JP2012185385A - Manufacturing method of near-infrared ray absorbent fluid dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluid dispersion including a near-infrared ray absorbent with excellent dispersibility.SOLUTION: The method includes a step A of obtaining a reaction mixture including a near-infrared ray absorbent by mixing a phosphonic acid compound represented by general formula (1), at least one kind of phosphoric ester compound selected from a phosphoric ester compound represented by general formula (2a) and a phosphoric ester compound represented by general formula (2b), and copper salt, in a solvent.

Description

  The present invention relates to a method for producing a near-infrared absorber dispersion.

  Copper ions are excellent in absorption characteristics of light in the near-infrared region (hereinafter also referred to as “near-infrared rays”), and optical materials using the near-infrared absorption characteristics of copper ions have been proposed ( For example, see Patent Documents 1 to 4). Patent Document 1 discloses an optical material containing a phosphate ester copper compound formed from a specific phosphate ester compound and a copper compound. Patent Document 2 discloses a display front plate formed from a resin composition containing a specific phosphate compound, a copper compound, and a resin. Patent Document 3 discloses an optical filter having a near-infrared absorbing layer containing a phosphate ester copper compound formed from a specific phosphate ester compound and a copper compound. Patent Document 4 discloses a near-infrared absorbing composition comprising a specific phosphate compound and copper ions.

  Conventionally proposed optical materials containing a near-infrared absorber containing copper ions have been produced by filling a polymerization cell with a near-infrared absorber and a monomer and performing polymerization. However, in the method for producing an optical material using the polymerization cell, it is difficult to obtain a large-sized optical material, and the production cost tends to increase.

  Moreover, in the conventional optical material containing the near-infrared absorber containing a copper ion, the dispersibility of the near-infrared absorber has not been sufficiently studied, and there is still room for improvement.

JP 2001-83318 A JP 2001-83890 A JP 2001-154015 A International Publication No. 01/77250 Pamphlet

  An object of this invention is to provide the dispersion liquid containing the near-infrared absorber excellent in the dispersibility in view of the said background art.

  As a result of intensive studies to solve the above problems, the present inventors have found that the near-infrared absorbent dispersion obtained through a specific process is excellent in dispersibility of the near-infrared absorbent. Completed the invention.

  That is, the manufacturing method of the near-infrared absorber of the present invention includes a phosphonic acid compound represented by the following general formula (1), a phosphoric acid ester compound represented by the following general formula (2a), and the following general formula (2b). Step A, in which at least one phosphate ester compound selected from the phosphate ester compounds represented by formula (I) and a copper salt are mixed in a solvent to obtain a reaction mixture containing a near-infrared absorber, in the reaction mixture Step B1 for sedimenting the solid content and removing the supernatant, Step C for drying the solid content to obtain a purified near-infrared absorber, and dispersing the purified near-infrared absorber in a dispersion medium It has the process D, It is characterized by the above-mentioned.

［式中、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。Ｒ²¹、Ｒ²²およびＲ²³は、−（ＣＨ₂ＣＨ₂Ｏ）_nＲ⁵で表される１価の基であり、ｎは４〜３５の整数であり、Ｒ⁵は、炭素数６〜２５のアルキル基又は炭素数６〜２５のアルキルフェニル基を示す。ただし、Ｒ²¹、Ｒ²²およびＲ²³は、それぞれ同一でも異なっていてもよい。］

[In the formula, R ¹ is a monovalent group represented by ^{_{-CH 2 CH 2 -R 11, R}} 11 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a fluorine having 1 to 20 carbon atoms, Represents an alkyl group. R ²¹ , R ²² and R ²³ are a monovalent group represented by — (CH ₂ CH ₂ O) _n R ⁵ , n is an integer of 4 to 35, and R ⁵ is a carbon number of 6 to 25 alkyl groups or C6-C25 alkylphenyl groups are shown. However, R ²¹ , R ²² and R ²³ may be the same or different. ]

  The step B1 in which the solid content in the reaction mixture is settled and the supernatant liquid is removed is a step in which the solid content is settled by allowing the reaction mixture to stand and the supernatant liquid is removed, or the reaction mixture is centrifuged. The solid content is preferably settled and the supernatant is removed.

