JP2000310948A - Near-infrared light-absorbing compound, method for producing the same, near-infrared light-absorbing agent and display front plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a near-infrared light which is excellent in near-infrared light absorption performance, excellent in thermal and chemical stability, and capable of improving production method, material selectivity and moldability. An external light absorbing compound is provided. SOLUTION: The near-infrared light absorbing compound of the present invention is a phosphoric acid ester copper compound obtained by reacting a phosphoric acid ester compound represented by the following formula (1) with a copper compound. . Embedded image [Wherein, R represents a group represented by the following formula (2) or the following formula (3), and n is 1 or 2. Embedded image (Wherein, R ¹ is an aryl group having 6 to 20 carbon atoms (provided that hydrogen of the aryl group is an alkyl group having 1 to 6 carbon atoms,
Or at least one may be substituted by halogen, and hydrogen of the alkyl group may be at least one substituted by halogen), R ² represents an alkyl group having 1 to 4 carbon atoms, and m represents It is an integer of 1 to 6. )]

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 compound having absorption properties for near-infrared light, a method for producing the same, and an absorption property for near-infrared light. The present invention relates to a near-infrared light absorber and a display front plate using the near-infrared light absorber.

[0002]

2. Description of the Related Art Conventional compounds having near-infrared light absorption properties are disclosed in JP-A-6-118228 and JP-A-10-108228.
-045995, JP-A-10-114848, JP-A-10-152598, JP-A-10-1
53964, JP-A-10-187055,
Examples thereof include a compound containing a phosphorus atom-containing compound and an ionic metal component containing copper ions as a main component, as described in JP-A-10-212373.

[0003]

The phosphorus atom-containing compound contained in the above-mentioned conventional near-infrared light absorbing compound has a polymerizable functional group (a group having an unsaturated double bond) in the molecule. Have. Therefore, such a phosphorus atom-containing compound and a copper salt thereof are provided as a near-infrared light absorbing compound because the polymerization reaction proceeds and gradually cures when exposed to ultraviolet light or heat is applied. Have been limited to polymerizable resin compositions. An optical member that absorbs near-infrared light is produced only by polymerizing this resin composition, and the production method and material selectivity are not sufficient.

[0004] As a method for molding such a resin composition, hot press molding of resin pellets, casting polymerization of a liquid material, and the like are widely used from the viewpoints of workability, productivity and economy. . However, the phosphorus atom-containing compound and its copper salt used in the conventional display front panel do not have sufficient heat stability as described above, and are not necessarily suitable for hot press molding. Further, at the time of casting polymerization, adhesion to the mold was difficult and mold release was difficult, and remolding by heat was difficult.

[0005] In view of the above problems, the present invention is excellent in near-infrared light absorption performance, is excellent in thermal and chemical stability as compared with the related art, and has a manufacturing method and material selection. It is an object of the present invention to provide a near-infrared light-absorbing compound capable of improving the properties and moldability, a method for producing the same, and a near-infrared light absorbing agent. Further, the present invention, by using such a near infrared light absorber, near infrared light absorption performance,
An object of the present invention is to provide a display front panel having excellent thermal and chemical stability.

[0006]

Means for Solving the Problems In order to achieve the above object, the present invention has conducted intensive studies on the spectroscopic properties and physical properties of a phosphate compound and a copper compound thereof. The present inventors have found a near-infrared light-absorbing compound which is excellent in chemical stability and can improve the selectivity of the production method and the material and the processability of the molding, and have reached the present invention. That is, the near infrared light absorbing compound of the present invention,
It is a phosphate copper compound obtained by reacting a phosphate compound represented by the following formula (1) with a copper compound.

[0007]

Embedded image [In the formula (1), R independently represents a group represented by the following formula (2) or the following formula (3), and n is 1 or 2.

[0008]

Embedded image (In the formulas (2) and (3), R ¹ independently has 6 carbon atoms.
To 20 aryl groups (provided that the hydrogen of the aryl group may be substituted with at least one alkyl group having 1 to 6 carbon atoms or halogen, and the hydrogen of the alkyl group may be substituted with at least one hydrogen atom. R ² is independently an alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 6. )]

The near-infrared light-absorbing compound of the present invention comprises
It is a phosphate copper compound obtained by reacting a phosphate compound represented by the following formula (4) with a copper compound.

[0010]

Embedded image [In the formula (4), R independently represents a group represented by the following formula (5) or the following formula (6), and n is 1 or 2.

[0011]

Embedded image (In the formulas (5) and (6), R ³ and R ^{4 each} independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group (provided that hydrogen of the aryl group is an alkyl group having 1 to 6 carbon atoms.) Group, or may be substituted by at least one halogen.
And at least one hydrogen of the alkyl group may be substituted by halogen). )]

Further, the near-infrared light absorbing compound of the present invention is a phosphoric acid ester copper compound obtained by reacting a phosphoric acid ester compound represented by the following formula (7) with a copper compound. I do.

[0013]

Embedded image [In the formula (7), R represents a group represented by the following formula (8), and n is 1 or 2.

[0014]

Embedded image (In the formula (8), R ⁵ represents an alkyl group having 1 to 20 carbon atoms or an aryl group (provided that at least one hydrogen of the aryl group is substituted by an alkyl group having 1 to 6 carbon atoms or halogen) And R ⁶ , R ⁷ , and R ^{8 each} independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms (provided that the hydrogen of the alkyl group may be substituted with at least one hydrogen atom). , R ⁶ , R ⁷ , and R ⁸ except for the case where all are hydrogen), and m is an integer of 1 to ^6. )]

According to the near-infrared light-absorbing compound of the present invention, the phosphate group of the phosphate compound binds to the copper ion through coordination bond and / or ionic bond, and this copper ion is Are dissolved or dispersed in the composition, and near-infrared light is selectively absorbed by the electronic transition between the d orbitals of the copper ions. Therefore, near-infrared light absorption performance equal to or higher than the conventional one is achieved.
Further, the phosphate ester compounds represented by the above formulas (1), (4) and (7) and the reaction product of the compound and the copper compound have an unsaturated double bond in the molecular structure. Without, it is hard to be cured by ultraviolet light or heat, so even if it is not polymerized with a resin and stabilized, for example, it is possible to obtain a liquid near-infrared light absorber dissolved or dispersed in a solvent. . Furthermore, the phosphate compound represented by the above formula (1), the formula (4) and the formula (7) and the reaction product of the compound and the copper compound have an unsaturated double bond in the molecular structure. It has no mold release and has good releasability when mixed with a resin and polymerized in a mold. Further, even when a thermal load is applied (for example, molding by hot pressing), there is almost no deterioration in spectral characteristics. Furthermore, the molded article has thermoplasticity,
In addition, because of its high thermal stability, it is easy to re-form by heat even after polymerization.

The method for producing a near-infrared light-absorbing compound of the present invention comprises the above formulas (1), (4) and (7).
And reacting at least one of the phosphoric acid ester compounds represented by the formula (1) with a copper compound to obtain a phosphoric acid ester copper compound. According to such a method, it has excellent near-infrared light absorption, is thermally and chemically stable, and can be used without being mixed with a resin. Near-infrared light absorption made of a copper phosphate ester compound that is easy to mold and has almost no deterioration in spectral characteristics even when a thermal load is applied (for example, molding by hot pressing). A compound is obtained.

In the above step, it is preferable that the phosphoric acid ester compound and the copper compound are reacted in an organic solvent to remove an acid component generated by the reaction and the organic solvent. In this manner, in the reaction between the phosphate compound and the copper compound, the acid component, which is an anion released from the copper compound, is removed, and near-infrared light caused when such an acid component is present is generated. A decrease in the moisture resistance and thermal stability of the absorbing compound and the near-infrared light absorber containing the compound are prevented.

The near-infrared light absorbing agent of the present invention is characterized by containing the above-mentioned near-infrared light absorbing compound of the present invention. Such a near-infrared light absorbing agent of the present invention is excellent in near-infrared light absorbing property, is thermally and chemically stable, and can be used without being mixed with a resin. It has excellent moldability and is easy to reshape. Even if a thermal load is applied (for example, shaping by hot pressing), there is almost no deterioration in spectral characteristics.

Further, it is more preferable that the resin composition is formed of a resin composition containing a near-infrared light absorbing compound in a resin. By using the resin composition as described above, it is possible to easily obtain various shapes of near-infrared light absorbers and those using the near-infrared light absorber according to the intended use. Here, as the resin, an acrylic resin which is excellent in terms of visible light transmittance, weather resistance, moldability and the like can be preferably used.

Further, the display front plate of the present invention is characterized by comprising a near-infrared light absorbing layer containing the above-mentioned near-infrared light absorbing agent of the present invention. According to such a display front plate, since it has a near-infrared light absorption layer capable of improving near-infrared light absorption, visible light transmission, heat resistance and chemical stability and moldability, It is possible to provide a display front panel having excellent performance.

