JP2016094512A - Method of producing near-infrared absorber fluid dispersion and near-infrared absorber fluid dispersion, and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a near-infrared absorber fluid dispersion capable of providing a resin composition excellent in light resistance, and a method of producing the fluid dispersion.SOLUTION: The method of producing the near-infrared absorber fluid dispersion has a step A of reacting at least one of copper organic acid salt and hydrate of the copper organic acid salt with a phosphonic acid compound represented by the general formula (1) [in the formula, Rrepresents a monovalent group represented by -CHCH-R, Rrepresents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group having 1 to 20 carbon atoms], in a solvent to obtain a reaction mixture containing a near-infrared absorber, a step B of removing at least a part of a liquid component in the reaction mixture, a step C of obtaining the near-infrared absorber fluid dispersion from a reaction mixture obtained by removing at least a part of liquid component obtained in the step B and a dispersant and a step D of removing at least a part of organic acid from a near-infrared absorber in the near-infrared absorber fluid dispersion and the resulting fluid dispersion contains a refined near-infrared absorber.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a near-infrared absorbent dispersion, a near-infrared absorbent dispersion, and uses thereof.

  Copper ions are excellent in absorption characteristics of light in the near-infrared region (hereinafter also referred to as “near-infrared rays”), and near-infrared absorbers utilizing the absorption characteristics of near-infrared light possessed by copper ions have been proposed. (For example, refer to Patent Document 1).

  In Patent Document 1, a specific phosphonic acid compound, a specific phosphate ester compound, and a copper salt are reacted to obtain a reaction mixture containing a near-infrared absorber, and then purified by a specific method. Discloses a method for producing a near-infrared absorbent dispersion containing a purified near-infrared absorbent obtained by the method described above. In Patent Document 1, the near-infrared absorbent dispersion obtained by the production method is excellent in dispersibility of the near-infrared absorbent, and the resin composition prepared from the dispersion is excellent in heat resistance. Is disclosed.

  Although it has been studied in the past to improve the properties of near-infrared absorbers by the raw materials used in the production of near-infrared absorbers and purification methods, the properties of near-infrared absorbers have been improved in order to be used more appropriately for various applications. It was desired to improve it further.

International Publication No. 2014/038035

  The present invention has been made in view of the above prior art, and an object thereof is to provide a near-infrared absorbent dispersion capable of obtaining a resin composition excellent in light resistance and a method for producing the dispersion.

  As a result of intensive studies to solve the above problems, the present inventors have found that the resin composition obtained using the near-infrared absorbent dispersion obtained by a specific method is excellent in light resistance. The headline and the present invention were completed.

That is, the method for producing a near-infrared absorber dispersion of the present invention comprises at least one of an organic acid copper salt and an organic acid copper salt hydrate and a phosphonic acid compound represented by the following general formula (1) as a solvent. In step A to obtain a reaction mixture containing a near infrared absorber,
Removing at least a portion of the liquid components in the reaction mixture, B
Step C for obtaining a near-infrared absorbent dispersion from the reaction mixture from which at least a part of the liquid component obtained in Step B has been removed, and a dispersion medium, and
It is a manufacturing method of the near-infrared absorber dispersion containing the refine | purified near-infrared absorber which has the process D which removes at least one part of an organic acid from the near-infrared absorber in the said near-infrared absorber dispersion.

［一般式（１）中、Ｒ¹は、−ＣＨ₂ＣＨ₂−Ｒ¹¹で表される１価の基であり、Ｒ¹¹は水素原子、炭素数１〜２０のアルキル基、または炭素数１〜２０のフッ素化アルキル基を示す。］

[In General Formula (1), R ¹ is a monovalent group represented by —CH ₂ CH ₂ —R ¹¹ , and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 carbon atom. Represents -20 fluorinated alkyl groups. ]

The step D is preferably at least one step selected from the following (1) to (9).
(1) Step of adding a near-infrared absorbent dispersion to obtain a near-infrared absorbent dispersion containing a purified near-infrared absorbent (2) Adding an alcohol to the near-infrared absorbent dispersion and a temperature of 40 to 150 The process of obtaining the near-infrared absorber dispersion containing the refined near-infrared absorber by heating at 0 ° C. (3) The near-infrared absorber purified by heating the near-infrared absorber dispersion at a temperature of 40 to 150 ° C. (4) A step of obtaining a near-infrared absorbent dispersion containing a purified near-infrared absorbent by irradiating the near-infrared absorbent dispersion with ultrasonic waves for 4 hours or more (4) 5) Step of adding a phosphonic acid compound represented by the general formula (1) to the near-infrared absorber dispersion to obtain a near-infrared absorber dispersion containing a purified near-infrared absorber (6) Near-infrared absorption The agent dispersion is 20 at 0-40 ° C. Step of obtaining a near-infrared absorber dispersion containing a purified near-infrared absorber for 200 days (7) A near-infrared ray containing a purified near-infrared absorber by adding a dispersant to the near-infrared absorber dispersion Step of obtaining an absorbent dispersion (8) Step of adding a dispersant to the near-infrared absorber dispersion and heating at a temperature of 40 to 150 ° C. to obtain a near-infrared absorber dispersion containing a purified near-infrared absorber. (9) A step of obtaining a near-infrared absorbent dispersion containing a purified near-infrared absorber using alcohol as at least a part of the dispersion medium in the step C. The reaction in the step A is performed in the presence of a dispersant. Is preferred.

  The dispersant used in Step A is at least selected from a phosphoric acid monoester represented by the following general formula (2), a phosphoric acid diester represented by the following general formula (3), and alkali metal salts thereof. It is preferable that it is one type of phosphate ester compound.

［一般式（２）および（３）中、Ｒ²、Ｒ³およびＲ⁴は、−（ＣＨ₂ＣＨ₂Ｏ）_nＲ¹²で表される１価の基であり、ｎは２〜６５の整数であり、Ｒ¹²は、炭素数６〜３５のアルキル基または炭素数６〜３５のアルキルフェニル基を示す。ただし、Ｒ²、Ｒ³およびＲ⁴は、それぞれ同一でも異なっていてもよい。］

[In General Formulas (2) and (3), R ² , R ³ and R ⁴ are monovalent groups represented by — (CH ₂ CH ₂ O) _n R ¹² , and n is from 2 to 65. It is an integer and R ¹² represents an alkyl group having 6 to 35 carbon atoms or an alkylphenyl group having 6 to 35 carbon atoms. However, R ² , R ³ and R ⁴ may be the same or different. ]

The method for producing a near-infrared absorbent dispersion of the present invention may further include a step E of removing a part of the dispersion medium and the organic acid in the near-infrared absorbent dispersion obtained in the step D. Good.
The near-infrared absorber dispersion liquid of the present invention is obtained by the above production method.
The near-infrared absorber of the present invention is obtained from the near-infrared absorber dispersion.
The resin composition of this invention contains the said near-infrared absorber and resin.
The interlayer film for laminated glass of the present invention is formed from the resin composition.
The laminated glass of the present invention has the interlayer film for laminated glass.

  By using the purified near-infrared absorbent dispersion obtained by the production method of the present invention, it is possible to obtain a resin composition having excellent light resistance.

Next, the present invention will be specifically described.
[Method for producing near-infrared absorbent dispersion]
The method for producing a near-infrared absorbent dispersion of the present invention comprises at least one of an organic acid copper salt and an organic acid copper salt hydrate and a phosphonic acid compound represented by the following general formula (1) in a solvent. Step A for obtaining a reaction mixture containing a near-infrared absorber, Step B for removing at least part of the liquid component in the reaction mixture, and at least part of the liquid component obtained in Step B were removed. It has the process C which obtains a near-infrared absorber dispersion liquid from a reaction mixture and a dispersion medium, and the process D which removes at least one part of an organic acid from the near-infrared absorber in the said near-infrared absorber dispersion liquid. In the manufacturing method of the near-infrared absorber dispersion liquid of the present invention, since the process D is included, the content of the organic acid contained in the near-infrared absorber itself is reduced as compared with the conventional manufacturing method of the near-infrared absorber dispersion liquid. It is possible. That is, the dispersion obtained by the method for producing a near-infrared absorber dispersion of the present invention contains a purified near-infrared absorber.

［一般式（１）中、Ｒ¹は、−ＣＨ₂ＣＨ₂−Ｒ¹¹で表される１価の基であり、Ｒ¹¹は水素原子、炭素数１〜２０のアルキル基、または炭素数１〜２０のフッ素化アルキル基を示す。］

[In General Formula (1), R ¹ is a monovalent group represented by —CH ₂ CH ₂ —R ¹¹ , and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 carbon atom. Represents -20 fluorinated alkyl groups. ]

  In the method of obtaining a near-infrared absorber by reacting a conventional organic acid copper salt or a hydrate thereof with a phosphonic acid compound, the present inventors include an organic acid copper salt or water thereof in the near-infrared absorber. It is considered that the organic acid derived from the Japanese product remains, the organic acid is present in a state bonded by a coordination bond or the like in the near-infrared absorber, and the near-infrared absorber is simply vacuum-dried, etc. It was found that this method is difficult to remove, and that the organic acid is a cause of blackening that occurs when a resin composition containing a near infrared absorber is irradiated with light. In the production method of the present invention, it is possible to reduce the organic acid present in the near-infrared absorber, and the resin composition containing the near-infrared absorber of the present invention is suppressed from blackening and has light resistance. Excellent.

[Step A]
The method for producing a near-infrared absorbent dispersion of the present invention comprises reacting at least one of an organic acid copper salt and an organic acid copper salt hydrate with a phosphonic acid compound represented by the general formula (1) in a solvent. Step A to obtain a reaction mixture containing a near-infrared absorber.

  In step A, a near-infrared absorber is contained by reacting at least one of an organic acid copper salt and an organic acid copper salt hydrate with a phosphonic acid compound represented by the general formula (1) in a solvent. Although a reaction mixture is obtained, the reaction may be performed using other raw materials. As another raw material, for example, a dispersant can be used.

  Examples of the dispersing agent include anionic dispersing agents such as a phosphoric acid dispersing agent and a sulfonic acid dispersing agent, and a phosphoric acid dispersing agent is preferable. As the phosphate dispersant, a phosphate ester dispersant is preferable. The phosphate ester dispersant is at least selected from a phosphoric acid monoester represented by the following general formula (2), a phosphoric acid diester represented by the following general formula (3), and alkali metal salts thereof. One type of phosphate compound is preferred.

［一般式（２）および（３）中、Ｒ²、Ｒ³およびＲ⁴は、−（ＣＨ₂ＣＨ₂Ｏ）_nＲ¹²で表される１価の基であり、ｎは２〜６５の整数であり、Ｒ¹²は、炭素数６〜３５のアルキル基または炭素数６〜３５のアルキルフェニル基を示す。ただし、Ｒ²、Ｒ³およびＲ⁴は、それぞれ同一でも異なっていてもよい。］
なお、本発明において、「一般式（１）で表されるホスホン酸化合物」を、「特定のホスホン酸化合物」とも記す。

[In General Formulas (2) and (3), R ² , R ³ and R ⁴ are monovalent groups represented by — (CH ₂ CH ₂ O) _n R ¹² , and n is from 2 to 65. It is an integer and R ¹² represents an alkyl group having 6 to 35 carbon atoms or an alkylphenyl group having 6 to 35 carbon atoms. However, R ² , R ³ and R ⁴ may be the same or different. ]
In the present invention, the “phosphonic acid compound represented by the general formula (1)” is also referred to as “specific phosphonic acid compound”.