  Between Step B1 and Step C, the solid content obtained by removing the supernatant liquid is washed by adding a solvent to the solid content, and then the solid content is settled and the supernatant liquid is removed. The step B2 may be performed one or more times. When the step B2 is performed, the step C is a step of drying the solid content obtained in the step B2 to obtain a purified near infrared absorber.

R ¹¹ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 2 to 8 carbon atoms.
In the step D, it is preferable to perform ultrasonic treatment.

  The near-infrared absorber dispersion obtained by the production method of the present invention is excellent in dispersibility of the near-infrared absorber. For this reason, even if it is a case where a near-infrared absorber dispersion liquid is preserve | saved for a long period of time, a near-infrared absorber does not precipitate, for example.

Next, the present invention will be specifically described.
The manufacturing method of a near-infrared absorber dispersion liquid is represented by the phosphonic acid compound represented by the following general formula (1), the phosphoric acid ester compound represented by the following general formula (2a), and the following general formula (2b). Step A in which at least one phosphate ester compound selected from phosphoric acid ester compounds and a copper salt are mixed in a solvent to obtain a reaction mixture containing a near infrared absorber, solid content in the reaction mixture Step B1 for removing the supernatant and removing the supernatant, Step C for drying the solid content to obtain a purified near-infrared absorber, and Step D for dispersing the purified near-infrared absorber in a dispersion medium It is characterized by having.

［式中、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。Ｒ²¹、Ｒ²²およびＲ²³は、−（ＣＨ₂ＣＨ₂Ｏ）_nＲ⁵で表される１価の基であり、ｎは４〜３５の整数であり、Ｒ⁵は、炭素数６〜２５のアルキル基又は炭素数６〜２５のアルキルフェニル基を示す。ただし、Ｒ²¹、Ｒ²²およびＲ²³は、それぞれ同一でも異なっていてもよい。］
以下、本発明の近赤外線吸収剤分散液の製造方法の各工程について説明する。

[In the formula, R ¹ is a monovalent group represented by ^{_{-CH 2 CH 2 -R 11, R}} 11 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a fluorine having 1 to 20 carbon atoms, Represents an alkyl group. R ²¹ , R ²² and R ²³ are a monovalent group represented by — (CH ₂ CH ₂ O) _n R ⁵ , n is an integer of 4 to 35, and R ⁵ is a carbon number of 6 to 25 alkyl groups or C6-C25 alkylphenyl groups are shown. However, R ²¹ , R ²² and R ²³ may be the same or different. ]
Hereinafter, each process of the manufacturing method of the near-infrared absorber dispersion liquid of this invention is demonstrated.

[Step A]
In the method for producing a near-infrared absorber dispersion of the present invention, first, the phosphonic acid compound represented by the general formula (1), the phosphate compound represented by the general formula (2a), and the general formula ( Step A is performed in which at least one phosphate ester compound selected from the phosphate ester compounds represented by 2b) and a copper salt are mixed in a solvent to obtain a reaction mixture containing a near-infrared absorber.

  In the present invention, the “phosphonic acid compound represented by the general formula (1)” is also referred to as “specific phosphonic acid compound”, and the phosphoric acid ester compound represented by the general formula (2a) and the general formula ( The “at least one phosphate ester compound selected from the phosphate ester compounds represented by 2b)” is also referred to as “specific phosphate ester compound”.

  The near-infrared absorber obtained in step A is considered to have near-infrared absorption characteristics mainly due to the copper ions of the phosphonic acid copper salt obtained by reacting the specific phosphonic acid compound with the copper salt. The phosphonic acid copper salt is considered to be maintained in a very fine state by the specific phosphate ester compound acting as a dispersant. The copper phosphonate is represented by the following general formula (3).