[0021] The display is a plasma display.
Preferably, it is a display panel. plasma·
The display panel has a high generation intensity of near-infrared light among electronic displays, and there is a high possibility that a device such as an infrared remote control placed around the plasma display panel malfunctions. By applying the display front panel to the plasma display panel, such a malfunction is effectively prevented. Further, the plasma display panel is a promising device as a large-sized display having a large-area screen, and the display front panel is also required to be large-sized in accordance with such a large-sized screen. The display front plate of the present invention has excellent moldability when the near-infrared light absorbing layer is formed as a resin composition, and can be formed by applying a liquid near-infrared light absorbing agent to a transparent substrate or the like. Since the infrared light absorbing layer can be formed, a display front plate corresponding to a display shape larger than before can be easily obtained.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention relate to a near-infrared light-absorbing compound, a method for producing the same, a near-infrared light absorber using the near-infrared light-absorbing compound, and a near-red light. A display front plate and the like using an external light absorber will be described. After that, another member using the near-infrared light absorbing compound of the present invention will be described.

<Near-Infrared Light-Absorptive Compound and Method for Producing the Same>
It is a phosphoric acid ester copper compound obtained by reacting a phosphoric acid ester compound represented by the above formula (4) or the above formula (7) (hereinafter referred to as “specific phosphoric acid ester compound”) with a copper compound. . Copper compound (hereinafter also referred to as copper salt)
Is for supplying copper ions, and specific examples thereof include organic acids such as copper acetate, copper formate, copper stearate, copper benzoate, copper ethyl acetoacetate, copper pyrophosphate, copper naphthenate, and copper citrate. Copper salt anhydrides and hydrates, or copper salt anhydrides and hydrates of inorganic acids such as copper hydroxide, copper chloride, copper sulfate, copper nitrate, basic copper carbonate, and the like. It is preferable to use copper acetate, and particularly preferable are copper acetate and copper benzoate. The near-infrared light absorbing compound of the present invention includes:
Metal ions other than copper ions (hereinafter “other metal ions”
That. ) May be contained. Specific examples of such other metal ions include ions of metals such as sodium, potassium, calcium, iron, manganese, magnesium, and nickel. The specific phosphate compound is produced, for example, by any one of the following first, second, and third methods.

[First Method]: The first method is a method in which an alcohol having a specific molecular structure is reacted with phosphorus pentoxide without a solvent or in an appropriate organic solvent. Here, as the alcohol having a specific molecular structure, an alcohol represented by the following formula (9) or (10) for obtaining the phosphate compound represented by the above formula (1) is used.

[0025]

Embedded image [In the formulas (9) and (10), R ¹ is independently an aryl group having 6 to 20 carbon atoms (provided that at least one hydrogen atom of the aryl group is selected from an alkyl group having 1 to 6 carbon atoms or a halogen atom) R ² may be independently an alkyl group having 1 to 4 carbon atoms, and m is 1 to 6 Is an integer. ]

Preferable specific examples of the alcohol represented by the above formula (9) include the following formula (11) or the following formula (12)
Are represented.

[0027]

Embedded image

The following formula (13) or the following formula (1) for obtaining the phosphate compound represented by the above formula (4):
The alcohol represented by 4) is used.

[0029]

Embedded image [In the formulas (13) and (14), R ³ and R ⁴ independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group (provided that
Hydrogen of the aryl group may be substituted by at least one alkyl group having 1 to 6 carbon atoms or halogen, and hydrogen of the alkyl group may be substituted by at least one halogen.). ]

Preferred specific examples of the alcohol represented by the above formula (13) include those represented by the following formula (15).

[0031]

Embedded image

Further, an alcohol represented by the following formula (16) is used for obtaining a phosphate compound represented by the above formula (7).

[0033]

Embedded image [In the formula (16), R ⁵ represents an alkyl group having 1 to 20 carbon atoms or an aryl group (provided that at least one hydrogen of the aryl group is substituted with an alkyl group having 1 to 6 carbon atoms or halogen) And R ⁶ , R ⁷ , and R ^{8 each} independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms (provided that the hydrogen of the alkyl group may be substituted with at least one hydrogen atom). , R ⁶ , R ⁷ , and R ⁸ except when all are hydrogen), and m is an integer of 1 to 6. ]

Preferred examples of the alcohol represented by the above formula (16) include those represented by the following formula (17).

[0035]

Embedded image

The alcohols represented by the above formulas (9), (10), (13), (14) and (16) are hereinafter also referred to as specific alcohols.

The organic solvent used for 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 and xylene. , Petroleum spirits and other hydrocarbon solvents, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene and other halogenated hydrocarbon solvents, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran and other ether solvents, acetone, methyl ethyl ketone, dibutyl ketone And the like ketone solvents and the like,
Of these, toluene and xylene are preferred. The reaction conditions of the specific alcohol and phosphorus pentoxide are such that the reaction temperature is 0 to 100 ° C, preferably 40 to 80 ° C, and the reaction time is 1 to 96 hours, preferably 4 to 72 hours.

In the first method, for example, a specific alcohol and phosphorus pentoxide are used in a molar ratio of 3: 1 to obtain the above formulas (1), (4) and (7). A) a phosphoric acid monoester compound having 2 hydroxyl groups (hereinafter simply referred to as “monoester”); and a phosphoric diester compound having 1 hydroxyl group (hereinafter simply referred to as “diester”). Is obtained in 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 the second method, a specific alcohol is reacted with phosphorus oxyhalide without a 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, 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, ether solvents such as dibutyl ether, 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.

Further, the above equations (10) and (14)
Alternatively, when a specific alcohol represented by the above formula (16) (where R ⁶ is a hydrogen atom) is used, the ratio of this specific alcohol to phosphorus oxyhalide and the reaction conditions are selected, and the reaction is carried out. Examples of the catalyst include Lewis acid catalysts such as titanium tetrachloride (TiCl ₄ ), magnesium chloride (MgCl ₂ ), and aluminum chloride (AlCl ₃ ). Examples of the catching agent for by-produced hydrochloric acid include amines such as triethylamine and tributylamine. , Pyridine and the like are preferably used. By using these reaction catalysts and hydrochloric acid catching agent, a mixture of a monoester and a diester can be 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 from 99: 1 to 1:99 in molar ratio. It is adjusted within a certain range.

When a specific alcohol represented by the above formula (9), the above formula (13) or the above formula (16) (where R ⁶ is an alkyl group) is used, the specific alcohol is used. By selecting the ratio with phosphorus oxyhalide and the reaction conditions and using a Lewis acid catalyst and a hydrochloric acid catching agent together, a mixture of a monoester and a diester is obtained, and the ratio is 99: 1
It is adjusted within a range of １ ： 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 thus, when a hydrochloric acid catching agent such as an amine is used, the formation of the 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 0.2 mol, preferably 0.01 to 0.05 mol, per 1 mol of phosphorus oxyhalide.

[Third Method]: In this third method, a phosphonic acid ester compound is synthesized by reacting a specific alcohol with phosphorus trihalide without 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 for the reaction between the specific alcohol and the phosphorus trihalide is an organic solvent that does not react with the phosphorus trihalide, 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, ether solvents such as dibutyl ether, among these, hexane, 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 compound, a phosphorohalolidate compound is synthesized by reacting the phosphonate compound with a halogen such as chlorine gas, and the phosphorohalolidate compound is hydrolyzed. Means to do this can be used. Here, the reaction temperature between the phosphonic acid ester compound and the halogen is preferably 0 to 40 ° C, particularly preferably 5 to 25 ° C.
It is. Before oxidizing the phosphonate ester compound, the phosphonate ester compound may be purified by distillation. In the third method, the diester can be obtained with high purity by using, for example, a specific alcohol and phosphorus trihalide in a molar ratio of 3: 1. Also, by selecting the ratio of the specific alcohol to the phosphorus trihalide and the reaction conditions, a mixture of a monoester and a diester can be obtained. It is adjusted within a certain range.

Next, the reaction between the specific phosphate compound and the copper salt is carried out by bringing them into contact with each other under appropriate conditions. Specifically, (a) a method in which a specific phosphate compound and a copper salt are mixed and reacted together,
(B) a method of reacting a specific phosphate compound with a copper salt in an appropriate organic solvent; (c) an organic solvent layer containing a specific phosphate compound in an organic solvent; A method in which a specific phosphoric acid ester compound is reacted with a copper salt by bringing into contact with a dissolved or dispersed aqueous layer, and the like. The reaction conditions of the specific phosphate compound and the copper salt are as follows:
The reaction temperature is 50 ° C, preferably 40 to 120 ° C, and the reaction time is 0.5 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, examples of the organic solvent used in the method (b) include aromatic compounds, ethers, esters, hexane, kerosene, (meth) acrylates, and aromatic vinyl compounds. .