  The near-infrared absorber contained in the reaction product obtained in step A is obtained mainly by the reaction between the specific phosphonic acid compound and at least one of an organic acid copper salt and an organic acid copper salt hydrate. It is thought that it has a near-infrared absorption characteristic with the copper ion which the phosphonic acid copper salt which is obtained. The copper phosphonate is represented by the following general formula (4).

The near-infrared absorber obtained in the step A has a structure represented by the following general formula (4), and when other raw materials are used, it also has a structure derived from the raw materials.
For example, when a dispersant is used, the near-infrared absorber is considered that the specific phosphonic acid compound is mainly coordinated with copper ions, and further a dispersant is present therearound. Moreover, when the phosphate ester type | system | group dispersing agent is used as a dispersing agent, it is thought that the said phosphate ester type | system | group dispersing agent coordinates to some copper ions.

  For this reason, the copper ion in the near-infrared absorber is excellent in stability to heat or the like. For example, when the near-infrared absorber is used together with a resin, the resin composition containing the near-infrared absorber and the resin Even when the molding is performed, the resin is not affected by copper ions, and is less colored and excellent in transparency.

［一般式（４）中、Ｒ¹は、−ＣＨ₂ＣＨ₂−Ｒ¹¹で表される１価の基であり、Ｒ¹¹は水素原子、炭素数１〜２０のアルキル基、または炭素数１〜２０のフッ素化アルキル基を示す。］

[In General Formula (4), R ¹ is a monovalent group represented by —CH ₂ CH ₂ —R ¹¹ , and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 carbon atom. Represents -20 fluorinated alkyl groups. ]

R ¹¹ in the general formulas (1) and (4) is hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl. Group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, perfluoroethyl group, perfluoropropyl group, perfluoro-n-butyl group, perfluorohexyl group, perfluorooctyl Group, perfluorodecyl group and the like.

Further, when producing a reaction mixture containing a near-infrared absorber in step A, the R ¹¹ in the general formulas (1) and (4) is a group having a large number of carbon atoms or a group having a long molecular chain. Since dispersibility tends to decrease, R ¹¹ is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 2 to 10 carbon atoms.

  The phosphate ester-based dispersant that can be used in the present invention is not particularly limited as long as it is a phosphate ester compound used as a dispersant, and is preferably represented by the following general formula (2). At least one phosphoric acid ester compound selected from phosphoric acid monoesters, phosphoric acid diesters represented by the following general formula (3), and alkali metal salts thereof is used.

［一般式（２）および（３）中、Ｒ²、Ｒ³およびＲ⁴は、−（ＣＨ₂ＣＨ₂Ｏ）_nＲ¹²で表される１価の基であり、ｎは２〜６５の整数であり、Ｒ¹²は、炭素数６〜３５のアルキル基または炭素数６〜３５のアルキルフェニル基を示す。ただし、Ｒ²、Ｒ³およびＲ⁴は、それぞれ同一でも異なっていてもよい。］

[In General Formulas (2) and (3), R ² , R ³ and R ⁴ are monovalent groups represented by — (CH ₂ CH ₂ O) _n R ¹² , and n is from 2 to 65. It is an integer and R ¹² represents an alkyl group having 6 to 35 carbon atoms or an alkylphenyl group having 6 to 35 carbon atoms. However, R ² , R ³ and R ⁴ may be the same or different. ]

  In the present invention, “at least one phosphoric acid selected from a phosphoric acid monoester represented by the general formula (2), a phosphoric acid diester represented by the general formula (3), and an alkali metal salt thereof” “Ester compound” is also referred to as “specific phosphate ester compound”.

In the general formulas (2) and (3), R ² , R ³ and R ⁴ are monovalent groups (polyoxyalkyl groups) represented by — (CH ₂ CH ₂ O) _n R ¹² . n is an integer of 2 to 65, preferably an integer of 4 to 65, more preferably 4 to 45, and particularly preferably an integer of 6 to 45. When n is less than 2, when a molded product is produced using a near-infrared absorber together with a resin, the molded product may have insufficient transparency. On the other hand, if n exceeds 65, the amount of the phosphoric acid ester compound necessary for obtaining a molded article having sufficient transparency increases, resulting in high costs.

R ¹² is an alkyl group having 6 to 35 carbon atoms or an alkylphenyl group having 6 to 35 carbon atoms, preferably an alkyl group having 6 to 35 carbon atoms, and an alkyl group having 6 to 25 carbon atoms. More preferably, it is particularly preferably an 8-20 alkyl group, and most preferably 12-20 alkyl group. If R ¹² is a group having less than 6 carbon atoms, the transparency of the molded product may be insufficient. Further, if R ¹² is a group having more than 35 carbon atoms, the amount of a phosphoric acid ester compound necessary for obtaining a molded article having sufficient transparency increases, resulting in high costs.

  When obtaining the near-infrared absorber in step A, at least selected from the phosphoric acid monoester represented by the general formula (2), the phosphoric acid diester represented by the general formula (3), and alkali metal salts thereof. When using one kind of phosphoric acid ester compound, either using only the phosphoric acid monoester represented by the general formula (2) or using only the phosphoric acid diester represented by the general formula (3), Only the alkali metal salt of the phosphoric acid monoester represented by the general formula (2) may be used, or only the alkali metal salt of the phosphoric acid diester represented by the general formula (3) may be used. 2) The phosphoric acid monoester represented by formula (3) and the phosphoric acid diester represented by formula (3) are used together, or the alkali metal salt of the phosphoric acid monoester represented by formula (2), Phosphoric acid die represented by the formula (3) It is preferable to use an alkali metal salt of an alkali metal salt of ether.

  The phosphoric acid monoester represented by the general formula (2) and the phosphoric acid diester represented by the general formula (3), or the alkali metal salt of the phosphoric acid monoester represented by the general formula (2) And the alkali metal salt of the alkali metal salt of the phosphoric acid diester represented by the general formula (3) is preferred because the molded article tends to be excellent in transparency and heat resistance. In these cases, the ratio of the phosphoric acid monoester represented by the general formula (2) and the phosphoric acid diester represented by the general formula (3) is not particularly limited, but usually a molar ratio ((2) : (3)) is 10:90 to 90:10.

  Moreover, as a phosphoric acid monoester represented by the said General formula (2), it may be used individually by 1 type, or 2 or more types may be used, As phosphoric acid diester represented by the said General formula (3), These may be used alone or in combination of two or more.

  When the alkali metal salt is used, the phosphoric acid monoester represented by the general formula (2) and the phosphoric acid diester represented by the general formula (3) are neutralized with an alkali metal compound. It is possible to obtain.

  Examples of the alkali metal compounds include alkali metal oxides, hydroxides, halides, hydrides, and organic acid salts such as hydrogen carbonate, carbonate, nitrate, hydrogen sulfate, sulfate, formate, and acetate. And alkali metal hydroxides, bicarbonates and carbonates are preferred.

  Examples of the metal species constituting the alkali metal compound include lithium, sodium, potassium, rubidium, cesium, and francium. Sodium, potassium, and cesium are preferable, and sodium is more preferable. That is, the alkali metal compound is preferably at least one salt selected from a sodium salt, a potassium salt, and a cesium salt, and more preferably a sodium salt.

In addition, as an alkali metal compound, 1 type may be used or 2 or more types may be used.
Further, as the dispersant, other phosphate esters can be used. Examples of other phosphate esters include phosphate triesters, and these phosphate triesters may be used alone or together with the specific phosphate ester compound.

  As the phosphoric acid monoester represented by the following general formula (2), the phosphoric acid diester represented by the following general formula (3), and at least one phosphoric acid ester compound selected from these alkali metal salts: Commercially available phosphate ester compounds can also be used.

  As at least one of the organic acid copper salt and organic acid copper salt hydrate, at least one of organic acid copper salt and organic acid copper salt hydrate capable of supplying divalent copper ions is usually used. Used. Examples of the hydrates of the organic acid copper salt and the organic acid copper salt include, for example, copper acetate anhydride, copper formate anhydride, copper stearate anhydride, copper benzoate anhydride, copper ethyl acetoacetate anhydride, copper pyrophosphate anhydride Products, organic acid copper salts such as copper naphthenate anhydride and copper citrate anhydride, and hydrates of the organic acid copper salts. In addition, as at least one of the organic acid copper salt and the hydrate of the organic acid copper salt, one kind may be used alone, or two or more kinds may be used.

  As at least one of the organic acid copper salt and the organic acid copper salt hydrate, copper acetate anhydride and copper acetate monohydrate are preferably used in terms of solubility and removal of by-products. In addition, when copper acetate anhydride and copper acetate monohydrate are used as at least one of organic acid copper salt and organic acid copper salt hydrate, the near-infrared absorber obtained in step A contains It is considered that acetic acid, which is an organic acid, exists in a state of being bound by a coordination bond or the like.

Moreover, the quantity of each said component used at the process A is as follows.
The specific phosphonic acid compound is preferably 0.4 mol or more and 0.5 to 1.5 mol per 1 mol of copper in the organic acid copper salt and the hydrate of the organic acid copper salt. Is more preferable, and 0.7 to 1.2 mol is particularly preferable. Within the said range, since the transparency and heat resistance of a molded object are especially excellent, it is preferable.

  Moreover, when using a specific phosphoric acid ester compound as a dispersing agent, it is preferable to use the said specific phosphonic acid compound 5 mol or more with respect to 1 mol of said phosphoric acid ester compounds, and using 8-100 mol. It is more preferable to use 10 to 80 mol.

  The solvent used for the reaction preferably includes at least one organic solvent selected from methanol, ethanol, isopropyl alcohol, n-butanol, N, N-dimethylformamide (DMF), and tetrahydrofuran (THF). Further, from the viewpoint of reactivity, it preferably contains at least one organic solvent selected from methanol, ethanol, THF, and DMF, and more preferably contains at least one organic solvent selected from methanol and ethanol. preferable. As said organic solvent, only these organic solvents may be contained and the other organic solvent may be included.

  The amount of the solvent used for the reaction is usually 500 to 20000 parts by mass, preferably 1000 to 15000 parts per 100 parts by mass of the copper salt (at least one of organic acid copper salt and organic acid copper salt hydrate). Part by mass.

  The organic solvent is at least one organic solvent selected from methanol, ethanol, isopropyl alcohol, n-butanol, DMF, and THF (preferably at least one selected from methanol, ethanol, THF, and DMF). The organic solvent is usually 0 to 50 parts by mass, preferably 0 to 30 parts by mass with respect to 100 parts by mass of the organic solvent, more preferably at least one organic solvent selected from methanol and ethanol. May be included. When two or more organic solvents are used as the organic solvent, specific examples thereof include denatured ethanol containing ethanol and a small amount of other organic solvents. The denatured ethanol usually contains 3 to 50 parts by mass, preferably 3 to 30 parts by mass of other organic solvents with respect to 100 parts by mass of ethanol. Examples of the modified ethanol include methanol-modified ethanol, isopropyl alcohol-modified ethanol, and toluene-modified ethanol.

  Step A is usually 0 to 80 ° C., preferably 10 to 60 ° C., more preferably room temperature to 60 ° C., particularly preferably 20 to 40 ° C., usually 0.5 to 60 hours, preferably Is carried out for 0.5 to 30 hours, more preferably 0.5 to 20 hours, particularly preferably 1 to 15 hours.