  Moreover, it is thought that the near-infrared absorber obtained at the process A mainly coordinates the said specific phosphonic acid compound with respect to a copper ion, and also exists the said specific phosphate ester compound around it. Moreover, it is thought that the said specific phosphate ester compound coordinates to some copper ions. Therefore, the copper ions in the near-infrared absorber are excellent in stability to heat and the like. For example, a molded product such as a near-infrared absorption filter containing the near-infrared absorber is not affected by the copper ions and is colored. Less transparency and excellent transparency.

［式中、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。］
前記一般式（１）および（３）におけるＲ¹¹としては、水素原子、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、パーフルオロエチル基、パーフルオロプロピル基、パーフルオロ−ｎ−ブチル基、パーフルオロへキシル基、パーフルオロオクチル基、パーフルオロデシル基等が挙げられる。

[In the formula, R ¹ is a monovalent group represented by ^{_{-CH 2 CH 2 -R 11, R}} 11 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a fluorine having 1 to 20 carbon atoms, Represents an alkyl group. ]
R ¹¹ in the general formulas (1) and (3) 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 (3) 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 10 carbon atoms, and more preferably an alkyl group having 2 to 8 carbon atoms. R ¹¹ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms because the dispersibility of the near-infrared absorber in the near-infrared absorber dispersion obtained by the production method of the present invention tends to be particularly excellent. . Further, it is preferable that R ¹¹ is an alkyl group having 2 to 8 carbon atoms because the solid content tends to be easily settled in Step B1 and Step B2 described later.

In at least one phosphate ester compound selected from the phosphate ester compound represented by the general formula (2a) and the phosphate ester compound represented by the general formula (2b), R ²¹ , R ²² and R ²³ is a monovalent group (polyoxyalkyl group) represented by — (CH ₂ CH ₂ O) _n R ⁵ . n is an integer of 4 to 35, and more preferably an integer of 6 to 25. When n is less than 4, when a molded product such as a near-infrared absorbing filter is produced using the near-infrared absorbent dispersion of the present invention, the transparency of the molded product becomes insufficient. On the other hand, when n exceeds 35, the amount of the phosphoric acid ester compound necessary to obtain a molded article such as a near infrared absorption filter having sufficient transparency increases, resulting in high costs.

R ⁵ is an alkyl group having 6 to 25 carbon atoms or an alkylphenyl group having 6 to 25 carbon atoms, preferably an alkyl group having 6 to 25 carbon atoms, and is an alkyl group having 12 to 20 carbon atoms. Is more preferable. When R ⁵ is a group having less than 6 carbon atoms, the transparency of a molded product such as a near infrared absorption filter becomes insufficient. Further, if R ⁵ is a group having more than 25 carbon atoms, the amount of the phosphoric acid ester compound required for obtaining a molded article such as a near-infrared absorption filter having sufficient transparency is increased, resulting in high costs. It becomes.

  When obtaining a near-infrared absorber in step A, at least one of the phosphoric acid ester compound represented by the general formula (2a) and the phosphoric acid ester compound represented by the general formula (2b) is used. It is preferable to use both the phosphate compound represented by the general formula (2a) and the phosphate compound represented by the general formula (2b). When the phosphoric acid ester compound represented by the general formula (2a) and the phosphoric acid ester compound represented by the general formula (2b) are used, the transparency and heat resistance of a molded article such as a near infrared absorption filter tend to be excellent. Is preferable. When both the phosphate compound represented by the general formula (2a) and the phosphate compound represented by the general formula (2b) are used, the phosphate compound represented by the general formula (2a) The ratio of the phosphoric acid ester compound represented by the general formula (2b) is not particularly limited, but is usually 10:90 to 90:10 in molar ratio ((2a) :( 2b)).

  Moreover, as a phosphate ester compound represented by the said General formula (2a), it may be used individually by 1 type, or 2 or more types may be used, As a phosphate ester compound represented by the said General formula (2b) May be used alone or in combination of two or more.

Moreover, when obtaining a near-infrared absorber in the process A, you may further use another phosphorus compound, for example, phosphoric acid triester.
As at least one phosphate ester compound selected from the phosphate ester compound represented by the general formula (2a) and the phosphate ester compound represented by the general formula (2b), commercially available phosphoric acid An ester compound can also be used.