In the reaction between a specific phosphate compound and a copper salt, an acid component as an anion is released from the copper salt. Since such an acid component can cause the moisture resistance and thermal stability of the acrylic resin composition to be reduced, it is preferable to remove the acid component as necessary. The above (a)
Alternatively, in the case of producing a phosphoric acid ester copper compound by the method of (b), after reacting a specific phosphoric acid ester compound with a copper salt, the acid component produced in the method of (b) is produced. 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 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 moves to the aqueous layer,
The generated specific copper phosphate compound migrates to the organic solvent layer, so that the acid component is removed by separating the aqueous layer and the organic solvent layer.

The specific phosphoric ester compound represented by the above formula (1), (4) or (7) has a certain degree of polar alkoxy group in its molecular structure. Good solubility or dispersibility in a medium such as a solvent and a resin. Here, in the specific phosphoric acid ester compound, the group R is an alkyl group or an aryl group to which an alkylene oxide group is bonded (a group in which hydrogen of an aryl group is substituted with an alkyl group (arylalkyl group)) or an aryl group. In which hydrogen is replaced by halogen). In addition, the number m of repeating units of the alkylene oxide group in the phosphate ester compounds represented by the above formulas (1) and (7) is an integer of 1 to 6, preferably 1 to 3. When the value of m exceeds 6, the hardness of the 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, the ability to disperse copper ions in the resin is significantly reduced.

Further, from the viewpoints of thermal stability and environmental resistance of the phosphate compound and the copper phosphate compound,
It is particularly preferable that the number m of repeating units of the alkylene oxide group is 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 in which m is 1 and a composition containing a copper phosphate ester compound is 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 have excellent environmental resistance as compared with 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. On the other hand, those having an alkylene oxide group in which m is an integer of 2 or more tend to deteriorate with time.

Further, as described above, the specific phosphate compound is a monoester wherein the number of hydroxyl groups is 2 in the above formula (1), (4) or (7).
And a diester having 1 hydroxyl group is used,
Triesters to which no hydroxyl group is bonded do not have a hydroxyl group capable of coordinating and / or ionic bonding with copper ions, and thus it is difficult to disperse copper ions in a resin when, for example, a resin composition is formed.

Further, R ¹ in the above formula (2) or (3) represents an aryl group having 6 to 20 carbon atoms (provided that hydrogen of the aryl group is an alkyl group having 1 to 6 carbon atoms, or May be substituted by at least one halogen, and hydrogen of the alkyl group may be substituted by at least one halogen.)
R ³ , R ⁴ and R ⁵ in the above formula (5), the above formula (6) or the above formula (8) each have 1 to 20, preferably 1 to carbon atoms.
10 alkyl groups or aryl groups (provided that the hydrogen of the aryl group may be substituted with at least one alkyl group having 1 to 6 carbon atoms or halogen, and the hydrogen of the alkyl group may be substituted with at least one halogen. ). These R ¹ , R ³ ,
If the carbon number of R ⁴ or R ⁵ exceeds 20, the compatibility with a resin such as an acrylic resin decreases, and it is difficult to disperse metal ions including copper ions in the resin. R ² in the above formula (2) or the above formula (3) has a carbon number of 1 to 1.
And R ⁶ , R ⁷ or R ⁸ in the above formula (8) is hydrogen or an alkyl group having 1 to 4 carbon atoms. That is, examples of the alkylene oxide group include a propylene oxide group and a butylene oxide group, and a propylene oxide group is particularly preferable.
These alkyl groups R ² , R ⁶ , R ⁷ or R ⁸ have 4 carbon atoms.
When the ratio exceeds the above range, it is difficult to disperse the resin in a high ratio in the resin.

The ratio of the specific phosphate compound to the copper ion is such that the hydroxyl group or the oxygen atom derived from the hydroxyl group in the specific phosphate compound is 0.5 to 10 mol, preferably 1 to 1 mol of the copper ion. It is preferably from 0.5 to 5 mol. When this ratio is less than 0.5 mol, it tends to be difficult to disperse copper ions in a resin such as an acrylic resin. If this proportion exceeds 10 mol, the proportion of hydroxyl groups that do not participate in coordination and / or ionic bonding with copper ions becomes excessively large. It tends to be larger. Therefore, when this ratio is set to 0.5 to 10 mol, the near-infrared ray composed of the resin composition in which copper ions are well dispersed in the resin, have excellent near-infrared light absorption properties, and do not have hygroscopicity. A light absorber can be obtained.

Further, when the near-infrared light absorbing compound of the present invention is contained in a resin such as an acrylic resin to form a resin composition, the content ratio of copper ions is 0.1% of the whole resin composition. The content is adjusted so as to be 1 to 60% by weight, preferably 0.1 to 20% by weight, more preferably 0.3 to 15% by weight, and still more preferably 0.5 to 5% by weight. When this ratio is less than 0.1% by weight, the ability to absorb near-infrared light with high efficiency tends not to be obtained. On the other hand, when this ratio exceeds 60% by weight, copper ions are contained in the resin. It tends to be extremely difficult to disperse. Therefore, the content ratio of copper ions is 0.1 to the total of the resin composition
By setting the content to 60% by weight, a near-infrared light-absorbing compound excellent in visible light transmittance can be surely obtained.

Further, the use ratio of the above-mentioned metal ions is as follows:
It is preferably at most 50% by weight, more preferably at most 30% by weight, based on all metal ions including copper ions,
More preferably, it is at most 20% by weight. This ratio is 50
When the content is more than 10% by weight, the bond coordination between the copper ion and the phosphate compound is affected by other metal ions. Tends to be difficult.

<Near-Infrared Light Absorbing Agent> The near-infrared light absorbing agent of the present invention contains the above-mentioned near-infrared light absorbing compound of the present invention. The external light absorbing compound itself, a liquid composition and a resin composition are preferred.

[Liquid composition]: The liquid composition as the near-infrared light absorbing agent of the present invention is obtained by dissolving or dispersing the above-mentioned near-infrared light absorbing compound of the present invention in an appropriate solvent. If the thin film formed by evaporating the solvent is optically transparent, the liquid composition itself may be transparent, translucent, or opaque. Here, water or an organic solvent can be used as the solvent. Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol, and glycol ethers such as methyl cellosolve and ethyl cellosolve. , Diethyl ether, ethers such as diisopropyl ether, acetone, methyl ethyl ketone,
Methyl isobutyl ketone, ketones such as cyclohexanone, ethyl acetate, isopropyl acetate, butyl acetate, esters such as butyl acetate cellosolve, benzene, toluene, aromatic compounds such as xylene, hexane, kerosene,
Petroleum ether or the like is used. Also, (meth) acrylates such as (meth) acrylate, styrene, α
-A polymerizable organic solvent such as an aromatic vinyl compound such as methylstyrene may also be used. Then, by applying such a liquid composition to, for example, a substrate surface and evaporating only the solvent, a thin film having excellent near-infrared light absorption characteristics can be easily obtained.

The content of the near-infrared light-absorbing compound of the present invention in the liquid composition depends on the type of solvent used,
Although it depends on the use or purpose of use of the obtained near-infrared light absorber, from the viewpoint of the viscosity after preparation, the liquid medium 10 is usually used.
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 0 parts by mass.

[Resin composition]: The near-infrared light absorbing compound of the present invention has good solubility or dispersibility in a resin as described above. For example, it has good dispersibility in acrylic resins, particularly (meth) acrylate resins, and has high compatibility with these resins. Other resins having high compatibility with the specific phosphate compound include polyethylene terephthalate (PET), polyethylene, polypropylene, polyvinyl chloride, polycarbonate, styrene, α-methylstyrene, chlorostyrene, dibromostyrene. And polymers such as aromatic vinyl compounds such as methoxystyrene, vinylbenzoic acid and hydroxymethylstyrene. Note that the meaning of “meth” enclosed in parentheses is used for convenience to simplify the description when it is necessary to describe both acrylic acid or a derivative thereof and methacrylic acid or a derivative thereof. This is a description method and is also adopted in this specification.

The resin composition as a near-infrared light absorbing agent of the present invention includes the above-mentioned near-infrared light absorbing compound of the present invention,
It is contained in the above resin. Here, an acrylic resin composition will be described first as an example of the resin composition, but the same applies to resin compositions other than the acrylic resin composition. This acrylic resin composition,
It is prepared by incorporating the near infrared light absorbing compound of the present invention into an acrylic resin.

As the acrylic resin, a polymer obtained from a (meth) acrylate monomer is preferably used. Specific examples of such (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate , Tertiary butyl (meth) acrylate, n-hexyl (meth) acrylate, n-
Alkyl (meth) acrylates such as octyl (meth) acrylate, glycidyl (meth) acrylate, 2-
Modified (meth) acrylates such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, isobornyl (meth) acrylate, methoxypolyethylene (meth) acrylate, and phenoxy (meth) acrylate , Ethylene glycol di (meth) 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, trimethylolpropane tri (meth) acrylate, pentaerythrit tri (meth) acrylate, pentaerythrit tetra (meth)
And polyfunctional (meth) acrylates such as acrylate. These monomers may be used alone or in combination of two or more.