  By the step A, a reaction mixture containing a near infrared absorber is obtained. In addition to the near-infrared absorber, the reaction mixture may contain a solvent, a by-product such as an organic acid depending on the raw material used, an unreacted raw material, and the like.

[Step B]
The manufacturing method of the near-infrared absorber dispersion liquid of this invention has the process B which removes at least one part of the liquid component in the said reaction mixture obtained at the process A. FIG.

  As a method for removing at least a part of the liquid component of the reaction mixture obtained in step A, for example, a method in which the solid content in the reaction mixture is settled and the liquid component is removed as a supernatant, or the reaction mixture is distilled. The method of removing a liquid component as a fraction is mentioned.

Examples of the method for precipitating the solid content include a method for precipitating the solid content by allowing the reaction mixture to stand, and a method for precipitating the solid content by centrifuging the reaction mixture.
In addition, when solid content is settled, it is preferable to perform centrifugation from the viewpoint of shortening the time required for sedimentation. Further, the smaller the particle size of the solid content, the longer the time required for sedimentation. Acetone, ethanol, water or the like may be added to the reaction mixture for the purpose of aggregating the solid content and increasing the time required for sedimentation. When adding acetone, ethanol, water, etc. to a reaction mixture, it is preferable to add 10-20000 mass parts per 100 mass parts of solid content, and it is more preferable to add 20-15000 mass parts.

As a method of removing the solvent, a method of removing the solvent as a fraction by distilling the reaction mixture is preferable from the viewpoint that a general apparatus can be used.
Distillation is preferably performed under reduced pressure from the viewpoint of preventing thermal deterioration of the reaction mixture. That is, step B is preferably a step of removing the liquid component as a fraction by distillation of the reaction mixture under reduced pressure.

  When performing vacuum distillation, although it changes with kinds of organic solvent, as conditions of vacuum distillation, it is normally performed by the pressure of 0.01-15 kPa. In addition, although the outflow temperature of a fraction changes with kinds and pressures of liquid components, such as an organic solvent, it is 30-150 degreeC normally.

  When almost all liquid components are removed by the step B, the near-infrared absorber can be obtained as a solid content. In Step B, when a part of the solvent is removed, a near-infrared absorber dispersion containing the near-infrared absorber at a higher concentration than the reaction mixture obtained in Step A is obtained.

  In Step B, it is possible to remove the organic acid present as a liquid in the reaction mixture, but it is possible to remove the organic acid present in a state of being bound to the near-infrared absorber itself by a coordination bond or the like. I could not do it. For this reason, the near-infrared absorbent obtained by the conventional method for producing a near-infrared absorbent dispersion contains an organic acid in the particles of the near-infrared absorbent, and the near-infrared absorbent is used as a resin composition. In some cases, blackening may occur due to organic acids. On the other hand, in the method for producing a near-infrared absorbent dispersion of the present invention, blackening is suppressed because a near-infrared absorbent with a reduced organic acid content can be obtained by performing Step D described later. It has excellent light resistance.

[Step C]
The method for producing a near-infrared absorber dispersion of the present invention comprises a step C of obtaining a near-infrared absorber dispersion from the reaction mixture from which at least a part of the liquid component obtained in the step B has been removed and a dispersion medium. Have.

  As a method for obtaining a near-infrared absorber dispersion from the reaction mixture from which at least a part of the liquid component obtained in Step B has been removed and the dispersion medium, for example, when the reaction mixture is a solid, A dispersion medium is added to the mixture, and the solid content is dispersed by a method such as stirring and ultrasonic treatment to obtain a near-infrared absorbent dispersion, and the reaction mixture is obtained in step A as a near-infrared absorbent. In the case of a near-infrared absorbent dispersion containing a higher concentration than the reaction mixture, a dispersion medium is further added to the dispersion, followed by stirring, ultrasonic treatment, etc. to obtain a near-infrared absorbent dispersion. A method is mentioned. In addition, when performing an ultrasonic treatment, irradiation of an ultrasonic wave is normally performed for 0.5 to 7 hours, Preferably it is 1 to 6 hours.

  Examples of the dispersion medium include toluene, xylene, alcohol, tetrahydrofuran (THF), dimethylformamide (DMF), methylene chloride, chloroform, triethylene glycol bis (2-ethylhexanoate), and the like. May be used singly or in combination of two or more.

Examples of the alcohol include methanol, ethanol, propanol and the like.
In addition, when performing the process of (9) mentioned later as the process D, alcohol is used as at least one part of a dispersion medium.

  In the near-infrared absorbent dispersion obtained in Step C, the dispersion medium is preferably 1 to 100 parts by mass, and more preferably 3 to 50 parts by mass with respect to 1 part by mass of the near-infrared absorbent. .

  In the method for producing a near-infrared absorbent dispersion of the present invention, the steps B and C may be repeated. For example, after the first process C, the process D may be performed after performing the second process B and the second process C.

  In addition, from the viewpoint of reducing impurities in the obtained near-infrared absorber, at least the steps B and C are repeated once. That is, after performing the first step B and step C, at least once again step B and step C. It is preferable to carry out. When step B and step C are repeated, steps B and C are preferably repeated 1 to 5 times. The second and subsequent processes B are also referred to as processes B ', and the second and subsequent processes C are also referred to as processes C'.

  The step B is a step of removing at least a part of the liquid component in the reaction mixture, but the step B 'is a step of removing at least a part of the liquid component in the near infrared absorbent dispersion. Step C is a step of obtaining a near-infrared absorbent dispersion from the reaction mixture from which at least a part of the liquid component obtained in Step B has been removed and a dispersion medium. In this step, a near-infrared absorber dispersion is obtained from the near-infrared absorber from which at least a part of the liquid component obtained in step B ′ has been removed or a dispersion thereof and a dispersion medium.

  In the method for producing a near-infrared absorber dispersion of the present invention, when Steps B and C are repeated once, the production method of the present invention includes at least one of an organic acid copper salt and an organic acid copper salt hydrate. Step A in which a phosphonic acid compound represented by the general formula (1) is reacted in a solvent to obtain a reaction mixture containing a near-infrared absorber; Step B in which at least a part of the liquid component in the reaction mixture is removed Step C for obtaining a near-infrared absorbent dispersion from the reaction mixture from which at least a part of the liquid component obtained in Step B has been removed, and a dispersion medium, at least one of the liquid components in the near-infrared absorbent dispersion Step B ′ for removing a part, Step C for obtaining a near-infrared absorber dispersion from a near-infrared absorber or a dispersion thereof from which at least a part of the liquid component obtained in Step B ′ has been removed, and a dispersion medium 'And the near infrared A step D of removing at least a portion of the organic acids from the near-infrared absorbing material of adsorbents dispersion.

  In the manufacturing method of the near-infrared absorber dispersion liquid of the present invention, since the process D is included, a near-infrared absorber having a low organic acid content can be obtained as compared with the conventional manufacturing method of the near-infrared absorber dispersion liquid. .

[Step D]
The manufacturing method of the near-infrared absorber dispersion liquid of this invention has the process D which removes at least one part of an organic acid from the near-infrared absorber in the said near-infrared absorber dispersion liquid.

  In the method for producing a near-infrared absorbent dispersion of the present invention, a purified near-infrared absorbent is used to remove at least a part of the organic acid from the near-infrared absorbent in the near-infrared absorbent dispersion in Step D. It is possible to obtain a resin composition that is excellent in light resistance by using a purified near infrared absorber.

  In Step D, it is sufficient that at least a part of the organic acid can be removed from the near infrared absorbent, and the removed organic acid may be present in the near infrared absorbent dispersion. That is, in the step D, the organic acid may be transferred from the near-infrared absorber that is a solid content to the dispersion medium that is a liquid component.

The step D is not particularly limited as long as the organic acid can be removed. For example, the step D is preferably at least one step selected from the following (1) to (9).
(1) Step of adding a near-infrared absorbent dispersion to obtain a near-infrared absorbent dispersion containing a purified near-infrared absorbent (2) Adding an alcohol to the near-infrared absorbent dispersion and a temperature of 40 to 150 The process of obtaining the near-infrared absorber dispersion containing the refined near-infrared absorber by heating at 0 ° C. (3) The near-infrared absorber purified by heating the near-infrared absorber dispersion at a temperature of 40 to 150 ° C. (4) A step of obtaining a near-infrared absorbent dispersion containing a purified near-infrared absorbent by irradiating the near-infrared absorbent dispersion with ultrasonic waves for 4 hours or more (4) 5) Step of adding a phosphonic acid compound represented by the general formula (1) to the near-infrared absorber dispersion to obtain a near-infrared absorber dispersion containing a purified near-infrared absorber (6) Near-infrared absorption The agent dispersion is 20 at 0-40 ° C. Step of obtaining a near-infrared absorber dispersion containing a purified near-infrared absorber for 200 days (7) A near-infrared ray containing a purified near-infrared absorber by adding a dispersant to the near-infrared absorber dispersion Step of obtaining an absorbent dispersion (8) Step of adding a dispersant to the near-infrared absorber dispersion and heating at a temperature of 40 to 150 ° C. to obtain a near-infrared absorber dispersion containing a purified near-infrared absorber. (9) Step of obtaining a near-infrared absorbent dispersion containing a purified near-infrared absorber using alcohol as at least a part of the dispersion medium in Step C. Steps (1) to (9) are described below.

(Step (1))
The step (1) is a step of obtaining a near-infrared absorbent dispersion containing a purified near-infrared absorbent by adding alcohol to the near-infrared absorbent dispersion.

  In the step (1), alcohol is added to the near-infrared absorbent dispersion obtained in step C. Examples of the alcohol include methanol, ethanol, propanol, and butanol.

  The amount of alcohol added to the near-infrared absorbent dispersion is preferably 10 to 2000 parts by mass, more preferably 30 to 1000 parts by mass, per 100 parts by mass of the near-infrared absorbent.

In the step (1), by adding an alcohol, the equilibrium of the reaction for obtaining a near-infrared absorber from at least one of an organic acid copper salt and an organic acid copper salt hydrate and a specific phosphonic acid compound is achieved. It is thought that it moves to the production system side, and since the organic acid moves from the near-infrared absorber, which is a solid content, to the liquid side, the organic acid content of the near-infrared absorber itself decreases, and a purified near-infrared absorber is used. It is possible to obtain.
In the step (1), stirring may be performed after adding alcohol.

(Step (2))
Step (2) is a step of adding a near-infrared absorbent dispersion and heating at a temperature of 40 to 150 ° C. to obtain a near-infrared absorbent dispersion containing a purified near-infrared absorbent.
In the step (2), alcohol is added to the near-infrared absorbent dispersion obtained in step C. Examples of the alcohol include methanol, ethanol, propanol, and butanol.

  The amount of alcohol added to the near-infrared absorbent dispersion is preferably 10 to 2000 parts by mass, more preferably 30 to 1000 parts by mass, per 100 parts by mass of the near-infrared absorbent.

  In the step (2), a reaction for obtaining a near-infrared absorber from at least one of an organic acid copper salt and an organic acid copper salt hydrate and a specific phosphonic acid compound by adding alcohol and heating. It is thought that the equilibrium of the product moves to the production system side, and the organic acid moves from the near-infrared absorber, which is a solid content, to the liquid side. It is possible to obtain an absorbent. In the step (2), the organic acid easily moves to the liquid side by heating.