  As the copper salt, a copper salt capable of supplying divalent copper ions is usually used. As said copper salt, what is necessary is just copper salts other than the phosphonic acid copper salt represented by the said General formula (3). Examples of the copper salt include copper of organic acids such as anhydrous copper acetate, anhydrous copper formate, anhydrous copper stearate, anhydrous copper benzoate, anhydrous ethyl acetoacetate copper, anhydrous pyrophosphate, anhydrous naphthenic acid copper, and anhydrous copper citrate. Salt, hydrate or hydrate of copper salt of organic acid; copper salt of inorganic acid such as copper oxide, copper chloride, copper sulfate, copper nitrate, basic copper carbonate, hydrate of copper salt of inorganic acid Or a hydrate; copper hydroxide is mentioned. In addition, as a copper salt, you may use individually by 1 type, or may use 2 or more types.

As the copper salt, anhydrous copper acetate and copper acetate monohydrate are preferably used from the viewpoint of solubility and removal of by-products.
The near-infrared absorber obtained in step A is represented by the phosphonic acid compound represented by the general formula (1), the phosphate compound represented by the general formula (2a), and the general formula (2b). It is obtained from at least one phosphate ester compound selected from phosphoric acid ester compounds and a copper salt. As the near-infrared absorber obtained in the step A, it is considered that the phosphonic acid copper salt obtained by reacting the specific phosphonic acid compound and the copper salt exists, and further the specific phosphate ester compound is present therearound. Further, it is considered that there is also a phosphonic acid copper salt in which a part of the specific phosphonic acid compound constituting the phosphonic acid copper salt is replaced with the specific phosphoric acid ester compound.

Moreover, the average particle diameter of the near-infrared absorber obtained at the process A becomes like this. Preferably it is 10-150 nm, More preferably, it is 20-120 nm.
Moreover, the quantity of each said component used at the process A is as follows. The specific phosphonic acid compound is preferably used in an amount of 5 mol or more, more preferably 8 to 100 mol, and particularly preferably 10 to 80 mol, per 1 mol of the specific phosphate compound. When the amount is less than 5 mol, the near infrared absorption characteristics of a molded article such as a near infrared absorption filter may deteriorate, or the heat resistance may decrease.

  The specific phosphonic acid compound is preferably 0.4 mol or more, more preferably 0.5 to 1.5 mol, and more preferably 0.7 to 1 per 1 mol of copper in the copper salt. Particularly preferred is 2 moles. Within the said range, since transparency and heat resistance of molded objects, such as a near-infrared absorption filter, are especially excellent, it is preferable.

  In step A, as described above, the specific phosphonic acid compound, the specific phosphoric acid ester compound, and the copper salt are mixed in a solvent to obtain a reaction mixture containing a near-infrared absorber. The following method can be used.

  In the step A, the specific phosphonic acid compound reacts with the copper salt mainly in the presence of the specific phosphoric ester compound, and by the reaction, particulate copper phosphonate that does not dissolve in the solvent A salt is formed. Since the phosphoric ester compound can act as a good dispersant during the reaction, the phosphonic acid copper salt can be kept highly dispersible and can suppress aggregation.

  In the step A, not only the reaction between the specific phosphonic acid compound and the copper salt, but also the specific phosphate compound and the copper salt may react, for example. In addition, the specific phosphonic acid compound, the specific phosphate ester compound, and a part of the copper salt may remain without reacting.

Examples of the solvent used in Step A include alcohols such as methanol and ethanol, tetrahydrofuran (THF), dimethylformamide (DMF), water, and the like, and ethanol, THF, or DMF is preferable from the viewpoint of satisfactory reaction. The reaction step is preferably performed at room temperature to 60 ° C, more preferably 20 to 40 ° C, preferably 0.5 to 5 hours, more preferably 1 to 3 hours.
By this reaction, a reaction mixture containing a near infrared absorber is obtained. In addition to the near-infrared absorber, the reaction mixture contains a by-product that depends on the solvent and the raw material used.