As another acrylic resin, other (meth) acrylic ester monomers and other copolymerizable copolymerizable with the (meth) acrylic ester monomers 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, 2-
Unsaturated carboxylic acids such as (meth) acryloyloxyethyl phthalic acid, acrylamides such as N, N-dimethylacrylamide, styrene, α-methylstyrene, chlorostyrene, dibromostyrene, methoxystyrene, vinylbenzoic acid, hydroxymethylstyrene And the like. These monomers are used alone or in combination of two or more.

The specific method for preparing such an acrylic resin composition is not particularly limited, but the following two methods are preferred. The content of the near-infrared light-absorbing compound in the acrylic resin composition as the near-infrared light absorbing agent of the present invention varies depending on the use or purpose of the obtained near-infrared light absorbing agent. From the viewpoint of (or moldability), usually 0.1 to 400 parts by mass, preferably 0.1 part by mass, per 100 parts by mass of the resin.
It is adjusted in the range of 3 to 200 parts by mass, particularly preferably 1 to 100 parts by mass. Further, as described above, in order to reliably obtain a resin composition having excellent visible light transmittance, the proportion of copper ions in the resin composition is, for example, 0.1 to 60% by weight of the entire acrylic resin composition. It is desirable that

[First Method]: In the first method, a mixture of a specific phosphate compound and a copper compound in a monomer for obtaining an acrylic resin and / or a reaction of both. This is a method of preparing a monomer composition containing the obtained phosphoric acid ester copper compound (the near-infrared light absorbing compound of the present invention) and subjecting this monomer composition to 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, a bulk (cast) polymerization method, Turbid polymerization method,
Known methods such as an emulsion polymerization method and a solution polymerization method can be used.

[Second Method] The second method is a method of mixing a specific phosphate compound and a copper compound in an acrylic resin and / or a copper phosphate obtained by a reaction of both. In this method, the compounds are added and mixed. This method is used when a thermoplastic resin is used as the acrylic resin. Specifically, a method in which a mixture of a specific phosphoric acid ester compound and a copper compound and / or a phosphoric acid ester copper compound obtained by a reaction of both are added and kneaded in a molten acrylic resin,
The acrylic resin is dissolved, dispersed or swelled in an appropriate organic solvent, and a mixture of a specific phosphate compound and a copper compound and / or a phosphate copper compound obtained by a reaction of both are added to the solution. After mixing, the organic solvent is removed from the solution.

In the above method, as a means for kneading a mixture of an acrylic resin, a specific phosphate compound and a copper compound, and / or a phosphate copper compound obtained by the reaction of both, thermoplastic thermoplastic resin is used. Means generally used as a method for melt-kneading a resin include, for example, means for melt-kneading with a mixing roll, means for pre-mixing with a Henschel mixer and the like, followed by melt-kneading with an extruder. 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 acrylic resin, and specific examples thereof include methyl alcohol, ethyl alcohol, Alcohols such as isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene and xylene, chlorine-based hydrocarbons such as methylene chloride, and amide compounds such as dimethylacrylamide and dimethylformamide. No.

In the preparation of the above acrylic resin composition, when a mixture of a specific phosphate compound and a copper compound is used, the reaction between the specific phosphate compound and the copper salt results in a copper salt. From the acid component which is an anion. Such an acid component is preferably removed as necessary for the same reason as described above. As a method therefor, (a) a method of extracting an acid component by immersing the acrylic resin composition in an appropriate organic solvent, and (b) a method of subjecting the monomer composition to polymerization before subjecting the monomer composition to polymerization. A method is exemplified in which a body composition is subjected to a cooling treatment to precipitate and separate an acid component.

As the organic solvent used in the above method (a), an acid component to be liberated can be dissolved, and has an appropriate affinity for the acrylic resin used (the acrylic resin does not dissolve, The material is not particularly limited as long as it has an affinity enough to penetrate into the acrylic resin. 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, diethyl ether,
Ethers such as petroleum ether, aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, chloroform, methylene chloride and carbon tetrachloride and their halides, and aromatics such as benzene, toluene and xylene Hydrocarbons and the like. On the other hand, in the above method (b), it is preferable to use, as a copper compound constituting a mixture of a specific phosphate compound and a copper compound, a compound in which an acid component to be liberated is hardly dissolved in a monomer. Specific examples include copper salts of carboxylic acids having an aromatic ring such as benzoic acid.

Other suitable resins used in the resin composition as a near-infrared light absorber of the present invention include polyvinyl butyral resins, ethylene-vinyl acetate copolymers, and partial saponification of the copolymers. Things can be mentioned. These polyvinyl butyral resins, ethylene-vinyl acetate copolymers or partially saponified products of the copolymers have excellent adhesiveness to substrates made of glass or plastic materials, and have flexibility themselves. In addition, since the temperature dependency is small, adhesion to the base material is ensured without using an adhesive, and thus a molded article having near-infrared light absorption excellent in moldability can be easily obtained. At the same time, it is possible to obtain a molded article that can improve the resistance to temperature changes.

Further, the resin composition as the near-infrared light absorber of the present invention can contain various plasticizers having compatibility with the resin component as other components.
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-based plasticizers such as acetyl ricinoleate and butyl succinate, butyl phthalyl butyl glycolate, triethylene glycol dibutyrate, and triethylene glycol di-
Examples include glycol-based plasticizers such as 2-ethyl butyrate and polyethylene glycol. Further, the resin composition as a near-infrared light absorber of the present invention may contain a benzotriazole-based, benzophenone-based or salicylic acid-based ultraviolet absorber, other antioxidants, stabilizers, and the like.

<Display Front Plate> The display front plate of the present invention is provided with a near-infrared light absorbing layer containing the above-mentioned near-infrared light absorbing agent of the present invention. FIG.
FIG. 13A is a diagram showing a preferred embodiment of a display front panel according to the present invention, and FIG.
(B) is a perspective view showing a laminated structure. The display front plate 1 shown in FIG. 13 is an optically transparent plate-like body attached to the front surface of a plasma display panel (hereinafter, referred to as PDP), and contains the near infrared light absorber of the present invention. On one surface of a substantially flat transparent member 11 having a near-infrared light absorbing layer formed as described above, a shield mesh 13 in which a conductive thin wire is braided vertically and horizontally to form a mesh is made of resin, for example, polyethylene terephthalate. It is attached so as to be covered with a transparent film 14 made of (PET). Further, a reflection reducing film 12 is formed on the entire area of the other surface of the transparent member 11. Furthermore, shield mesh 1
An anti-reflection film 15 as an anti-reflection layer is formed on the surface of the transparent film 14 that is not in contact with 3.

As the transparent member 11 employed in this embodiment, the following three types are suitable. [First embodiment]: The near-infrared light absorbing agent is bonded to a resin composition as the near-infrared light absorbing agent of the present invention, or to a transparent substrate made of glass or a transparent resin plate. What was done. [Second embodiment]: A near-infrared light absorbing film 16 as a near-infrared light absorbing layer made of the near-infrared light absorbing agent of the present invention is formed on a transparent substrate made of glass or a transparent resin plate. Things. [Third embodiment]: A material formed of a near-infrared light absorbing agent containing only the near-infrared light absorbing compound of the present invention, or a near-infrared light-absorbing compound formed on a transparent substrate made of glass or a transparent resin plate. One to which a light absorbing agent is attached.

In any of the above-mentioned embodiments, the characteristic characteristic of copper ions that selectively absorbs near-infrared light is exhibited, while the near-infrared light-absorbing compound of the present invention exhibits light (visible light) in the visible region. Since it does not have an energy level corresponding to the wavelength of visible light, visible light is not absorbed. Therefore, according to the display front panel 1 of the present invention containing the near-infrared light absorbing agent of the present invention, excellent near-infrared light absorbing performance and visible light transmitting performance that are equal to or superior to those of the related art are achieved. Is done.

The first embodiment is produced by polymerizing and curing the resin composition as the near-infrared light absorbing agent of the present invention. At this time, since the specific phosphate compound does not have an unsaturated double bond in the molecular structure, when the resin composition is polymerized and cured in a mold, the releasability of the cured resin composition is reduced. It is much higher than before. This is presumed to be due to a lower degree of polymerization shrinkage than the conventional resin composition containing a phosphorus atom-containing compound having a double bond because the degree of crosslinking of the resin composition is lower than in the past. obtain. Further, since the resin composition has thermoplasticity and is thermally stable, it is suitable for re-molding by heat after molding. Therefore, according to the display front plate 1 including the transparent member 11 of the first embodiment, it is possible to significantly improve the formability in comparison with the related art.

