafter referred to as “A
PP ").

(3) Analysis of the mixture of phosphate ester compounds by gas chromatography: 15 mg of the above APP
Was collected in a 10 ml test tube with a screw cap, and BSA (N-O
-Bistrimethylsilylacetamide) 2.5 ml, T
0.5 ml of a mixed solution of 10 ml of MSC (trimethylchlorosilane) and 10 ml of pyridine was added, shaken well, and 1-2 μl of the supernatant was injected into the following gas chromatography to obtain a chromatogram. As a result of analysis by gas chromatography, two peaks corresponding to the phosphoric acid monoester and three peaks corresponding to the phosphoric acid diester were obtained. The retention times of these peaks are 6.26 minutes and 6.38 minutes for the two types of phosphoric acid monoesters, respectively, and 11.26 minutes, 11.46 minutes, and 11.1 minutes for the three types of phosphate diesters. It was 56 minutes. Based on this analysis result, A
The content ratio of the phosphate compound represented by the formula (18) -a and the formula (18) -b in PP was determined to be 33.2% by weight and 49.6% by weight, respectively. (Conditions for gas chromatography): ・ Equipment: Gas chromatography G300 manufactured by Hitachi, Ltd.
0 ・ Column: TC-17 0.25 × 30 m ・ Carrier: Helium 0.66 ml / min, split ratio 1:75 ・ Injection: 290 ° C. ・ Detector: FID 3000c ・ Column temperature: 170 ° C.-3.5 min. 10 ° C / min-temperature rise, 220 ° C-10 minutes hold

(4) Preparation of Liquid Composition and Measurement of Spectral Absorbance: A light blue transparent material was prepared in the same manner as in Example 1 except that APP was used as the second phosphate compound instead of MPP. A liquid composition was obtained. The spectral absorbance of this liquid composition was measured in the same manner as in Example 1 above. The results are shown in FIGS.

FIG. 5 shows that as the content ratio of DIPHP increases, the value of the ratio on the vertical axis gradually decreases, and
Was contained at about 75% by weight, the value of the ratio showed the minimum value and was about 52%. In addition, the content of DIPHP is 8
If it exceeds 5%, suspension has occurred in the liquid composition after 6 days. From this result, the liquid composition of the near-infrared light-absorbing composition containing DIPHP (first phosphate ester compound) and APP (second phosphate ester compound) shows a selective absorption of near-infrared light. It is excellent in the properties and the selective transmittance of visible light, and in particular, it is understood that when the content ratio of DIPHP and APP is 10:90 to 85:15 by weight, more excellent effects are exhibited. Is done. This trend is
The same applies to FIG.

Example 4 Instead of MPP, di-n-butyl phosphate represented by the formula (19) -q (manufactured by Tokyo Chemical Industry Co., Ltd .; hereinafter referred to as "D
Inventive Example 1 except that “InBP” was used.
In the same manner as in the above, a light blue transparent liquid composition was obtained. The spectral absorbance of this liquid composition was measured in the same manner as in Example 1 above. The results are shown in FIG. 6 and FIG.

From FIG. 6, it was difficult to measure the absorbance when only DInBP was used, but the content of DIPHP was 2%.
As it increased above 5% by weight, the value of the ratio on the vertical axis gradually decreased, and when DIPHP was included at about 75% by weight, the value of the ratio showed the minimum value and was about 58%. On the other hand, when the content of DIPHP exceeded about 90%, the liquid composition after 6 days gradually became suspended.
From these results, the liquid composition of the near-infrared light-absorbing composition containing DIPHP (the first phosphate compound) and DInBP (the second phosphate compound) shows a selective absorption of near-infrared light. It is understood that it is excellent in the property and the selective transmittance of visible light, and in particular, when the content ratio of DIPHP and MPP is 30:70 to 85:15 by weight, more excellent effects are achieved. Is done. This tendency was almost the same in FIG.

Example 5 Di (2-ethylhexyl) phosphate represented by the formula (19) -r as a second phosphate compound instead of MPP (manufactured by Tokyo Chemical Industry Co., Ltd .;
Hereinafter referred to as “DI2EHP”)
A light blue transparent liquid composition was obtained in the same manner as in Example 1 above. The spectral absorbance of this liquid composition was measured in the same manner as in Example 1 above. The results are shown in FIG. 7 and FIG.
It is shown in FIG.