In the step (2), after adding the alcohol, the near-infrared absorbent dispersion is heated at a temperature of 40 to 150 ° C. The heating is more preferably 50 to 120 ° C. The heating time is preferably 0.5 to 12 hours, more preferably 2 to 7 hours.
In the step (2), after adding alcohol, stirring or the like may be performed.

(Step (3))
The step (3) is a step of heating the near-infrared absorber dispersion at a temperature of 40 to 150 ° C. to obtain a near-infrared absorber dispersion containing the purified near-infrared absorber.
In the step (3), by heating the near-infrared absorber dispersion liquid, the specific phosphonic acid and the dispersant that were present in the system in an unreacted state are combined with the organic acid in the near-infrared absorber. It is thought that the organic acid moves to the liquid side from the near-infrared absorber in which the organic acid is a solid content, so that the organic acid content of the near-infrared absorber itself is reduced and a purified near-infrared absorber is obtained. It is possible.

In the step (3), the near-infrared absorbent dispersion is heated at a temperature of 40 to 150 ° C. The heating is more preferably 50 to 120 ° C. The heating time is preferably 0.5 to 12 hours, more preferably 2 to 7 hours.
In the step (3), stirring or the like may be performed simultaneously with the heating.

(Step (4))
The step (4) is a step of obtaining a near-infrared absorbent dispersion containing a purified near-infrared absorbent by irradiating the near-infrared absorbent dispersion with ultrasonic waves for 4 hours or more.
In the step (4), the near-infrared absorbent dispersion is subjected to ultrasonic irradiation for 4 hours or more, so that the specific phosphonic acid and the dispersant that are present in the system unreacted are contained in the near-infrared absorbent. It is thought that it reacts with the part where the organic acid is bonded, and the organic acid moves from the near infrared absorber, which is a solid content, to the liquid side, so that the organic acid content of the near infrared absorber itself is reduced and purified. It is possible to obtain a near infrared absorber.

In the step (4), the near-infrared absorbent dispersion is irradiated with ultrasonic waves for 4 hours or longer, preferably 4 to 24 hours, more preferably 6 to 18 hours, and particularly preferably 10 to 16 hours.
In addition, although it does not specifically limit as temperature at the time of performing ultrasonic irradiation, Usually, 5-40 degreeC, Preferably it is 10-35 degreeC.

(Step (5))
The step (5) is a step of adding a phosphonic acid compound represented by the general formula (1) to the near-infrared absorber dispersion to obtain a near-infrared absorber dispersion containing a purified near-infrared absorber. is there.
The amount of the phosphonic acid compound represented by the general formula (1) added to the near-infrared absorber dispersion is preferably 0.1 to 10 parts by mass per 100 parts by mass of the near-infrared absorber. More preferably, it is 5-5 mass parts. The phosphonic acid compound may be added as a solution of the phosphonic acid compound.

When added as a solution of a phosphonic acid compound, examples of the solvent include methanol, ethanol, propanol, butanol and the like.
As the phosphonic acid compound represented by the general formula (1), it is preferable to use the same phosphonic acid compound as used in Step A for cost reduction and impurity type suppression.

In the step (5), it is considered that the phosphonic acid compound represented by the general formula (1) reacts with a portion to which the organic acid in the near-infrared absorbent is bonded, and the near-infrared in which the organic acid is a solid content. Since it moves from the absorber to the liquid side, the organic acid content of the near-infrared absorber itself is reduced, and a purified near-infrared absorber can be obtained.
In the step (5), stirring may be performed after adding the phosphonic acid compound.

(Step (6))
Step (6) is a step of obtaining a near-infrared absorbent dispersion containing a purified near-infrared absorbent by holding the near-infrared absorbent dispersion at 0 to 40 ° C. for 20 to 200 days.
In the step (6), the near-infrared absorbent dispersion is kept at 0 to 40 ° C. for 20 to 200 days, so that the specific phosphonic acid and the dispersant that are present in the system in an unreacted state are near infrared. The organic acid in the absorber is considered to react with the bonded part, and the organic acid moves from the solid near-infrared absorber, which is a solid content, to the liquid side, so the organic acid content of the near-infrared absorber itself decreases. It is possible to obtain a purified near-infrared absorber.

  In the step (6), the temperature for holding the near-infrared absorbent dispersion is 0 to 40 ° C., preferably 10 to 35 ° C., and the holding time is 20 to 200 days, preferably 25 to 150. Day.

(Step (7))
The process of (7) is a process of adding a dispersing agent to a near-infrared absorber dispersion liquid, and obtaining the near-infrared absorber dispersion liquid containing the refined near-infrared absorber.
The amount of the dispersant added to the near-infrared absorber dispersion is preferably 3 to 150 parts by mass, more preferably 5 to 100 parts by mass, per 100 parts by mass of the near-infrared absorber. The dispersant may be added as a dispersant solution.

  When added as a dispersant solution, the solvent includes methanol, ethanol, propanol, butanol, toluene, xylene, chloroform, methylene chloride, and the like.

  Examples of the dispersing agent include anionic dispersing agents such as a phosphoric acid dispersing agent and a sulfonic acid dispersing agent, and a phosphoric acid dispersing agent is preferable. As the phosphate dispersant, a phosphate ester dispersant is preferable. As the phosphate ester dispersant, at least one selected from the phosphoric acid monoester represented by the general formula (2), the phosphoric acid diester represented by the general formula (3), and alkali metal salts thereof. Phosphate ester compounds are preferred. When a dispersant is used in step A, it is preferable to use the same dispersant in step (7).

In the step (7), it is considered that the dispersant reacts with the portion where the organic acid in the near infrared absorber is bonded, and the organic acid moves from the near infrared absorber, which is a solid content, to the liquid side. In addition, the organic acid content of the near-infrared absorber itself is reduced, and a purified near-infrared absorber can be obtained.
In the step (7), stirring may be performed after adding the dispersant.

(Step (8))
The step (8) is a step of adding a dispersant to the infrared absorbent dispersion and heating at a temperature of 40 to 150 ° C. to obtain a near infrared absorbent dispersion containing a purified near infrared absorbent.
The amount of the dispersant added to the near-infrared absorber dispersion is preferably 3 to 150 parts by mass, more preferably 5 to 100 parts by mass, per 100 parts by mass of the near-infrared absorber. The dispersant may be added as a dispersant solution.

  When added as a dispersant solution, the solvent includes methanol, ethanol, propanol, butanol, toluene, xylene, chloroform, methylene chloride, and the like.

  Examples of the dispersing agent include anionic dispersing agents such as a phosphoric acid dispersing agent and a sulfonic acid dispersing agent, and a phosphoric acid dispersing agent is preferable. As the phosphate dispersant, a phosphate ester dispersant is preferable. As the phosphate ester dispersant, at least one selected from the phosphoric acid monoester represented by the general formula (2), the phosphoric acid diester represented by the general formula (3), and alkali metal salts thereof. Phosphate ester compounds are preferred. When a dispersant is used in step A, it is preferable to use the same dispersant in step (8).

  In the step (8), it is considered that the dispersant reacts with the portion where the organic acid in the near infrared absorber is bonded, and the organic acid moves from the near infrared absorber, which is a solid content, to the liquid side. In addition, the organic acid content of the near-infrared absorber itself is reduced, and a purified near-infrared absorber can be obtained. In the step (8), the organic acid easily moves to the liquid side by heating.

In the step (8), after adding the dispersant, the near-infrared absorbent dispersion is heated at a temperature of 40 to 150 ° C. The heating is more preferably 50 to 120 ° C. The heating time is preferably 0.5 to 12 hours, more preferably 2 to 7 hours.
In the step (8), stirring may be performed after adding the dispersant.

(Step (9))
The step (9) is a step of obtaining a near-infrared absorber dispersion liquid containing a purified near-infrared absorber by using alcohol as at least a part of the dispersion medium in the step C.
In the process (9), alcohol is used as at least a part of the dispersion medium in the process C as a premise.
Examples of the alcohol include methanol, ethanol, propanol, butanol and the like. When alcohol is used as at least a part of the dispersion medium in Step C, the alcohol is preferably 5 to 100 parts by mass and more preferably 10 to 90 parts by mass in 100 parts by mass of the dispersion medium.

  In the step (9), by adding an alcohol, the equilibrium of the reaction for obtaining a near-infrared absorber from at least one of an organic acid copper salt and a hydrate of an organic acid copper salt and a specific phosphonic acid compound is achieved. It is thought that it moves to the production system side, and since the organic acid moves from the near-infrared absorber, which is a solid content, to the liquid side, the organic acid content of the near-infrared absorber itself decreases, and a purified near-infrared absorber is used. It is possible to obtain.

In the step (9), stirring or the like may be performed.
In step D, at least one of the steps (1) to (9) is performed, a plurality of steps may be performed, and each step may be performed a plurality of times.

  Of the steps (1) to (9), the steps (1) to (5), (7), and (8) are preferable from the viewpoint of ease of operation and light resistance improvement effect. , (2), (5), (7), (8) are more preferred, and (2), (5), (7), (8) are particularly preferred.

  Moreover, from the viewpoint of the effect of improving long-term heat resistance, among the steps (1) to (9), the steps (1) to (4), (6), (7), and (9) are preferable. In step (5), the phosphonic acid compound used in step (5) may be present in the resin composition when a resin composition containing a near infrared absorber is prepared. Heat resistance may be deteriorated. In step (8), a dispersant is used, and the dispersant may be modified by heating. When a resin composition containing a near-infrared absorber is prepared, a modified product of the dispersant may be present in the resin composition, but the component may deteriorate long-term heat resistance. For example, when a phosphate ester dispersant is used as the dispersant, it may be partially modified by heating to become phosphoric acid. For this reason, among the steps (1) to (9), the steps (1) to (4), (6), (7), and (9) are preferable. Moreover, when implementing process (5) and (8), it is preferable to perform the method of removing liquid components, such as a dispersion medium and an organic acid, as a supernatant liquid in process E mentioned later. By carrying out this method, it is possible to prevent the phosphonic acid compound used in step (5) and the modified product of the dispersant used in step (8) from being present in the resin composition, and long-term heat resistance From the viewpoint of sex.

[Step E]
Although the manufacturing method of the near-infrared absorber dispersion liquid of this invention has the above-mentioned process A-process D, it may have the process E further.

Step E is a step of removing a part of the dispersion medium and the organic acid in the near-infrared absorbent dispersion obtained in Step D.
In Step E, by removing a part of the dispersion medium and the organic acid, it is possible to reduce the organic acid from the liquid component of the near-infrared absorbent dispersion liquid. In addition, the amount of organic acid contained in the composition can be easily reduced.

  The method for removing a part of the dispersion medium and the organic acid is not particularly limited, for example, a method of precipitating a near-infrared absorber that is a solid content and removing a liquid component such as the dispersion medium and the organic acid as a supernatant, The method of removing liquid components, such as a dispersion medium and an organic acid, as a fraction by distilling is mentioned. When removing at least a part of the dispersion medium and the organic acid by these methods, liquid components other than the dispersion medium and the organic acid may be removed at the same time.

  As a method for precipitating the near-infrared absorber, for example, a method of precipitating the near-infrared absorber by allowing the near-infrared absorber dispersion to stand, or a method of precipitating the near-infrared absorber dispersion, The method of making it settle is mentioned.