On the other hand, the transparent member 11 of the second embodiment is
For example, it is produced by applying the liquid composition as the near-infrared light absorbing agent of the present invention to a substrate surface and evaporating the solvent. Alternatively, the near-infrared light-absorbing compound itself of the present invention, or a powder containing the near-infrared light-absorbing compound of the present invention may be adhered by spraying with a powder spray or the like on the substrate surface. The conductive film 16 can be formed. Note that these powders may be attached via a sticky substance such as an adhesive. In this manner, the near-infrared light-absorbing compound of the present invention does not contain an unsaturated double bond having high sensitivity to ultraviolet light and heat in its molecular structure.
Near-infrared light absorbing film 1 formed in the second embodiment
6 is stable against ultraviolet rays and heat. Therefore, even if the resin composition is not polymerized and cured, it is possible to obtain the display front panel 1 which is excellent in near-infrared light absorption performance, is thermally and chemically stable, and hardly deteriorates. That is, it is possible to improve the method of manufacturing the display front panel 1 and the selectivity of the material.

On the other hand, the transparent member 11 of the third embodiment is
The component comprising only the near-infrared light-absorbing compound of the present invention is produced as a film-like or plate-like molded product by, for example, pressure molding. The transparent member 11 of the third embodiment
By using, it is possible to excel in near-infrared light absorption characteristics and to eliminate some visible light absorption 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, a wavelength of 800 nm to
Display front plate 1 in wavelength region of 1000 nm
Near infrared light transmittance of 20% or less, preferably 1
The type of the near-infrared light absorber (or near-infrared light-absorbing compound) so as to be 0% or less, particularly preferably 5% or less,
The concentration and the layer thickness (the thickness of the layer when applied or laminated, or the thickness of the resin layer when dispersed in the resin layer) are 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. There is no risk of malfunction.

The shield mesh 13 is, for example,
It is knitted with plastic fibers coated with a transition metal such as copper or nickel, and has a function of effectively shielding electromagnetic waves in a frequency range of several MHz to several hundred MHz. Further, both the reflection reducing film 12 and the antireflection film 15
For example, 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 are alternately laminated.

FIG. 14 is a perspective view showing a use state of the above-described embodiment according to the display front plate of the present invention. FIG.
As shown in FIG. 14, the display front panel 1 having the laminated structure shown in FIG. 3 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 transparent member 11 as a near-infrared light absorbing layer and has an intensity of 20% or less, preferably 10% or less, particularly preferably 5% or less. Reduced to

On the other hand, the visible light emitted simultaneously with the near-infrared light from the panel surface 21 of the PDP 2 is not absorbed by the near-infrared light absorbing compound contained in the display front plate 1 as described above. Absorption of visible light is very small as compared with near-infrared light. Therefore, even if devices that operate with near-infrared light are placed around the PDP 2 shown in FIG. 14, 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 the image and 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. Such electromagnetic waves are effectively shielded by the shield mesh 13 shown in FIG. Not be exposed to Further, since the shield mesh 13 has the same conductivity as metal, the display front plate 1 is hardly charged with static electricity, and the display front plate 1 is charged by static electricity.
This prevents dust and the like from adhering to the surface. Further, since 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 enters the anti-reflection film 15 of the display front panel 1, the reflection is prevented by the action of the multilayers having different refractive indexes that form the anti-reflection film 15. 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 small part of the external light passes through the anti-reflection film 15, and the transmitted light is reflected by the reflection reducing film 12 formed on the surface of the transparent member 11.
As a result, reflection is reduced, so that it is further prevented that an image or the like reflected on the panel surface 21 becomes difficult to see due to reflection of external light.

Here, near-infrared light and infrared light are heat rays,
The near-infrared light-absorbing compound of the present invention described above can also be applied to members that require heat ray absorption. Hereinafter, as such members, a heat ray absorbing coating agent, a heat ray absorbing composite, a heat ray absorbing adhesive, and the like will be described.

<Heat Absorbing Coating Agent> As the heat ray absorbing coating agent, a liquid composition as the near-infrared light absorbing agent of the present invention is useful, and a thin film formed by evaporating a liquid solvent is an optical film. As long as it is transparent, the heat ray absorbing coating agent itself may be transparent, translucent or opaque. Here, as the liquid medium, water or an organic solvent can be used, and as the organic solvent, alcohols such as methyl alcohol, ethyl alcohol, 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,
Esters such as ethyl acetate, isopropyl acetate, butyl acetate and butyl acetate cellosolve, aromatic compounds such as benzene, toluene and xylene, hexane, kerosene, petroleum ether and the like are used. Further, polymerizable organic solvents such as (meth) acrylates such as (meth) acrylate and aromatic vinyl compounds such as styrene and α-methylstyrene are also preferably used.

Further, a solubilizing agent or the like for improving the solubility or dispersibility of the above-mentioned near-infrared light absorbing compound in a liquid medium and the flatness of the surface coated with the heat ray absorbing coating agent is added as an additive. You may. As such additives, for example, various surfactants as a leveling agent and an antifoaming agent are preferably used. Further, if liquid, a resin may be added. The content ratio of the near-infrared light-absorbing compound of the present invention 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, usually, 0.1 to 1900 parts by mass, preferably 1 to 9 parts by mass with respect to 100 parts by mass of the liquid medium.
The amount is 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 layer comprising a near-infrared light absorbing agent is provided on one surface of a light-transmitting substrate. Is useful, and another substrate having translucency 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. Furthermore, 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, a layer made of another light-transmitting material may be provided on the base 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 to form a liquid. What evaporated the medium (solvent) is used preferably. 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.

For the near-infrared light absorbing layer, it is also preferable to use the resin composition as the near-infrared light absorbing agent of the present invention. As such a resin component, those having excellent translucency are preferably used, and specifically, a vinyl chloride resin, an acrylic resin, a polycarbonate resin, a polyester resin, a polyurethane resin, a polyvinyl butyral resin Resins, ethylene-vinyl acetate copolymers and partially saponified products thereof, and the like. These resins are used alone or in combination of two or more. Of these, polyvinyl butyral, an ethylene-vinyl acetate copolymer, or a partially saponified product of the copolymer is preferably used, particularly from the viewpoint of adhesion to glass materials and plastic materials. In addition, an acrylic resin is preferably used from the viewpoints of visible light transmittance and moldability.

The near-infrared light absorbing layer made of a resin composition containing these resins contains, as other components, the above-mentioned various plasticizers compatible with the resin component, and the above-mentioned benzotriazole-based and benzophenone-based plasticizers. Alternatively, a salicylic acid-based ultraviolet absorber, other antioxidants, stabilizers and the like may be contained. Further, in order to obtain a heat-absorbing composite by forming a near-infrared light absorbing layer made of a resin composition on a substrate, for example,
By mixing the near-infrared light-absorbing compound of the present invention, the above-mentioned resin component, and the other components used as necessary, a material for forming a near-infrared light-absorbing layer is prepared. A method of forming a near-infrared light absorbing layer by forming the film into a film or a sheet can be used. However, the method of forming the near-infrared light absorbing layer to obtain the heat ray absorbing composite is not limited to this. Then, the near-infrared light absorbing layer is bonded to a base material prepared in advance.

As means for preparing the material for forming the near-infrared light absorbing layer by mixing the above components, means for mixing with a mixer such as a Henschel mixer, a roll kneader,
Alternatively, means for kneading and mixing with a kneading extruder or the like can be used. In addition, means for dispersing each component in an appropriate organic solvent and removing the organic solvent from the dispersion can be used. In addition, as a means for producing the molded article 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. As a means for bonding the near-infrared light absorbing layer to the substrate, a pressing method, a multi-roll method, a means for bonding by pressure or reduced pressure such as a reduced pressure method, a means for bonding by heating using an autoclave or the like, or Means based on these combinations can be used. When using polyvinyl butyral, an ethylene-vinyl acetate copolymer or a partially saponified product thereof as the resin component, the heat ray absorbing composite in which the near infrared light absorbing layer and the base material are bonded with sufficient strength is used. Is obtained.

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 preferred 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, when 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 the heat ray absorbing composite preferably has a near-infrared light absorbing layer made of the above-mentioned acrylic resin composition. 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. 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 nm
May be mixed in the resin composition with a metal ion-containing component or the like containing a cobalt ion that selectively absorbs the above.

<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 compound of the present invention are useful. An acrylic resin having adhesiveness can be preferably used as such an adhesive resin. Such an acrylic resin having adhesiveness can be obtained by polymerizing a monomer composition containing an acrylic resin monomer constituting an adhesive component. As the acrylic resin monomer used as the adhesive component, the alkyl group has 4 to 12 carbon atoms and the glass transition point of the homopolymer is −
Alkyl acrylate having a temperature of 70 ° C to -30 ° C can be suitably used, and specific examples include n-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, and decyl acrylate.

[0092] In addition to the acrylic resin monomer used as the above-mentioned adhesive component, a monomer constituting an aggregating component and a monomer component 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 action of increasing the glass transition point of the obtained copolymer is used, specifically,
Examples thereof include an alkyl acrylate having a lower alkyl group having 1 to 3 carbon atoms, an alkyl methacrylate, vinyl acetate, vinylidene chloride, acrylonitrile, and styrene. In addition, as the monomer used as the modifying component, a monomer which 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. No. When the monomer composition is polymerized by an emulsion polymerization method, various known emulsifiers used in ordinary emulsion polymerization can be used.