[Step B1]
In the manufacturing method of the near-infrared absorber dispersion liquid of the present invention, after performing the step A, the step B1 is performed in which the solid content in the reaction mixture is settled and the supernatant liquid is removed.

  In step B1, the solid content in the reaction mixture obtained in step A is precipitated. Examples of the sedimentation method include a method in which the solid content is settled by allowing the reaction mixture to stand, and a method in which the solid content is sedimented by centrifuging the reaction mixture.

  As a method of settling, natural settling is preferable from the viewpoint of cost. However, when the particle size of the near-infrared absorbing agent is small, natural sedimentation may be difficult, or natural sedimentation may be required for a long time. In such a case, it is preferable to precipitate the near-infrared absorber by centrifuging.

  In Step B1, the supernatant is removed after the solid content is settled. In step B1, the solid content can be obtained by removing the supernatant. The method for removing the supernatant liquid varies depending on the scale for carrying out the present invention, and examples thereof include a method for removing the supernatant liquid using a Pasteur pipette, a dropper and the like, and a method for removing the supernatant liquid by decantation.

In Step B1, the solid content from which the solvent in the reaction mixture and the by-products soluble in the solvent are removed can be obtained by removing the sediment and the supernatant liquid.
Although the reason why the near-infrared absorbent dispersion obtained by the production method of the present invention is excellent in dispersibility is not clear, the present inventors have obtained a by-product that is soluble in the solvent by performing Step B1. It was estimated that this contributed to the improvement of the dispersibility of the near-infrared absorbent dispersion.
Moreover, in the manufacturing method of this invention, the process C may be performed using the solid content obtained by process B1, and the process B2 may be performed using the solid content obtained by process B1.

[Step B2]
In the manufacturing method of the near-infrared absorber dispersion liquid of the present invention, the solid content is obtained by adding a solvent to the solid content obtained by removing the supernatant liquid between Step B1 and Step C and stirring. You may perform 1 time or more of process B2 which wash | cleans and solidifies a solid content after that and removes a supernatant liquid.

  In step B2, the solid content obtained in B1 is first washed with a solvent. Washing is usually performed by mixing the solid content and a solvent and stirring. When there is a by-product that is soluble in the solvent that could not be removed in Step B1, the by-product can be dissolved in the solvent. In addition, the amount ratio of the solid content and the solvent at the time of washing is not particularly limited, but an amount that can be suitably washed by stirring or the like is preferable. Specifically, the solid content is 100 parts by mass. The solvent is preferably 300 to 10000 parts by mass, and more preferably 500 to 5000 parts by mass.

  In addition, as a solvent, what is necessary is just to be able to melt | dissolve a raw material (The said copper salt, a specific phosphonic acid compound, a specific phosphate ester compound), For example, methanol, ethanol, 2-propanol etc. are mentioned, Ethanol is preferable. The solvent may be a mixed solvent composed of a plurality of components.

In step B2, the washed solid content is allowed to settle. As a method of settling, it can carry out similarly to the method as described in process B1.
In Step B2, the supernatant is removed after the solid content is settled. As a method for removing the supernatant, it can be carried out in the same manner as in the method described in Step B1.

  In step B2, when the by-product soluble in the solvent is present in the solid content, the solid content from which the by-product has been removed is obtained by performing washing, sedimentation, and removal of the supernatant. be able to.

  Moreover, when performing process B2, process B2 may be performed once and may be performed in multiple times. By performing Step B2 a plurality of times, it is possible to further reduce the by-products in the solid content. For example, performing Step B2 twice means that the solid content obtained in Step B1 is subjected to washing, sedimentation, and removal of the supernatant liquid, and using the obtained solid content, the washing, sedimentation, and supernatant liquid are again used. Means removal. In addition, it is preferable to perform process B2 1 to 6 times, and it is more preferable to perform 1 to 4 times.

[Step C]
In the manufacturing method of the near-infrared absorber dispersion liquid of this invention, the process C which dries the said solid content and obtains the refined near-infrared absorber is performed.