FIG. 7 shows that as the content ratio of DIPHP increases, the value of the ratio on the vertical axis gradually decreases.
Was contained at about 75% by weight, the ratio value showed a minimum value and was about 57%. In addition, the content of DIPHP is 8
When it exceeded 5%, the liquid composition after 6 days gradually became suspended. Immediately before suspension occurs (DI
(PHP content is about 85%), the value of the ratio on the vertical axis was smaller than that in the case where DIPHP was not contained. From these results, DIPHP (first phosphate compound) and DI2EHP (second phosphate compound)
The liquid composition of the near-infrared light-absorbing composition containing is excellent in the selective absorption of near-infrared light and the selective transmittance of visible light, and particularly, the content ratio of DIPHP and DI2EHP is
It is understood that, when the weight ratio is 10:90 to 85:15, a more excellent effect is achieved. This tendency is illustrated in FIG.
4 was almost the same.

<Comparative Example 1> Instead of MPP, formula (16)
-A phenyl phosphate (Tokyo Kasei Kogyo Co., Ltd.)
A light blue transparent liquid composition was obtained in the same manner as in Example 1 above, except that “MOPHP” was used. The spectral absorbance of this liquid composition was measured in the same manner as in Example 1 above. FIG. 8 shows the results.

FIG. 8 shows that as the content of DIPHP increases, the value of the ratio on the vertical axis gradually decreases, but the minimum value of the ratio is about 87% when DIPHP is contained at about 70% by weight. Stayed. From these results, the liquid composition of the near-infrared light-absorbing composition containing DIPHP and MOPHP, that is, only the first phosphoric acid ester compound of the present invention, shows the near-infrared light absorbing composition of the present invention. It is understood that the composition does not have sufficient selective absorption of near-infrared light and selective permeability of visible light as compared with the examples using the composition.

Comparative Example 2 A pale blue transparent liquid composition was obtained in the same manner as in Example 1 except that a mixture of the above PMOE and the above DI2EHP was used as the phosphate compound. The spectral absorbance of this liquid composition was measured in the same manner as in Example 1 above. FIG. 9 shows the results. FIG. 9 shows DI in the liquid composition.
(Wavelength 700 with respect to the content ratio (wt%) of 2EHP
It is a graph which shows the value of the ratio of (absorbance of nm) / (absorbance of wavelength 800nm).

It is apparent from FIG. 9 that the ratio value on the vertical axis gradually increases as the content ratio of DI2EHP increases. In other words, the best result was obtained when only PMOE was included, but the minimum value of the ratio of the vertical axis at this time was about 60%. From this result, DI2
EHP and PMOE, that is, the liquid composition of the near-infrared light absorbing composition containing only the second phosphate compound of the present invention uses the near-infrared light absorbing composition of the present invention. It can be understood that they do not show sufficient selective absorption of near-infrared light and selective transmittance of visible light as compared with the Examples.

[0130]

As described above, according to the present invention, the wavelength range (approximately 750 nm) which falls on the boundary between visible light and near-infrared light.
m; hereinafter, referred to as “boundary wavelength region”), the absorbance for light in the near infrared region and the transmittance for light in the visible region are increased, and the selective absorption of near infrared light and visible light It is possible to obtain a near-infrared light-absorbing composition and a near-infrared light-absorbing agent which are sufficiently excellent in the selective transmittance of light and also excellent in storage stability.

[Brief description of the drawings]

FIG. 1 is a structural view showing an example of a display front plate using the near-infrared light absorbing composition of the present invention, and FIG.
Is a sectional view, and FIG. 1B is an exploded perspective view showing a laminated structure.

FIG. 2 is a perspective view showing a use state of the display front panel shown in FIG. 1;

FIG. 3 is a graph showing a value of a ratio of (absorbance at a wavelength of 700 nm) / (absorbance at a wavelength of 800 nm) with respect to the content (% by weight) of DIPHP in the liquid composition of Example 1.

FIG. 4 is a graph showing the value of the ratio of (absorbance at a wavelength of 700 nm) / (absorbance at a wavelength of 800 nm) with respect to the content (% by weight) of DIPHP in the liquid composition of Example 2.

FIG. 5 is a graph showing a value of a ratio of (absorbance at a wavelength of 700 nm) / (absorbance at a wavelength of 800 nm) with respect to the content (% by weight) of DIPHP in the liquid composition of Example 3.

FIG. 6 is a graph showing a value of a ratio of (absorbance at a wavelength of 700 nm) / (absorbance at a wavelength of 800 nm) with respect to the content (% by weight) of DIPHP in the liquid composition of Example 4.