Then, 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 of the present invention can be obtained by mixing the near-infrared light-absorbing compound of the present invention with the polymer solution or latex thus obtained, and if necessary, a specific wavelength. A visible light absorbing agent that absorbs visible light, for example, a metal ion-containing component containing a cobalt ion that selectively absorbs a wavelength of 500 nm to 600 nm, and other additives may be mixed. The content of the near-infrared light-absorbing compound of the present invention in the heat-ray-absorbing pressure-sensitive adhesive is desirably as large as possible within a range that does not impair the translucency and the tackiness of the acrylic resin having tackiness. The amount is adjusted within the range of 0.1 to 400 parts by mass, preferably 0.3 to 200 parts by mass, and more preferably 1 to 100 parts by mass with respect to 100 parts by mass of the acrylic resin having properties.

The heat ray absorbing coating agent, the heat ray absorbing composite and the heat ray absorbing pressure-sensitive adhesive described above are preferably applied to a light-transmitting member or the like which is required to shield 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 heat ray absorbing coating agent described above,
The window material to which the heat ray-absorbing composite and the heat ray-absorbing pressure-sensitive adhesive are applied has a heat ray absorption property equal to or higher than that of a case where a light-blocking member that absorbs visible light is used to obtain heat ray shielding property. In addition, since it has excellent visible light transmittance, it has excellent visibility of the scenery outside the window, and tends to easily obtain a feeling of openness. In addition, it is possible to obtain a translucent optical member which is excellent in thermal and chemical stability and environmental resistance and is hardly deteriorated.

Another application 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 above-mentioned heat ray absorbing coating agent, heat ray absorbing composite and heat ray absorbing adhesive are applied, such an excessive rise in temperature can be effectively suppressed, so that the usage period of the greenhouse facility can be extended. Thus, the operation rate can be improved. In addition, since it has excellent visible light transmittance, the visibility of the inside from the outside of the greenhouse is also improved. In addition, it becomes possible to obtain a coating material which is excellent in thermal and chemical stability and environmental resistance and hardly deteriorates.

[0098]

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

<Example 1> 103.4 g of phenol
(1.1 mol) was dissolved in 225 ml of dimethoxyethane (hereinafter also referred to as DME), 2.1 g of caustic soda and 66 g (1.1 mol) of propylene oxide were added, and the mixture was refluxed at 80 ° C. for 24 hours. DME was distilled off under reduced pressure, extracted with toluene, washed with alkaline water, and toluene was distilled off under reduced pressure. Thereafter, distillation under reduced pressure (（1 mmHg, 70-75 ° C.) gave 139 g of a colorless oil. When the component ratio of the produced alcohol was measured by gas chromatography, 1-
Phenoxy-2-propanol and 2-phenoxy-1-
The mixture had a propanol ratio of 9: 1. 125 g (0.8 mol) of the obtained alcohol mixture was added to toluene 1
The solution was dissolved in 60 ml, and at about 5 ° C., 37.8 g of phosphorus pentoxide was added little by little. After stirring at room temperature for 2 days, 15 ml of water was added at 60 ° C for 4 hours, and the mixture was stirred at 80 ° C for 3 hours. Thereafter, toluene was distilled off under reduced pressure to obtain 164 g of a viscous oil. When the mixture component was identified using a nuclear magnetic resonance (hereinafter referred to as NMR) measuring device or the like, the oil was found to have the following formulas (18), (19), (20), and (21) ) And a phosphate compound represented by the following formula (22), and the acid value as determined by alkali titration was 5.28 mmol / g. All the phosphorus pentoxides are monoesters represented by the following formulas (18) and (19) and the following formulas (20), (21) and (22).
Assuming that the diester is represented by the following formula, the molar ratio between the monoester and the diester is 61:39 based on the acid value.

[0100]

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Next, 51.3 g of the obtained phosphate ester was obtained.
Was dissolved in 150 ml of toluene, 27 g of copper acetate was added thereto, and the mixture was dehydrated and refluxed. After dehydration and deacetic acid removal, the solvent is distilled off, and a green-blue viscous copper complex 5 as a near-infrared light absorbing compound 5
9.9 g were obtained. This copper complex was freely dissolved in toluene, ethyl acetate, dimethoxyethane, and methyl methacrylate, and became a light blue transparent liquid as a liquid near-infrared light absorber.

Example 2 5 g of the copper complex obtained in Example 1 was dissolved in 95 g of methyl methacrylate.
After adding 0.2 g of α-methylstyrene and 1 g of t-butylperoxyneodecanate, the mixture was poured into a glass mold, and was heated at 40 ° C. for 8 hours, at 65 ° C. for 2 hours, at 100 ° C.
The mixture was heated at a different temperature for one hour to perform cast polymerization, thereby obtaining a 3 mm-thick, light blue, transparent, near-infrared light-absorbing plate-like body made of the resin composition.

Example 3 A mixture of 201 g of glycidyl phenyl ether, 200 ml of methanol, and 10 g of 28% sodium methoxide was stirred at room temperature for 2 days.
Stirred at C for 5 hours. The methanol was distilled off under reduced pressure, and the residue was extracted with toluene, washed with water, and distilled off with toluene.
2 mmHg, 96-100 ° C)
172 g of phenoxy-2-propanol were obtained. 164 g (0.9 mol) of the obtained alcohol was added to toluene 1
The solution was dissolved in 80 ml, and at about 5 ° C., 42.5 g of phosphorus pentoxide was added little by little. After stirring at room temperature for 3 days, 15 ml of water was added at 60 ° C for 3 hours, and the mixture was stirred at 80 ° C for 3 hours. The toluene was distilled off under reduced pressure to obtain 209.5 g of a viscous oil. When the mixture component was identified using an NMR measurement device or the like, this oil was found to have the following formula (23) and the following formula (2)
A mixture of phosphate ester compounds represented by 4),
The acid number by alkali titration was 4.92 mmol / g. Assuming that all of the phosphorus pentoxide is a monoester represented by the following formula (23) and a diester represented by the following formula (24), the molar ratio of the monoester to the diester is 60:40 from the above acid value. .

[0104]

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Next, 47.8 g of the obtained phosphate ester
Was dissolved in 150 ml of toluene, 23.5 g of copper acetate was added, and the mixture was dehydrated and refluxed. After dehydration and deacetic acid removal, the solvent was distilled off to obtain 56.2 g of a green-blue semisolid copper complex as a near-infrared light absorbing compound. This copper complex was freely dissolved in toluene, ethyl acetate, dimethoxyethane, and methyl methacrylate, and became a light blue transparent liquid as a liquid near-infrared light absorber.

Example 4 5 g of the copper complex obtained in Example 3 was dissolved in 95 g of methyl methacrylate.
After adding 0.2 g of α-methylstyrene and 1 g of t-butylperoxyneodecanate, the mixture was poured into a glass mold, and was heated at 40 ° C. for 8 hours, at 65 ° C. for 2 hours, at 100 ° C.
The mixture was heated at a different temperature for one hour to perform cast polymerization, thereby obtaining a 3 mm-thick, light blue, transparent, near-infrared light-absorbing plate-like body made of the resin composition.

<Example 5> 60% sodium hydride 41
g was washed with hexane, 350 ml of DME was added, and 84 g of propylene glycol was slowly added dropwise. 161 g of 4-chlorobenzyl chloride / 50 ml of DME were added, and the mixture was stirred at 80 ° C. overnight. DME was distilled off under reduced pressure, extracted with toluene, washed with water, and distilled off with toluene to obtain 185 g of an oil. This was distilled under reduced pressure (1-2 mmHg, 91-98).
C) to give 122 g of a colorless oil. When the component ratio of the produced alcohol was measured by gas chromatography, a mixture of 1- (4-chlorobenzyloxy) -2-propanol and 2- (4-chlorobenzyloxy) -1-propanol having a ratio of 9: 1 was used. Met. 100 g (0.5 mol) of the obtained alcohol mixture was added to toluene 10
The solution was dissolved in 0 ml, and 23.6 g of phosphorus pentoxide was added little by little at about 5 ° C. After stirring at room temperature for 2 days, 3 ml of water was added at 60 ° C for 3 hours, and the mixture was stirred at 100 ° C for 4 hours. Thereafter, toluene was distilled off under reduced pressure to obtain 124.5 g of a viscous oil. When the mixture component was identified using an NMR measurement device or the like, this oil was represented by the following formulas (25), (26), (27), (28), and (29). Is a mixture of the phosphoric acid ester compounds to be obtained, and the acid value by alkali titration is 4.32 mmol / g.
Met. Assuming that all the phosphorus pentoxides are converted into monoesters represented by the following formulas (25) and (26) and diesters represented by the following formulas (27), (28) and (29), From the above acid number, the molar ratio between the monoester and the diester is 60:40.