  As a method for removing a part of the liquid component such as the dispersion medium and the organic acid, from the viewpoint of improving dispersibility, a method of removing the liquid component such as the dispersion medium and the organic acid as a supernatant liquid by precipitating the near infrared absorber. Is preferred.

  In addition, when the near-infrared absorber is allowed to settle, it is preferable to perform centrifugation from the viewpoint of shortening the time required for sedimentation. Further, the smaller the particle size of the near infrared absorber, the longer the time required for sedimentation. Acetone, ethanol, water or the like may be added to the near-infrared absorber dispersion for the purpose of aggregating the near-infrared absorber and increasing the time required for sedimentation. When adding acetone, ethanol, water or the like to the near-infrared absorbent dispersion, it is preferably added in an amount of 10 to 20000 parts by mass per 100 parts by mass of the near-infrared absorber, and 20 to 15000 parts by mass may be added. More preferred.

  As a method for removing the liquid component such as the dispersion medium and the organic acid, a method of removing the dispersion medium as a fraction by distilling the near-infrared absorbent dispersion from the viewpoint that a general apparatus can be used is preferable.

  Distillation is preferably performed under reduced pressure from the viewpoint of preventing thermal degradation of the near infrared absorber. That is, it is preferable to remove liquid components such as a dispersion medium and an organic acid as a fraction by distilling the near-infrared absorbent dispersion under reduced pressure.

  When performing vacuum distillation, although it changes with kinds of a dispersion medium and an organic acid, as conditions for vacuum distillation, it is normally performed by the pressure of 0.01-15 kPa. In addition, although the outflow temperature of a fraction changes with kinds and pressures of a liquid component, it is 30-150 degreeC normally.

  In step E, the dispersion medium and part of the organic acid are removed to obtain a near-infrared absorbent dispersion. When removing the dispersion medium and the organic acid, etc., (almost) all of the liquid components are removed. The purified near-infrared absorber can be obtained as a solid content.

  In addition, when the process D is the process of (5), the added phosphonic acid compound may or may not be removed at the same time when the dispersion medium and a part of the organic acid are removed. Good. When the method of removing a part of the dispersion medium and the organic acid is a method of removing the liquid component such as the dispersion medium and the organic acid as a fraction by distillation, usually the phosphonic acid compound is not removed and the solid In the case of a method in which a near-infrared absorber, which is a component, is allowed to settle and a liquid component such as a dispersion medium and an organic acid is removed as a supernatant, the phosphonic acid compound is also usually removed.

  In addition, when the process D is the process of (7) or the process of (8), the added dispersant may be removed simultaneously when removing a part of the dispersion medium and the organic acid, It does not have to be removed. When the method of removing a part of the dispersion medium and the organic acid is a method of removing liquid components such as the dispersion medium and the organic acid as a fraction by distillation, the dispersant is usually not removed and the solid content is removed. In the case of a method in which the near-infrared absorber is settled and the liquid component such as the dispersion medium and the organic acid is removed as a supernatant, the dispersant is also usually removed.

[Near-infrared absorber dispersion]
The near-infrared absorbent dispersion of the present invention is obtained by the method for producing the near-infrared absorbent dispersion.
As a dispersion containing a near infrared absorber, the dispersion medium is preferably 1 to 100 parts by mass, and more preferably 3 to 50 parts by mass with respect to 1 part by mass of the near infrared absorber.

  The near-infrared absorbent contained in the near-infrared absorbent dispersion of the present invention is such that the amount of organic acid measured by high-performance liquid chromatography (HPLC) is 1 mol of copper salt constituting the near-infrared absorbent, that is, copper. It is preferable that it is 0.0075 mol or less with respect to 1 mol of atoms, and it is more preferable that it is 0.0001-0.0070 mol.

  Since the near-infrared absorbent dispersion of the present invention is obtained by the above production method, the amount of organic acid contained in the near-infrared absorbent is reduced compared to the conventional production method of a near-infrared absorbent dispersion. Yes. For this reason, the resin composition of the present invention has excellent light resistance because blackening that occurs when irradiated with light is suppressed.

[Near infrared absorber]
The near-infrared absorber of the present invention is obtained from the near-infrared absorber dispersion. The near-infrared absorber of the present invention is usually obtained by recovering the near-infrared absorber as a solid content from the near-infrared absorber dispersion.

  As a method for obtaining a near-infrared absorber, for example, in the method described in the step E, it can be obtained by removing (almost) all liquid components. Further, after removing the liquid component, drying may be performed under normal pressure or under reduced pressure.

  In addition, you may use the near-infrared absorber of this invention as a near-infrared absorber dispersion liquid again disperse | distributed to the dispersion medium for various uses. As a near-infrared absorber dispersion liquid, it is preferable that a dispersion medium is 1-100 mass parts with respect to 1 mass part of near-infrared absorbers, and it is more preferable that it is 3-50 mass parts. The near-infrared absorbent contained in the near-infrared absorbent dispersion is such that the amount of organic acid measured by high-performance liquid chromatography (HPLC) is 1 mole of copper atom relative to 1 mole of copper salt constituting the near-infrared absorbent. The amount is preferably 0.0075 mol or less, and more preferably 0.0001 to 0.0070 mol.

[Resin composition and resin solution]
The resin composition of this invention contains the said near-infrared absorber and resin.
As a method for producing a resin composition, the near infrared absorbent dispersion, a method of removing a liquid component such as a dispersion medium or a solvent of a resin solution containing a resin, the near infrared absorbent dispersion, and a resin And a method of mixing the near-infrared absorber and a resin. From the viewpoint of preventing the near-infrared absorber from aggregating again, the method for producing the resin composition is preferably a method for removing the liquid component of the resin solution. That is, the resin composition of the present invention is preferably obtained from a resin solution.

  Examples of the method for producing the resin solution include a method of mixing the near-infrared absorber dispersion and the resin, a method of mixing the near-infrared absorber dispersion and the resin solution, and the near-infrared absorber dispersion. And a method of mixing a resin and a solvent.

  In addition, when using a solvent for manufacture of the said resin solution, what is necessary is just to be able to melt | dissolve resin, For example, toluene, ethanol, methanol, a methylene chloride, chloroform etc. are mentioned. As the solvent, one kind may be used alone, or two or more kinds may be used.

  When the liquid component is removed, the removal method is not particularly limited, but it is usually performed by drying such as drying under normal pressure or vacuum drying. In addition, when an organic acid exists in the liquid component of a near-infrared absorber dispersion liquid, when removing the liquid component of a resin solution, it is possible to remove simultaneously.

  In addition, when obtaining the molded object which consists of this resin composition, you may obtain a molded object by performing manufacture and shaping | molding of this resin composition simultaneously, and after manufacturing this resin composition as a pellet etc., desired A molded body may be obtained by molding into a shape of, and after obtaining the resin composition as a master batch such as pellets, the master batch and the resin are used to perform various processes such as extrusion molding, cast molding, injection molding, etc. A molded body such as an interlayer film for laminated glass may be obtained by a molding method.

The resin is not particularly limited as long as it can disperse the above-described near-infrared absorber. For example, the following resins can be used.
The resin used in the present invention is selected from polyvinyl acetal resin, ethylene-vinyl acetate copolymer, (meth) acrylic acid resin, polyester resin, polyurethane resin, vinyl chloride resin, polyolefin resin, polycarbonate resin, and norbornene resin. It is preferable that at least one type of resin can disperse the near-infrared absorber well and is excellent in visible light transmittance.

  The resin used in the present invention is more preferably at least one resin selected from polyvinyl acetal resin or ethylene-vinyl acetate copolymer, polyvinyl butyral resin (PVB), or ethylene-vinyl acetate copolymer. Particularly preferred is at least one resin selected from coalescence. When polyvinyl acetal resin is used, it is excellent in dispersibility of the above-mentioned near-infrared absorber, and, for example, when an interlayer film for laminated glass is produced using the resin composition of the present invention, it has excellent adhesion to glass or the like. In addition, the resin composition is preferable because it is flexible. Moreover, as polyvinyl acetal resin, it is preferable to use polyvinyl butyral resin (PVB) from the viewpoints of glass adhesion, dispersibility, transparency, heat resistance, light resistance, and the like.

  The polyvinyl acetal resin may be a blend of two or more types depending on the required physical properties, or may be a polyvinyl acetal resin obtained by acetalizing by combining aldehydes during acetalization.

  The aldehyde is not particularly limited, and examples thereof include aldehydes having 1 to 10 carbon atoms, and more specifically, for example, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutylartaldehyde. N-hexylaldehyde, n-octylaldehyde, n-nonylaldehyde, n-decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Of these, n-butyraldehyde, n-hexylaldehyde, n-valeraldehyde and the like are preferable. More preferred is butyraldehyde having 4 carbon atoms.

Use of an ethylene-vinyl acetate copolymer is preferable from the viewpoints of excellent dispersibility of the above-mentioned near-infrared absorber and glass adhesion, dispersibility, transparency, heat resistance, light resistance, and the like.
Moreover, the resin composition of this invention may contain a plasticizer. The plasticizer is not particularly limited. For example, triethylene glycol bis (2-ethylhexanoate), triethylene glycol bis (2-ethylbutyrate), tetraethylene glycol bis (2-ethylhexanoate), Examples include tetraethylene glycol diheptanoate, dihexyl adipate, tributoxyethyl phosphate, and isodecylphenyl phosphate.

  It is preferable that the resin composition of this invention contains 0.5-30 mass parts of near-infrared absorbers per 100 mass parts of said resin, and it is more preferable to contain 1-25 mass parts. If the amount is less than 0.5 parts by mass, sufficient near-infrared absorption characteristics may not be obtained. If the amount is more than 30 parts by mass, the heat resistance, light resistance, transparency, and adhesion to glass of the resin are greatly reduced. There is a risk.

  When the resin composition of this invention contains the said plasticizer, it is preferable to contain 10-60 mass parts of plasticizers per 100 mass parts of said resin, and it is more preferable to contain 20-50 mass parts.

The resin composition of the present invention is excellent in light resistance and can be suitably used as an intermediate film for structural materials such as laminated glass.
Moreover, various additives may be contained in the resin composition of the present invention. Examples of the additive include a dispersant, an antioxidant, an ultraviolet absorber, and a light stabilizer. These additives may be added when manufacturing the resin composition of the present invention, or may be added when manufacturing a near-infrared absorber or resin.

[Use of resin composition]
The resin composition of the present invention is usually used for applications where it is desired to absorb near infrared rays.
Since the resin film formed from the resin composition of the present invention is excellent in light resistance, it can be suitably used as an intermediate film for structural materials such as an intermediate film for laminated glass.

  Moreover, the laminated glass of this invention has the said intermediate film for laminated glasses. There is no limitation in particular as glass which comprises the laminated glass of this invention, A conventionally well-known thing can be used.

EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.
[Measurement of acetic acid content of near-infrared absorber]
The amount of acetic acid contained in the near-infrared absorbent in the near-infrared absorbent dispersions obtained in Examples and Comparative Examples described below was measured by the following method.

  To a glass centrifuge tube having a capacity of 50 ml, 1.91 g of the copper salt toluene dispersion (near infrared absorber dispersion) obtained in each of the examples and comparative examples was taken, and 20 g of acetone was added. Using a table top centrifuge 4000 (Kubota Corp.), centrifugation was performed at 4200 rpm for 30 minutes to remove the transparent supernatant. However, n-butylphosphonic acid copper salt toluene dispersion (6) obtained in Example 6 was used instead of 1.91 g, 4.57 g, and n-butylphosphonic acid copper salt obtained in Comparative Example 2. For the toluene dispersion (c2) and the n-butylphosphonic acid copper salt toluene dispersion (7) obtained in Example 7, 5.21 g was used instead of 1.91 g.