  The solid content used in the step C means the solid content obtained in the step B1 when the step B2 is not performed, and the solid content obtained in the step B2 when the step B2 is performed. means.

  In Step C, the solid content is dried to obtain a purified near-infrared absorber. The solid content obtained in Step B1 or Step B2 is generally in a state of being wetted with a solvent or the like. By drying the solid content in Step C, a purified near-infrared absorber is obtained.

  In the step C, the solid or the like is usually heated to remove the solvent or the like attached to the solid, but the heating condition is usually room temperature to 70 ° C., preferably 40 to 60 ° C. The step C may be performed under normal pressure or under reduced pressure. When step C is performed under reduced pressure, heating may not be performed or the heating temperature may be low.

[Step D]
In the manufacturing method of the near-infrared absorber dispersion liquid of the present invention, Step D of dispersing the purified near-infrared absorber in a dispersion medium is performed.

  In the step D, the purified near-infrared absorber obtained in the step C is dispersed in a dispersion medium. Examples of the dispersion medium include toluene, xylene, tetrahydrofuran (THF), dimethylformamide (DMF), methylene chloride, chloroform, triethylene glycol bis (2-ethylhexanoate), and the like.

  The method for dispersing the purified near-infrared absorber in the dispersion medium is not particularly limited. A method in which the purified near-infrared absorber is added to the dispersion medium and dispersed by ultrasonic treatment (dispersed by irradiating with ultrasonic waves) And a method of adding a purified near-infrared absorber to the dispersion medium and stirring to disperse, a method of adding the purified near-infrared absorber to the dispersion medium, and pulverizing and dispersing with a ball mill. .

  The amount of the dispersion medium used in the step D is not particularly limited, but from the viewpoint of the size of the production equipment, the dispersion medium is usually 300 to 50000 parts by mass when the purified near-infrared absorber is 100 parts by mass. Used.

  In Step D, the purified near infrared absorber may be dispersed in a dispersion medium in the presence of a dispersant to obtain a dispersion. As the dispersant used in Step D, the dispersant described in Step A, that is, a specific phosphate compound can be used. If a dispersant is used in step D, the dispersibility of the obtained near-infrared absorbent dispersion may be further improved.

  The amount of the dispersant used in Step D is not particularly limited, but when the specific phosphate ester compound is used as the dispersant, the specific phosphate ester compound used in Step A is 100 parts by mass. Then, it is preferable that it is 1-100 mass parts. The specific phosphate ester compound used in step A and the specific phosphate ester compound used in step D may be the same compound or different compounds.

  In addition, when performing the process D in presence of a dispersing agent, you may add a dispersing agent to a dispersion medium, and what mixed the near-infrared absorber refine | purified previously and the dispersing agent obtained by the process C previously. , It may be used in Step D.

In the step D, other additives may be added to the solvent. Other additives include plasticizers (for example, 3GO (triethylene glycol bis (2-ethylhexanoate)), antioxidants, UV absorbers, light stabilizers, dehydrating agents, adhesive strength modifiers, silane cups A ring agent, a pigment, etc. are mentioned.
By the process D, the near-infrared absorber dispersion liquid in which the purified near-infrared absorber is dispersed in a dispersion medium can be obtained.

[Near-infrared absorber dispersion]
The near-infrared absorber dispersion obtained by the production method of the present invention is excellent in dispersibility of the near-infrared absorber contained in the dispersion. For this reason, the near-infrared absorber dispersion liquid of the present invention can be used for each application without precipitation of the near-infrared absorber even when stored at room temperature for a long time (for example, one month).

  The average particle diameter of the near infrared absorbent dispersed in the near infrared absorbent dispersion obtained by the production method of the present invention is preferably 10 to 150 nm, more preferably 20 to 120 nm.