[0108]

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Next, 45.6 g of the obtained phosphate ester
Was dissolved in 150 ml of toluene, 19.6 g of copper acetate was added, and the mixture was dehydrated and refluxed. After dehydration and deacetic acid removal, the solvent was distilled off, and a green-blue copper complex 5 as a near-infrared light absorbing compound was obtained.
2.4 g were obtained. This copper complex was freely dissolved in toluene, ethyl acetate, dimethoxyethane, and methyl methacrylate, and became a light blue transparent liquid as a liquid near-infrared light absorber.

<Example 6> 5 g of the copper complex obtained in Example 5 was dissolved in 95 g of methyl methacrylate.
After adding 0.2 g of α-methylstyrene and 1 g of t-butylperoxyneodecanate, the mixture was poured into a glass mold, and was heated at 40 ° C. for 8 hours, at 65 ° C. for 2 hours, at 100 ° C.
The mixture was heated at a different temperature for one hour to perform cast polymerization, thereby obtaining a 3 mm-thick, light blue, transparent, near-infrared light-absorbing plate-like body made of the resin composition.

Example 7 104 g (1 mol) of 3-methoxy-1-butanol was dissolved in 200 ml of toluene, and 47.3 g of phosphorus pentoxide was added little by little at about 5 ° C.
After stirring at room temperature for 2 days, 15 ml of water was added at 60 ° C for 4 hours, and the mixture was stirred at 80 ° C for 3 hours. The toluene was distilled off under reduced pressure to obtain 148 g of a viscous oil. When the mixture component was identified, this oil was a mixture of the phosphate compound represented by the following formula (30) and the following formula (31), and the acid value by alkali titration was 7.23 mmol / g.
Met.

Assuming that all of the phosphorus pentoxide is a monoester represented by the following formula (30) and a diester represented by the following formula (31), the molar ratio of the monoester to the diester is 60: 40.

[0113]

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Next, 30 g of the obtained phosphoric acid ester was dissolved in 100 ml of toluene, 21.7 g of copper acetate was added, and the mixture was dehydrated and refluxed. After dehydration and deacetic acid removal, the solvent was distilled off, and a green-blue powdery copper complex 37 as a near-infrared light-absorbing compound was obtained.
g was obtained. This copper complex was well dissolved in toluene, ethyl acetate, dimethoxyethane, and methyl methacrylate, and became a light blue transparent liquid as a liquid near-infrared light absorber.

Example 8 5 g of the copper complex obtained in Example 7 was dissolved in 95 g of methyl methacrylate.
After adding 0.2 g of α-methylstyrene and 1 g of t-butylperoxyneodecanate, the mixture was poured into a glass mold, and was heated at 40 ° C. for 8 hours, at 65 ° C. for 2 hours, at 100 ° C.
The mixture was heated at a different temperature for one hour to perform cast polymerization, thereby obtaining a 3 mm-thick, light blue, transparent, near-infrared light-absorbing plate-like body made of the resin composition.

Comparative Example 1 2-butoxyethanol 15
0 g was dissolved in 200 ml of toluene, and 60 g of phosphorus pentoxide was added little by little at about 5 ° C. After stirring at room temperature for 2 days,
15 ml of water was added at 60 ° C. for 4 hours, and the mixture was stirred at 80 ° C. for 3 hours. The toluene was distilled off under reduced pressure to obtain 204 g of a viscous oil. The acid value of the oil by alkali titration was 6.65 mmol / g. Assuming that all the phosphorus pentoxide is a monoester and a diester, the molar ratio of the monoester and the diester is 60:40 based on the acid value. 40 g of the obtained phosphoric acid ester was dissolved in toluene 130
Then, 26.7 g of copper acetate was added, and the mixture was dehydrated and refluxed. After dehydration and deacetic acid removal, the solvent was distilled off to obtain 49 g of a pale blue powdery copper complex. This copper complex hardly dissolved in toluene, ethyl acetate, dimethoxyethane, and methyl methacrylate. As described above, it was not possible to prepare a transparent solution or resin plate at a practical concentration with this copper complex.

<Comparative Example 2> 95 g of 4-methoxy-1-butanol was dissolved in 180 ml of toluene, and 43 g of phosphorus pentoxide was added little by little at about 5 ° C. After stirring at room temperature for 2 days, 15 ml of water was added at 60 ° C for 4 hours, and the mixture was stirred at 80 ° C for 3 hours. The toluene was distilled off under reduced pressure to obtain 129 g of a viscous oil. The acid value of the oil by alkali titration was 7.54 mmol / g. Assuming that all of the phosphorus pentoxide is a monoester and a diester, the molar ratio of the monoester and the diester is 60:40 based on the acid value.
Becomes 40 g of the obtained phosphoric acid ester was dissolved in toluene 13
The solution was dissolved in 0 ml, and 30.3 g of copper acetate was added, followed by dehydration and reflux. After dehydration and deacetic acid removal, the solvent was distilled off to obtain 53 g of a green-blue grease-like copper complex. This copper complex hardly dissolved in toluene, ethyl acetate, dimethoxyethane, and methyl methacrylate. As described above, it was not possible to prepare a transparent solution or resin plate at a practical concentration with this copper complex.

Comparative Example 3 8.66 g of a mixture of a phosphoric acid ester compound represented by the following formulas (32) and (33) and having a polymerizable unsaturated double bond in its molecular structure, and copper acetate 3 .80 g, and mixed with methyl methacrylate 9
It was added to 1.34 g and dissolved. 0.30 g of α-methylstyrene, 1.0 g of a polymerization initiator t-butylperoxyneodecanate, and 0.10 g of a release agent alkyl phosphate ester salt were added thereto, and the mixture was composed of two glass substrates. Pour into molds, 8 hours at 40 ° C., 2 hours at 65 ° C., 10
Polymerization was performed at 0 ° C. for 1 hour using a polymerization program to obtain a plate-like body.

[0119]

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<Comparative Test 1 Regarding Thermal Stability> (1) A spectral transmittance curve of the plate-like body manufactured in Example 4 was measured using a spectrophotometer (U-4000 manufactured by Hitachi, Ltd.). did. Then, 150 ℃, 40k
The plate was heated and pressed at a pressure of gf / cm ² for 10 minutes, and the spectral transmittance curve of the plate was measured again. FIG. 1 shows the measurement results of the spectral transmittance curves before and after the heating press. As shown in FIG. 1, it was confirmed that this plate-shaped body had good absorption characteristics in the near-infrared region and excellent light transmittance in the visible region. From FIG. 1, it is understood that the plate-shaped body hardly changes its light transmittance in the visible region before and after the heating press under the above conditions.
When this plate-like body was visually observed, there was no change in color before and after the heating press. (2) The spectral transmittance curve of the plate-shaped body manufactured in Example 6 was measured using a spectrophotometer (U-4000 manufactured by Hitachi, Ltd.). Then, 150 ℃, 40k
The plate was heated and pressed at a pressure of gf / cm ² for 10 minutes, and the spectral transmittance curve of the plate was measured again. FIG. 2 shows the measurement results of the spectral transmittance curves before and after the heating press. As shown in FIG. 2, it was confirmed that this plate-shaped body had good absorption characteristics in the near-infrared region and excellent light transmittance in the visible region. From FIG. 2, it can be seen from FIG. 2 that before and after the heating press under the above conditions, the spectral characteristics in the near infrared region hardly change, and the light transmittance in the visible region decreases by only about 2% at the maximum. It is understood that there is almost no change. When this plate-like body was visually observed, there was no change in color before and after the heating press. (3) The spectral transmittance curve of the plate-like body manufactured in Example 8 was measured using a spectrophotometer (U-4000 manufactured by Hitachi, Ltd.). Then, 150 ℃, 40k
The plate was heated and pressed at a pressure of gf / cm ² for 10 minutes, and the spectral transmittance curve of the plate was measured again. FIG. 3 shows the measurement results of the spectral transmittance curves before and after the heating press. As shown in FIG. 3, it was confirmed that this plate-like body had good absorption characteristics in the near-infrared region and excellent light transmittance in the visible region. From FIG. 3, it can be seen that the plate has a maximum light transmittance of 2 in the visible to near-infrared region before and after the heating press under the above conditions.
It is understood that there is only a decrease in the percentage and almost no change.
When this plate-like body was visually observed, there was no change in color before and after the heating press. (4) The spectral transmittance curve of the plate manufactured in Comparative Example 3 was measured using a spectrophotometer (U-4000 manufactured by Hitachi, Ltd.). Then, 150 ℃, 40k
The plate was heated and pressed at a pressure of gf / cm ² for 10 minutes, and the spectral transmittance curve of the plate was measured again. FIG. 4 shows the measurement results of the spectral transmittance curves before and after the heating press. As shown in FIG. 4, the light transmittance of this plate after the heat press under the above conditions is closer to the visible region than the plate according to the present invention shown in the above (1) to (3). It was confirmed that the temperature significantly decreased in a wide region up to the infrared region. Visual observation of this plate-like body confirmed that yellowing occurred after hot pressing.