When the supernatant did not become transparent, the centrifugation was continued until it became transparent, and then the supernatant was removed.
20 g of acetone was added to the resulting precipitate, and the precipitate lump was crushed using a stirring shaker and an ultrasonic washer to obtain a suspension.

  The suspension was centrifuged at 4200 rpm for 30 minutes to remove the transparent supernatant. The obtained precipitate was dried at 40 ° C. for 1 hour using a vacuum dryer to obtain 175 mg of a dried solid.

100 mg of this solid (near infrared absorber) was taken in a 10 ml volumetric flask, and 300 mg of 35% hydrochloric acid was added. When solid content did not melt | dissolve, it melt | dissolved using the ultrasonic cleaner and was made up with water.
20 μl of this liquid was injected into high performance liquid chromatography (HPLC) (Shimadzu Corporation, LC-1000), and the amount of acetic acid in the near infrared absorbent was calculated.

[Comparative Example 1]
(Preparation of copper salt dispersion (near infrared absorber dispersion))
To a 1 L eggplant-shaped flask, 10.0 g (50.09 mmol) of copper acetate monohydrate and 500 g of ethanol were added and stirred at 25 ° C. for 1 hour to obtain a liquid A.

In a separate container, a solution (Liquid B) in which 2.0 g of Prisurf A219B (Daiichi Kogyo Seiyaku) and 6.85 g of n-butylphosphonic acid were dissolved in 50 g of ethanol was prepared.
B liquid was dripped over 3 hours with respect to A liquid. The reaction was stirred at 25 ° C. for 18 hours.

Then, the solvent was distilled off with an evaporator (water bath 40-60 ° C.).
To this was added 440 g of toluene, and it was distilled off with an evaporator until it became a constant weight and no acetic acid odor occurred.

  A blue-green solid with a yield of 12.0 g (yield 100%) was obtained. To this, 103.5 g of toluene was added, and ultrasonic irradiation was performed for 3.5 hours to prepare an n-butylphosphonic acid copper salt toluene dispersion (c1) (near infrared absorber dispersion).

  The obtained n-butylphosphonic acid copper salt toluene dispersion (c1) was measured for the amount of acetic acid in the near-infrared absorber in accordance with the item [Measurement of acetic acid amount in the near-infrared absorber]. Acetic acid was contained in an amount of 0.0077 mol with respect to 1 mol of the acid copper salt.

(Preparation of copper salt fine particle dispersed resin (resin composition))
To a 300 ml Erlenmeyer flask, 1.90 g of triethylene glycol bis (2-ethylhexanoate), 40 g of ethanol, 100 g of toluene, and 5.00 g of polyvinyl butyral (PVB) were added. It stirred at 25 degreeC for 10 hours, and confirmed that PVB melt | dissolved completely.

  To this was added 1.35 g of the n-butylphosphonic acid copper salt toluene dispersion (c1) (containing 0.583 mmol of copper salt and 140 mg of a near infrared absorber (phosphonic acid copper salt and dispersing agent)). This dispersion was spread on a Teflon (registered trademark) vat and air-dried at 25 ° C. for 12 hours. Further, vacuum drying was performed at 40 ° C. for 5 hours and at 70 ° C. for 3.5 hours to completely remove the solvent, thereby obtaining a PVB resin (c1) (resin composition) in which copper salt fine particles were dispersed.

(Evaluation)
After the PVB resin (c1) in which the copper salt fine particles are dispersed is preheated at 120 ° C. and 3 MPa for 1 minute using a 0.8 mm thick formwork and a compression molding machine manufactured by Shinto Metal Industries, Ltd. Were pressed at 15 MPa for 3 minutes to obtain a resin sheet (c1).

<Preparation of measurement sample (c1)>
Both surfaces of the resin sheet (c1) were sandwiched between slide glasses (thickness 1.2 to 1.5 mm), and laminated glass (c1) on a 70 ° C. plate.

  The laminated glass (c1) was heated in an autoclave under a nitrogen atmosphere at a pressure of 1.5 MPa and 130 ° C. for 0.5 hours to obtain a measurement sample (c1) in which slide glasses were disposed on both surfaces of the resin sheet. .

<Preparation of measurement sample (c2)>
The resin sheet (c1) was further preheated at 200 ° C. and 3 MPa for 1 minute using a 0.8 mm-thick mold and a compression molding machine manufactured by Shindo Metal Industry Co., Ltd., and then at 10 MPa for 5 minutes. The resin sheet (c2) was obtained by pressing.

  Except that the resin sheet (c1) was replaced with the resin sheet (c2), the measurement sample (c2) was obtained in the same manner as the measurement sample (c1). .

<Evaluation of heat resistance>
The spectra of the measurement samples (c1) and (c2) were measured by the following methods, respectively.
The spectrum of the measurement sample was measured using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.) in the wavelength range of 250 to 2500 nm. Tristimulus values (X, Y, Z) were calculated using a C light source.

The measurement sample (c1) had a YI (yellowness index) of 3.5, and the measurement sample (c2) had a YI of 5.8. The YI value was calculated according to the following formula.
YI = (128X−106Z) / Y
When the difference between the YI of the measurement sample (c1) and the YI of the measurement sample (c2) (YI of the measurement sample (c2) −YI of the measurement sample (c1)) is ΔYI, ΔYI was 2.3.

<Evaluation of long-term heat resistance>
The long-term heat resistance test was conducted by the following method. The measurement sample (c1) was put in an oven at 100 ° C. and stored for 1000 hours, and then the spectrum was measured to obtain YI.
YI after 1000 hours was 10.4, and ΔYI was 6.9 (10.4−3.5), where ΔYI was the difference from YI before the long-term heat resistance test.

<Evaluation of light resistance>
The light resistance test was conducted by the following method. Put the measurement sample (c2) in a super xenon weather meter (manufactured by Suga Test Instruments Co., Ltd.), store it for 180 hours under the conditions of 180 W / m ² , no rain, and then measure the spectrum to measure YI , Tvis (visible light transmittance) was determined.

Tvis after 150 hours was 38.0%, and Tvis of the measurement sample (c2) before the light resistance test was 86.7%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 48 .7.
YI after 150 hours was 23.9, and ΔYI was 18.1 (23.9-5.8), where ΔYI was the difference from YI before the light resistance test.

[Example 1]
(Preparation of copper salt dispersion (near infrared absorber dispersion))
0.3 g of methanol was added to 3.28 g of n-butylphosphonic acid copper salt toluene dispersion (c1) obtained in Comparative Example 1 (containing 340 mg of near-infrared absorber (phosphonic acid copper salt and dispersing agent)), The mixture was stirred at 70 ° C. for 6 hours to prepare an n-butylphosphonic acid copper salt toluene dispersion (1) (near infrared absorber dispersion).

  For the obtained n-butylphosphonic acid copper salt toluene dispersion (1), the amount of acetic acid in the near-infrared absorber was measured in accordance with the above item [Measurement of acetic acid amount in near-infrared absorber]. Acetic acid was contained in an amount of 0.0022 mol with respect to 1 mol of the acid copper salt.

(Preparation of copper salt fine particle dispersed resin (resin composition))
1.35 g of n-butylphosphonic acid copper salt toluene dispersion (c1) (0.583 mmol of copper salt, 140 mg of near-infrared absorber (phosphonic acid copper salt and dispersing agent) included), n-butylphosphonic acid copper salt Toluene dispersion (1) 1.47 g (copper salt 0.583 mmol, including near-infrared absorber (phosphonic acid copper salt and dispersing agent 140 mg included)) A PVB resin (1) (resin composition) in which fine particles were dispersed was obtained.

(Evaluation)
The measurement sample (1) and the measurement sample (2) were performed in the same manner as in Comparative Example 1 except that the PVB resin (c1) in which the copper salt fine particles were dispersed was replaced with the PVB resin (1) in which the copper salt fine particles were dispersed. Created.

<Evaluation of heat resistance>
The spectra of the measurement sample (1) and the measurement sample (2) were measured by the same method as that described in the section <Evaluation of heat resistance> of Comparative Example 1.
YI of the measurement sample (1) was 4.6, and YI of the measurement sample (2) was 6.6. ΔYI of the measurement sample (1) and the measurement sample (2) was 2.0.

<Evaluation of long-term heat resistance>
YI was determined in the same manner as in the section <Evaluation of long-term heat resistance> in Comparative Example 1 except that the measurement sample (c1) was replaced with the measurement sample (1).
YI after 1000 hours was 10.0, and ΔYI was 5.4 (10.0-4.6), where ΔYI was the difference from YI before the long-term heat resistance test.

<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Comparative Example 1 except that the measurement sample (c2) was replaced with the measurement sample (2).
The Tvis after 150 hours was 62.5%, and the Tvis of the measurement sample (2) before the light resistance test was 86.7%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 24 .2.
YI after 150 hours was 15.5, and ΔYI was 8.9 (15.5-6.6) when the difference from YI before the light resistance test was ΔYI.

[Example 2]
(Preparation of copper salt dispersion (near infrared absorber dispersion))
0.9 g of methanol was added to 3.28 g of n-butylphosphonic acid copper salt toluene dispersion (c1) obtained in Comparative Example 1 (containing 340 mg of a near-infrared absorber (phosphonic acid copper salt and dispersing agent)), The mixture was stirred at 25 ° C. for 4 hours to prepare n-butylphosphonic acid copper salt toluene dispersion (2) (near infrared absorber dispersion).

  The obtained n-butylphosphonic acid copper salt toluene dispersion (2) was measured for the amount of acetic acid in the near-infrared absorber in accordance with the item [Measurement of acetic acid amount in the near-infrared absorber]. The acetic acid was contained 0.0062 mol with respect to 1 mol of acid copper salts.

(Preparation of copper salt fine particle dispersed resin (resin composition))
1.35 g of n-butylphosphonic acid copper salt toluene dispersion (c1) (0.583 mmol of copper salt, 140 mg of near-infrared absorber (phosphonic acid copper salt and dispersing agent) included), n-butylphosphonic acid copper salt The same procedure as in Comparative Example 1 was carried out except that 1.72 g of toluene dispersion (2) (0.583 mmol of copper salt and 140 mg of near-infrared absorber (copper salt of phosphonic acid and dispersant) was included) was obtained. A PVB resin (2) (resin composition) in which fine particles were dispersed was obtained.

(Evaluation)
The measurement sample (3) and the measurement sample (4) were performed in the same manner as in Comparative Example 1 except that the PVB resin (c1) in which the copper salt fine particles were dispersed was replaced with the PVB resin (2) in which the copper salt fine particles were dispersed. Created.

<Evaluation of heat resistance>
The spectra of the measurement sample (3) and the measurement sample (4) were measured by the same method as that shown in the section <Evaluation of heat resistance> of Comparative Example 1.
YI of the measurement sample (3) was 4.1, and YI of the measurement sample (4) was 6.2. ΔYI of the measurement sample (3) and the measurement sample (4) was 2.1.

<Evaluation of long-term heat resistance>
YI was determined in the same manner as in the section <Evaluation of long-term heat resistance> in Comparative Example 1 except that the measurement sample (c1) was replaced with the measurement sample (3).
YI after 1000 hours was 10.0, and ΔYI was 5.9 (10.0-4.1), where ΔYI was the difference from YI before the long-term heat resistance test.