FIG. 7 is a graph showing a value of a ratio of (absorbance at a wavelength of 700 nm) / (absorbance at a wavelength of 800 nm) with respect to the content (% by weight) of DIPHP in the liquid composition of Example 5.

FIG. 8 is a graph showing a value of a ratio of (absorbance at a wavelength of 700 nm) / (absorbance at a wavelength of 800 nm) with respect to the content (% by weight) of DIPHP in the liquid composition of Comparative Example 1.

FIG. 9 is a graph showing a value of a ratio of (absorbance at a wavelength of 700 nm) / (absorbance at a wavelength of 800 nm) to the content (% by weight) of DI2EHP in the liquid composition of Comparative Example 2.

FIG. 10 is a graph showing the value of (absorbance at a wavelength of 800 nm−absorbance at a wavelength of 700 nm) with respect to the content (% by weight) of DIPHP in the liquid composition of Example 1.

FIG. 11 is a graph showing the value of (absorbance at a wavelength of 800 nm−absorbance at a wavelength of 700 nm) with respect to the content (% by weight) of DIPHP in the liquid composition of Example 2.

FIG. 12 is a graph showing the value of (absorbance at a wavelength of 800 nm-absorbance at a wavelength of 700 nm) with respect to the content (% by weight) of DIPHP in the liquid composition of Example 3.

FIG. 13 is a graph showing the value of (absorbance at a wavelength of 800 nm-absorbance at a wavelength of 700 nm) with respect to the content (% by weight) of DIPHP in the liquid composition of Example 4.

FIG. 14 is a graph showing the value of (absorbance at a wavelength of 800 nm-absorbance at a wavelength of 700 nm) with respect to the content (% by weight) of DIPHP in the liquid composition of Example 5.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Display front plate, 2 ... PDP (display), 16 ... Near-infrared light absorption film (near-infrared light absorption layer which consists of a near-infrared light absorption composition).

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C09D 7/12 C09D 7/12 Z C09J 11/06 C09J 11/06 (72) Inventor Masuhiro Shoji Nishikicho, Iwaki-shi, Fukushima 16 Ochiai F-term in Kureha Chemical Industry Nishiki Plant Co., Ltd. FA101 FA131 FA212 FA282 GA07 GA27 HD24 JB09 KA27 KA43 LA05 LA10 MA05 NA12

Claims (6)

[Claims] 1. A near-infrared light-absorbing composition comprising the following component (A) and / or the following component (B). Component (A): a component comprising copper ion, a first phosphate compound represented by the following formula (1), and a second phosphate compound represented by the following formula (2): Component (B): A first phosphoric acid ester copper compound obtained by reacting the first phosphoric acid ester compound with a copper compound, and a second phosphoric acid obtained by reacting the second phosphoric acid ester compound with a copper compound Component consisting of an ester copper compound Wherein X ¹ represents an aryl group or an arylalkyl group, and X ² represents a group represented by the following formula (3), (4), (5), (6) or (7), or Represents an alkyl group, and j and n are each independently 1 or 2. ] [However, in the formulas (3) to (7), R ¹ represents an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ represents 1-6 carbon atoms
R ⁴ represents an alkylene group having 1 to 10 carbon atoms, R ⁵ represents a hydrogen atom or a methyl group,
Further, m is an integer of 1 to 6, k is an integer of 0 to 5, p is an integer of 2 to 6, and r is an integer of 1 to 5. ] 2. The near-infrared light absorbing composition according to claim 1, wherein the first phosphate compound has a phenyl group as X ¹ in the formula (1). 3. The near-infrared light absorbing composition according to claim 1, wherein j in the formula (1) is 1 in the first phosphate compound. 4. The first phosphate compound and / or
Alternatively, the content ratio of the first phosphoric acid ester copper compound to the second phosphoric acid ester compound and / or the second phosphoric acid ester copper compound is 10:90 to 9 by weight.
The near-infrared light absorbing composition according to any one of claims 1 to 3, wherein the composition is 0:10. 5. The second phosphoric ester compound wherein R ⁵ in the above formula (7) is a methyl group, p in the above formula (7) is 2, and the above formula (7) near infrared absorbing composition according to any one of claims 1 to 4 r is characterized by having a group X ² is a 1 in. 6. A near-infrared light absorbing agent obtained by dissolving or dispersing the near-infrared light absorbing composition according to any one of claims 1 to 5 in a solvent.