From the results of the above (1) to (4), the plate according to the present invention is more thermally stable than the conventional plate containing a polymerizable phosphate compound. And it is understood that it is suitable for thermoforming.

<Comparative Test 2 for Thermal Stability> Under the same heating press conditions as in Comparative Test 1 for the thermal stability, the results of Examples 4, 6, 6, and 8 were compared. The results of measuring the spectral absorptance curves of the manufactured plate-like body before and after the heating press are shown in FIGS.
7 and 8. From the results of the measurement of the spectral absorptivity curve, as confirmed in the above-mentioned comparative test 1 on thermal stability, the plate-like body containing the copper phosphate ester used in the present invention is a conventional polymer. It is understood that the material is more thermally stable than that containing a phosphoric acid ester compound having properties and is suitable for thermoforming.

<Comparative Test 3 Regarding Thermal Stability> (1) The thermal decomposition characteristics of the copper complex (copper phosphate compound) obtained in Example 3 were measured using the following apparatus and conditions. a) Measuring device: TA4000 thermal analysis system manufactured by METTLER b) Measuring conditions-Heating rate: 10 ° C / min-Temperature range: 30 to 300 ° C-Atmosphere: Nitrogen atmosphere Fig. 9 shows copper phosphate ester according to Example 3. It is a graph which shows the thermal decomposition chart of a compound. As shown in FIG. 9, the weight change of the phosphoric acid ester copper compound according to Example 3 to around 200 ° C. was scarcely observed. (2) The thermal decomposition characteristics of the copper complex (phosphate copper compound) obtained in Example 5 were measured using the same apparatus and conditions as in (1) above. FIG. 10 is a graph showing a pyrolysis chart of the copper phosphate compound according to Example 5. As shown in FIG. 10, the phosphoric ester copper compound according to Example 5 showed almost no change in weight up to around 200 ° C. (3) The thermal decomposition characteristics of the copper complex (copper phosphate compound) obtained in Example 7 were measured using the same apparatus and conditions as in (1) above. FIG. 11 is a graph showing a pyrolysis chart of the copper phosphate compound according to Example 7. As shown in FIG. 11, the phosphoric acid ester copper compound according to Example 7 did not substantially change in weight up to around 230 ° C. (4) Copper complex (phosphate copper compound) obtained from the phosphate compound and copper acetate used in Comparative Example 3 above
Was measured using the same apparatus and conditions as in (1) above. FIG. 12 is a graph showing a pyrolysis chart of the copper phosphate compound according to Comparative Example 3. From FIG.
The weight of the conventional phosphoric acid ester copper compound according to Comparative Example 3 gradually decreases from around 150 ° C., and the temperature is lower than that of the phosphoric acid ester copper compound according to the present invention in (1) to (3). It was found that thermal decomposition occurred.

From the results of the above (1) to (4), the phosphoric acid ester copper compound as the heat ray absorbing compound according to the present invention is more thermally than the conventional polymerizable phosphoric acid ester copper compound. It is understood that it is stable. Then, when the results of Comparative Tests 1 and 2 relating to the above thermal stability are evaluated together, a phosphate copper compound as a near-infrared light absorbing compound according to the present invention and a near-infrared light absorbing agent containing this compound In addition, it is understood that a material using this near-infrared light absorber, for example, a display front plate has excellent thermal stability as compared with the conventional one, and is suitable for heat processing such as hot pressing. Is done.

[0125]

As described above, according to the present invention, the near-infrared light absorption performance is excellent, the thermal and chemical stability is excellent as compared with the prior art, and the production method and material selectivity are excellent. In addition, it is possible to obtain a near-infrared light-absorbing compound capable of improving molding processability, a method for producing the same, and a near-infrared light absorbing agent. Further, according to the present invention, by using such a near-infrared light absorbing agent, it is possible to obtain a display front panel excellent in near-infrared light absorbing performance and thermal and chemical stability.

[Brief description of the drawings]

FIG. 1 is a graph showing a spectral transmittance curve of a plate-like body according to Example 4 before and after hot pressing.

FIG. 2 is a graph showing spectral transmittance curves of a plate-like body according to Example 6 before and after hot pressing.

FIG. 3 is a graph showing a spectral transmittance curve of a plate-like body according to Example 8 before and after hot pressing.

FIG. 4 is a graph showing spectral transmittance curves of a plate-like body according to Comparative Example 3 before and after hot pressing.

FIG. 5 is a graph showing spectral absorptance curves before and after hot pressing of a plate-like body according to Example 4.

FIG. 6 is a graph showing a spectral absorptance curve before and after hot pressing of a plate-like body according to Example 6.

FIG. 7 is a graph showing spectral absorptance curves of a plate-shaped body according to an example 8 before and after hot pressing.

FIG. 8 is a graph showing spectral absorptance curves of a plate-like body according to Comparative Example 3 before and after hot pressing.

FIG. 9 is a graph showing a pyrolysis chart of a copper phosphate compound according to Example 3.

FIG. 10 is a graph showing a pyrolysis chart of a copper phosphate ester compound according to Example 5.

FIG. 11 is a graph showing a pyrolysis chart of a copper phosphate ester compound according to Example 7.

FIG. 12 is a graph showing a thermal decomposition chart of a copper phosphate ester compound according to Comparative Example 3.

FIG. 13 is a view showing one embodiment of a display front plate of the present invention, wherein FIG. 13 (a) is a sectional view and FIG. 13 (b) is an exploded perspective view showing a laminated structure.

FIG. 14 is a perspective view showing a use state of one embodiment of the display front plate of the present invention.

[Explanation of symbols]

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

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Mitsunori Hakozaki 16 Nishikicho Ochiai, Iwaki City, Fukushima Prefecture Inside Kureha Chemical Industry Co., Ltd. Reference) 2H048 CA04 CA09 CA12 CA19 CA24 2K009 AA02 BB14 BB24 4J002 BB031 BB121 BC031 BC091 BC111 BC121 BD041 BG011 BG041 BG051 BG061 BG071 BG131 CD191 CF061 CG001 CH051 EW046 FD020 FD046 5G435 A435

Claims (9)

[Claims] 1. A near-infrared light-absorbing compound which is a phosphoric acid ester copper compound obtained by reacting a phosphoric acid ester compound represented by the following formula (1) with a copper compound. Embedded image [In the formula (1), R independently represents a group represented by the following formula (2) or the following formula (3), and n is 1 or 2. Embedded image (In the formulas (2) and (3), R ¹ independently has 6 carbon atoms.
To 20 aryl groups (provided that the hydrogen of the aryl group may be substituted with at least one alkyl group having 1 to 6 carbon atoms or halogen, and the hydrogen of the alkyl group may be substituted with at least one hydrogen atom. R ² is independently an alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 6. )] 2. A near-infrared light-absorbing compound which is a phosphoric acid ester copper compound obtained by reacting a phosphoric acid ester compound represented by the following formula (4) with a copper compound. Embedded image [In the formula (4), R independently represents a group represented by the following formula (5) or the following formula (6), and n is 1 or 2. Embedded image (In the formulas (5) and (6), R ³ and R ^{4 each} independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group (provided that hydrogen of the aryl group is an alkyl group having 1 to 6 carbon atoms.) Group, or may be substituted by at least one halogen.
And at least one hydrogen of the alkyl group may be substituted by halogen). )] 3. A near-infrared light-absorbing compound, which is a phosphoric acid ester copper compound obtained by reacting a phosphoric acid ester compound represented by the following formula (7) with a copper compound. Embedded image [In the formula (7), R represents a group represented by the following formula (8), and n is 1 or 2. Embedded image (In the formula (8), R ⁵ represents an alkyl group having 1 to 20 carbon atoms or an aryl group (provided that at least one hydrogen of the aryl group is substituted by an alkyl group having 1 to 6 carbon atoms or halogen) And R ⁶ , R ⁷ , and R ^{8 each} independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms (provided that the hydrogen of the alkyl group may be substituted with at least one hydrogen atom). , R ⁶ , R ⁷ , and R ⁸ except for the case where all are hydrogen), and m is an integer of 1 to ^6. )] 4. A phosphoric acid ester copper compound by reacting at least one of the phosphoric acid ester compounds represented by the formulas (1), (4) and (7) with a copper compound. A method for producing a near-infrared light-absorbing compound, comprising the step of: 5. In the step, the phosphate compound and the copper compound are reacted in an organic solvent,
The method according to claim 4, wherein the acid component generated by the reaction and the organic solvent are removed. 6. A near-infrared light absorbing agent comprising at least one compound among the near-infrared light absorbing compounds according to claim 1. Description: 7. The near-infrared light absorber according to claim 6, wherein the near-infrared light absorber is formed of a resin composition in which the compound is contained in a resin. 8. A display front plate comprising a near infrared light absorbing layer containing the near infrared light absorbing agent according to claim 6. 9. The display front panel according to claim 8, wherein the display is a plasma display panel.