<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Comparative Example 1 except that the measurement sample (c2) was replaced with the measurement sample (4).
The Tvis after 150 hours was 46.8%, and the Tvis of the measurement sample (4) before the light resistance test was 86.6%. Therefore, if the difference in Tvis before and after the test is ΔTvis, ΔTvis is 39 .8.
YI after 150 hours was 21.8, and ΔYI was 15.6 (21.8-6.2), where ΔYI was the difference from YI before the light resistance test.

Example 3
(Preparation of copper salt dispersion (near infrared absorber dispersion))
3.28 g of n-butylphosphonic acid copper salt toluene dispersion (c1) obtained in Comparative Example 1 (containing 340 mg of near-infrared absorber (phosphonic acid copper salt and dispersing agent)) at 120 ° C. for 6.5 hours The mixture was stirred to prepare n-butylphosphonic acid copper salt toluene dispersion (3) (near infrared absorber dispersion).

  The obtained n-butylphosphonic acid copper salt toluene dispersion (3) was measured for the amount of acetic acid in the near-infrared absorber in accordance with the item [Measurement of acetic acid amount in the near-infrared absorber]. Acetic acid was contained in an amount of 0.0068 mol per 1 mol of the acid copper salt.

(Preparation of copper salt fine particle dispersed resin (resin composition))
1.35 g of n-butylphosphonic acid copper salt toluene dispersion (c1) (0.583 mmol of copper salt, 140 mg of near-infrared absorber (phosphonic acid copper salt and dispersing agent) included), n-butylphosphonic acid copper salt Toluene dispersion (3) The same procedure as in Comparative Example 1 was conducted except that 1.35 g (0.583 mmol of copper salt and 140 mg of near-infrared absorber (copper salt of phosphonic acid and dispersant) was included) was obtained. A PVB resin (3) (resin composition) in which fine particles were dispersed was obtained.

(Evaluation)
The measurement sample (5) and the measurement sample (6) were performed in the same manner as in Comparative Example 1 except that the PVB resin (c1) in which the copper salt fine particles were dispersed was replaced with the PVB resin (3) in which the copper salt fine particles were dispersed. Created.

<Evaluation of heat resistance>
The spectra of the measurement sample (5) and the measurement sample (6) were measured by the same method as that described in the section <Evaluation of heat resistance> of Comparative Example 1.
YI of the measurement sample (5) was 3.9, and YI of the measurement sample (6) was 6.1. ΔYI of the measurement sample (5) and the measurement sample (6) was 2.2.

<Evaluation of long-term heat resistance>
YI was determined in the same manner as in the section <Evaluation of long-term heat resistance> in Comparative Example 1 except that the measurement sample (c1) was replaced with the measurement sample (5).
YI after 1000 hours was 9.4, and ΔYI was 5.5 (9.4-3.9), where ΔYI was the difference from YI before the long-term heat resistance test.

<Evaluation of light resistance>
Except that the measurement sample (c2) was replaced with the measurement sample (6), YI and Tvis were obtained in the same manner as in the section <Evaluation of light resistance> in Comparative Example 1.
Tvis after 150 hours was 46.5%, and Tvis of the measurement sample (6) before the light resistance test was 86.1%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 39 .6.
YI after 150 hours was 19.4, and ΔYI was 13.3 (19.4-6.1), where ΔYI was the difference from YI before the light resistance test.

Example 4
(Preparation of copper salt dispersion (near infrared absorber dispersion))
12.5 hours of ultrasonic waves for 3.28 g of the n-butylphosphonic acid copper salt toluene dispersion (c1) obtained in Comparative Example 1 (containing 340 mg of near-infrared absorber (phosphonic acid copper salt and dispersing agent)) Irradiation was performed to prepare an n-butylphosphonic acid copper salt toluene dispersion (4) (near infrared absorber dispersion).

  The obtained n-butylphosphonic acid copper salt toluene dispersion (4) was measured for the amount of acetic acid in the near-infrared absorber in accordance with the item [Measurement of acetic acid amount in the near-infrared absorber]. The acetic acid was contained 0.0041 mol with respect to 1 mol of acid copper salts.

(Preparation of copper salt fine particle dispersed resin (resin composition))
1.35 g of n-butylphosphonic acid copper salt toluene dispersion (c1) (0.583 mmol of copper salt, 140 mg of near-infrared absorber (phosphonic acid copper salt and dispersing agent) included), n-butylphosphonic acid copper salt Toluene dispersion (4) 1.35g (0.583mmol of copper salt, 140mg of near-infrared absorber (phosphonic acid copper salt and dispersant) included) A PVB resin (4) (resin composition) in which fine particles were dispersed was obtained.

(Evaluation)
The measurement sample (7) and the measurement sample (8) were performed in the same manner as in Comparative Example 1 except that the PVB resin (c1) in which the copper salt fine particles were dispersed was replaced with the PVB resin (4) in which the copper salt fine particles were dispersed. Created.

<Evaluation of heat resistance>
The spectra of the measurement sample (7) and the measurement sample (8) were measured by the same method as that described in the section <Evaluation of heat resistance> of Comparative Example 1.
YI of the measurement sample (7) was 5.4, and YI of the measurement sample (8) was 8.0. ΔYI of the measurement sample (7) and the measurement sample (8) was 2.6.

<Evaluation of long-term heat resistance>
YI was determined in the same manner as in the section <Evaluation of long-term heat resistance> in Comparative Example 1 except that the measurement sample (c1) was replaced with the measurement sample (7).
YI after 1000 hours was 11.8, and ΔYI was 6.4 (11.8-5.4), where ΔYI was the difference from YI before the long-term heat resistance test.

<Evaluation of light resistance>
Except that the measurement sample (c2) was replaced with the measurement sample (8), YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Comparative Example 1.
The Tvis after 150 hours was 58.2%, and the Tvis of the measurement sample (8) before the light resistance test was 86.0%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 27 .8.
YI after 150 hours was 15.8, and ΔYI was 7.8 (15.8−8.0), where ΔYI was the difference from YI before the light resistance test.

Example 5
(Preparation of copper salt dispersion (near infrared absorber dispersion))
N-butylphosphonic acid copper salt toluene dispersion (c1) 3.28 g obtained in Comparative Example 1 (containing 340 mg of near-infrared absorber (phosphonic acid copper salt and dispersing agent)), n-butylphosphonic acid 7 A solution prepared by dissolving 9 mg in 0.2 ml of ethanol was added and stirred at 25 ° C. for 2 hours to prepare an n-butylphosphonic acid copper salt toluene dispersion (5) (near infrared absorber dispersion).

  The obtained n-butylphosphonic acid copper salt toluene dispersion (5) was measured for the amount of acetic acid in the near-infrared absorber in accordance with the item [Measurement of acetic acid amount in the near-infrared absorber]. Acetic acid was contained in an amount of 0.0005 mol with respect to 1 mol of the acid copper salt.

(Preparation of copper salt fine particle dispersed resin (resin composition))
1.35 g of n-butylphosphonic acid copper salt toluene dispersion (c1) (0.583 mmol of copper salt, 140 mg of near-infrared absorber (phosphonic acid copper salt and dispersing agent) included), n-butylphosphonic acid copper salt The same procedure as in Comparative Example 1 was conducted except that the toluene dispersion (5) was replaced with 1.41 g (containing 0.583 mmol of copper salt and 143 mg of a near-infrared absorber (phosphonic acid copper salt and dispersant)). A PVB resin (5) (resin composition) in which fine particles were dispersed was obtained.

(Evaluation)
The measurement sample (9) and the measurement sample (10) were performed in the same manner as in Comparative Example 1 except that the PVB resin (c1) in which the copper salt fine particles were dispersed was replaced with the PVB resin (5) in which the copper salt fine particles were dispersed. Created.

<Evaluation of heat resistance>
The spectra of the measurement sample (9) and the measurement sample (10) were measured by the same method as that described in the section <Evaluation of heat resistance> of Comparative Example 1.
YI of the measurement sample (9) was 7.3, and YI of the measurement sample (10) was 9.5. ΔYI of the measurement sample (9) and the measurement sample (10) was 2.2.

<Evaluation of long-term heat resistance>
YI was determined in the same manner as in the section <Evaluation of long-term heat resistance> in Comparative Example 1 except that the measurement sample (c1) was replaced with the measurement sample (9).
YI after 1000 hours was 15.0, and ΔYI was 7.7 (15.0-7.3), where ΔYI was the difference from YI before the long-term heat resistance test.

<Evaluation of light resistance>
Except that the measurement sample (c2) was replaced with the measurement sample (10), YI and Tvis were obtained in the same manner as in the section <Evaluation of light resistance> in Comparative Example 1.
The Tvis after 150 hours was 81.1%, and the Tvis of the measurement sample (10) before the light resistance test was 83.0%. Therefore, when the difference in Tvis before and after the test is ΔTvis, ΔTvis is 1 .9.
YI after 150 hours was 11.3, and ΔYI was 1.8 (11.3-9.5), where ΔYI was the difference from YI before the light resistance test.

Example 6
(Preparation of copper salt dispersion (near infrared absorber dispersion))
Plysurf A219B (first) with respect to 3.28 g of n-butylphosphonic acid copper salt toluene dispersion (c1) obtained in Comparative Example 1 (containing 340 mg of near-infrared absorber (phosphonic acid copper salt and dispersing agent)) Kogyo Pharmaceutical Co., Ltd.) Add a solution of 143.1 mg in 5 ml of toluene and stir at 70 ° C. for 2.5 hours to prepare an n-butylphosphonic acid copper salt toluene dispersion (6) (near infrared absorber dispersion). did.

  The obtained n-butylphosphonic acid copper salt toluene dispersion (6) was measured for the amount of acetic acid in the near-infrared absorber in accordance with the item [Measurement of acetic acid amount in the near-infrared absorber]. Acetic acid was contained in an amount of 0.0028 mol with respect to 1 mol of the acid copper salt.

  About 3.19 g of the obtained n-butylphosphonic acid copper salt toluene dispersion (6), the solvent was distilled off with an evaporator (water bath 40 ° C.). To this was added 2.8 g of toluene to prepare an n-butylphosphonic acid copper salt toluene dispersion (6 ') (near infrared absorber dispersion).

(Preparation of copper salt fine particle dispersed resin (resin composition))
1.35 g of n-butylphosphonic acid copper salt toluene dispersion (c1) (0.583 mmol of copper salt, 140 mg of near-infrared absorber (phosphonic acid copper salt and dispersing agent) included), n-butylphosphonic acid copper salt The same procedure as in Comparative Example 1 was repeated except that 3.00 g of toluene dispersion (6 ′) (0.583 mmol of copper salt and 199 mg of near-infrared absorber (copper salt of phosphonic acid and dispersant) was included) was performed. A PVB resin (6) (resin composition) in which salt fine particles were dispersed was obtained.

(Evaluation)
The measurement sample (11) and the measurement sample (12) were performed in the same manner as in Comparative Example 1 except that the PVB resin (c1) in which the copper salt fine particles were dispersed was replaced with the PVB resin (6) in which the copper salt fine particles were dispersed. Created.

<Evaluation of heat resistance>
The spectra of the measurement sample (11) and the measurement sample (12) were measured by the same method as that described in the section <Evaluation of heat resistance> of Comparative Example 1.
YI of the measurement sample (11) was 4.2, and YI of the measurement sample (12) was 6.3. ΔYI of the measurement sample (11) and the measurement sample (12) was 2.1.

<Evaluation of long-term heat resistance>
YI was determined in the same manner as in <Evaluation of long-term heat resistance> in Comparative Example 1 except that the measurement sample (c1) was replaced with the measurement sample (11).
YI after 1000 hours was 14.6, and ΔYI was 10.4 (14.6-4.2), where ΔYI was the difference from YI before the long-term heat resistance test.

<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Comparative Example 1 except that the measurement sample (c2) was replaced with the measurement sample (12).
The Tvis after 150 hours was 48.4%, and the Tvis of the measurement sample (12) before the light resistance test was 87.4%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 39 0.0.
YI after 150 hours was 6.6, and ΔYI was 0.3 (6.6-6.3), where ΔYI was the difference from YI before the light resistance test.

[Comparative Example 2]
(Preparation of copper salt dispersion (near infrared absorber dispersion))
To a 500 ml eggplant flask, 7.00 g (35.06 mmol) of copper acetate monohydrate and 140 g of methanol were added and stirred at 20 ° C. for 1 hour to obtain Liquid A.

In a separate container, a solution (Liquid B) in which 1.75 g of Prisurf A219B (Daiichi Kogyo Seiyaku) and 4.82 g of n-butylphosphonic acid were dissolved in 100 g of methanol was prepared.
B liquid was dripped over 3 hours with respect to A liquid. The reaction was stirred at 20 ° C. for 10 hours.

Then, the solvent was distilled off with an evaporator (water bath 60 ° C.).
Toluene (100 g) was added thereto, and the mixture was made constant, and distilled off with an evaporator until the acetic acid odor disappeared.

  A blue-green solid with a yield of 8.75 g (100% yield) was obtained. To this was added 211 g of toluene, and ultrasonic irradiation was performed for 6 hours to prepare an n-butylphosphonic acid copper salt toluene dispersion (c2) (near infrared absorber dispersion).

  The obtained n-butylphosphonic acid copper salt toluene dispersion (c2) was measured for the amount of acetic acid in the near-infrared absorber in accordance with the item [Measurement of acetic acid amount in the near-infrared absorber]. The acetic acid was contained 0.0049 mol with respect to 1 mol of acid copper salts.

(Preparation of copper salt fine particle dispersed resin (resin composition))
To a 300 ml Erlenmeyer flask, 1.90 g of triethylene glycol bis (2-ethylhexanoate), 250 ml of toluene, and 5.00 g of polyvinyl butyral (PVB) were added.

  To this, 3.65 g of the n-butylphosphonic acid copper salt toluene dispersion (c2) (containing 0.583 mmol of copper salt and 145 mg of near-infrared absorber (phosphonic acid copper salt and dispersing agent)) was added, and 20 ° C. After stirring for 10 hours, ultrasonic irradiation was performed for 1.5 hours to uniformly dissolve PVB.

  This dispersion was spread on a Teflon (registered trademark) vat and air-dried at 20 ° C. for 12 hours. Further, vacuum drying was performed at 40 ° C. for 5 hours and at 70 ° C. for 3.5 hours to completely remove the solvent, thereby obtaining a PVB resin (c2) (resin composition) in which copper salt fine particles were dispersed.

(Evaluation)
The measurement sample (c3) and the measurement sample (c4) were performed in the same manner as in Comparative Example 1 except that the PVB resin (c1) in which the copper salt fine particles were dispersed was replaced with the PVB resin (c2) in which the copper salt fine particles were dispersed. Created.

<Evaluation of heat resistance>
The spectra of the measurement sample (c3) and the measurement sample (c4) were measured by the same method as the method described in the section <Evaluation of heat resistance> of Comparative Example 1.
The YI of the measurement sample (c3) was 5.5, and the YI of the measurement sample (c4) was 8.1. ΔYI of the measurement sample (c3) and the measurement sample (c4) was 2.6.

<Evaluation of long-term heat resistance>
YI was determined in the same manner as in the section <Evaluation of long-term heat resistance> in Comparative Example 1 except that the measurement sample (c1) was replaced with the measurement sample (c3).
YI after 1000 hours was 11.0, and ΔYI was 5.5 (11.0-5.5) when the difference from YI before the long-term heat resistance test was ΔYI.

<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Comparative Example 1 except that the measurement sample (c2) was replaced with the measurement sample (c4).
The Tvis after 150 hours was 44.0%, and the Tvis of the measurement sample (c4) before the light resistance test was 86.3%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 42 .3.
YI after 150 hours was 24.6, and ΔYI was 16.5 (24.6-8.1) when the difference from YI before the light resistance test was ΔYI.

Example 7
(Preparation of copper salt dispersion (near infrared absorber dispersion))
8.86 g of the n-butylphosphonic acid copper salt toluene dispersion (c2) obtained in Comparative Example 2 (containing 352 mg of near-infrared absorber (phosphonic acid copper salt and dispersing agent)) was stored at room temperature for 3 months. , N-butylphosphonic acid copper salt toluene dispersion (7) (near infrared absorber dispersion) was prepared.

  The obtained n-butylphosphonic acid copper salt toluene dispersion (7) was measured for the amount of acetic acid in the near-infrared absorber in accordance with the item [Measurement of acetic acid amount in the near-infrared absorber]. Acetic acid was contained in an amount of 0.0018 mol per 1 mol of the acid copper salt.

(Preparation of copper salt fine particle dispersed resin (resin composition))
3.65 g of n-butylphosphonic acid copper salt toluene dispersion (c2) (containing 0.583 mmol of copper salt and 145 mg of near-infrared absorber (phosphonic acid copper salt and dispersing agent)), n-butylphosphonic acid copper salt Toluene dispersion (7) 3.65 g (0.583 mmol of copper salt, 145 mg of near-infrared absorbing agent (copper phosphonate and dispersant) included) A PVB resin (7) (resin composition) in which fine particles were dispersed was obtained.

(Evaluation)
The measurement sample (13) and the measurement sample (14) were performed in the same manner as in Comparative Example 1 except that the PVB resin (c1) in which the copper salt fine particles were dispersed was replaced with the PVB resin (7) in which the copper salt fine particles were dispersed. Created.

<Evaluation of heat resistance>
The spectra of the measurement sample (13) and the measurement sample (14) were measured by the same method as that described in the section <Evaluation of heat resistance> of Comparative Example 1.

  YI of the measurement sample (13) was 10.4, and YI of the measurement sample (14) was 13.2. ΔYI of the measurement sample (13) and the measurement sample (14) was 2.8.

<Evaluation of long-term heat resistance>
YI was determined in the same manner as in the section <Evaluation of long-term heat resistance> in Comparative Example 1 except that the measurement sample (c1) was replaced with the measurement sample (13).
YI after 1000 hours was 13.8, and ΔYI was 3.4 (13.8-10.4), where ΔYI was the difference from YI before the long-term heat resistance test.

<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Comparative Example 1 except that the measurement sample (c2) was replaced with the measurement sample (14).
Tvis after 150 hours was 73.5%, and Tvis of the measurement sample (14) before the light resistance test was 82.4%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 8 .9.

YI after 150 hours was 17.7, and ΔYI was 4.5 (17.7-13.2) when the difference from YI before the light resistance test was ΔYI.
When Comparative Example 1 is compared with Examples 1 to 6 and Comparative Example 2 and Example 7 are compared, it is understood that the light resistance of the resin composition is improved by performing Step D.

Claims (10)

A step of reacting at least one of an organic acid copper salt and an organic acid copper salt hydrate with a phosphonic acid compound represented by the following general formula (1) in a solvent to obtain a reaction mixture containing a near-infrared absorber. A,
Removing at least a portion of the liquid components in the reaction mixture, B
Step C for obtaining a near-infrared absorbent dispersion from the reaction mixture from which at least a part of the liquid component obtained in Step B has been removed, and a dispersion medium, and
The manufacturing method of the near-infrared absorber dispersion containing the refine | purified near-infrared absorber which has the process D which removes at least one part of an organic acid from the near-infrared absorber in the said near-infrared absorber dispersion.

[In General Formula (1), R ¹ is a monovalent group represented by —CH ₂ CH ₂ —R ¹¹ , and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 carbon atom. Represents -20 fluorinated alkyl groups. ] The method for producing a near-infrared absorbent dispersion according to claim 1, wherein the step D is at least one step selected from the following (1) to (9).
(1) Step of adding a near-infrared absorbent dispersion to obtain a near-infrared absorbent dispersion containing a purified near-infrared absorbent (2) Adding an alcohol to the near-infrared absorbent dispersion and a temperature of 40 to 150 The process of obtaining the near-infrared absorber dispersion containing the refined near-infrared absorber by heating at 0 ° C. (3) The near-infrared absorber purified by heating the near-infrared absorber dispersion at a temperature of 40 to 150 ° C. (4) A step of obtaining a near-infrared absorbent dispersion containing a purified near-infrared absorbent by irradiating the near-infrared absorbent dispersion with ultrasonic waves for 4 hours or more (4) 5) Step of adding a phosphonic acid compound represented by the general formula (1) to the near-infrared absorber dispersion to obtain a near-infrared absorber dispersion containing a purified near-infrared absorber (6) Near-infrared absorption The agent dispersion is 20 at 0-40 ° C. Step of obtaining a near-infrared absorber dispersion containing a purified near-infrared absorber for 200 days (7) A near-infrared ray containing a purified near-infrared absorber by adding a dispersant to the near-infrared absorber dispersion Step of obtaining an absorbent dispersion (8) Step of adding a dispersant to the near-infrared absorber dispersion and heating at a temperature of 40 to 150 ° C. to obtain a near-infrared absorber dispersion containing a purified near-infrared absorber. (9) A step of obtaining a near-infrared absorbent dispersion containing a purified near-infrared absorber using alcohol as at least a part of the dispersion medium in the step C.   The manufacturing method of the near-infrared absorber dispersion liquid of Claim 1 or 2 with which reaction in the said process A is performed in dispersing agent presence. The dispersant used in Step A is at least selected from a phosphoric acid monoester represented by the following general formula (2), a phosphoric acid diester represented by the following general formula (3), and alkali metal salts thereof. The manufacturing method of the near-infrared absorber dispersion liquid of Claim 3 which is 1 type of phosphate ester compounds.

[In General Formulas (2) and (3), R ² , R ³ and R ⁴ are monovalent groups represented by — (CH ₂ CH ₂ O) _n R ¹² , and n is from 2 to 65. It is an integer and R ¹² represents an alkyl group having 6 to 35 carbon atoms or an alkylphenyl group having 6 to 35 carbon atoms. However, R ² , R ³ and R ⁴ may be the same or different. ]   Furthermore, the near-infrared absorber as described in any one of Claims 1-4 which has the process E which removes a part of dispersion medium and organic acid in the near-infrared absorber dispersion liquid obtained at the process D. A method for producing a dispersion.   The near-infrared absorber dispersion liquid obtained with the manufacturing method as described in any one of Claims 1-5.   The near-infrared absorber obtained from the near-infrared absorber dispersion liquid of Claim 6.   The resin composition containing the near-infrared absorber of Claim 7, and resin.   An interlayer film for laminated glass formed from the resin composition according to claim 8.   A laminated glass having the interlayer film for laminated glass according to claim 9.