  The use of the near-infrared absorbent dispersion is not particularly limited. For example, the dispersion medium and the monomer are mixed and then the dispersion medium is distilled off to prepare a near-infrared absorbent-containing monomer and polymerize the monomer. It is obtained by mixing a molded body such as a near-infrared absorption filter, a resin obtained by dissolving the dispersion in a solvent, preparing a near-infrared absorbent-containing resin solution, and molding by a solvent casting method or the like. And molded articles such as near infrared absorption filters.

  Moreover, the masterbatch which consists of a near-infrared absorber and resin can be obtained by disperse | distributing powdery resin to a near-infrared absorber dispersion liquid, and removing a dispersion medium. Using the masterbatch and the resin, a molded body such as a near-infrared absorption filter can be obtained by various molding methods such as extrusion molding, cast molding, and injection molding.

  Examples of the molded body other than the near-infrared absorbing filter include a near-infrared absorbing film for display, a visibility correction filter arranged in a light receiving part such as a photodiode, and the like.

  The resin is at least 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 one type of resin can disperse the near-infrared absorber well and is excellent in visible light transmittance. Moreover, it is preferable to use the monomer which can obtain the said resin by superposing | polymerizing as said monomer.

  The resin is more preferably at least one resin selected from polyvinyl acetal resin and ethylene-vinyl acetate copolymer, and selected from polyvinyl butyral resin (PVB) and ethylene-vinyl acetate copolymer. Particularly preferred is at least one resin selected from the group consisting of polyvinyl butyral resin and ethylene-vinyl acetate copolymer.

  EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.

[Example 1]
A solution (a1) obtained by dissolving 0.70 g (3.5 × 10 ⁻³ mol) of copper acetate monohydrate in 35 g of ethanol, and equimolar decylphosphonic acid 0 with respect to copper acetate monohydrate A solution (b1) prepared by dissolving 0.78 g and 0.5 g of the following phosphate ester compound (A) in 5 g of ethanol was prepared.

The phosphate ester compound (A) includes a phosphate ester compound (monoester) represented by the general formula (2a) and a phosphate ester compound (diester) represented by the general formula (2b). And a triester in which the hydrogen atom of the hydroxyl group in the general formula (2b) is further substituted with the same group, wherein n is 25, and R ²¹ , R ²² and R ²³ are It is an alkyl group having 13 to 15 carbon atoms. In addition, the abundance ratio (molar ratio) of the monoester, diester, and triester in the phosphoric ester compound (A) is approximately 1: 1: 1.

Next, the solution (a1) and the solution (b1) obtained above were mixed and reacted by stirring at room temperature for 2 hours.
After the reaction, the solution was allowed to stand to precipitate, so the transparent portion of the supernatant was removed using a dropper.

The remaining precipitate was dried under reduced pressure at 50 ° C. to obtain 1.39 g of a solid (near infrared absorber).
Toluene (near-infrared absorbent dispersion liquid) in which the obtained solid substance and 20 g of toluene were added to a glass container, and the near-infrared absorbent was dispersed by placing the whole glass container in an ultrasonic cleaner for 2 hours and carrying out a dispersion treatment. ) The near-infrared absorber (copper complex) in this dispersion had an average particle size of 46 nm, and no precipitation was observed even after storage at room temperature for 1 month. In addition, the average particle diameter was calculated | required using Otsuka Electronics Co., Ltd. ELSZ-2.

[Example 2]
A solution (a1) obtained by dissolving 0.70 g (3.5 × 10 ⁻³ mol) of copper acetate monohydrate in 35 g of ethanol, and equimolar decylphosphonic acid 0 with respect to copper acetate monohydrate A solution (b1) in which 0.58 g of the same phosphate ester compound (A) as used in Example 1 was dissolved in 5 g of ethanol was prepared.

Next, the solution (a1) and the solution (b1) obtained above were mixed and reacted by stirring at room temperature for 2 hours.
After the reaction, the solution was allowed to stand to precipitate, so the transparent portion of the supernatant was removed using a dropper.

50 g of ethanol was added to the container containing the precipitate and stirred for 10 minutes, and the supernatant obtained by standing was removed using a dropper to obtain a precipitate.
Next, 50 g of ethanol was added to the container containing the precipitate, stirred for 10 minutes, and the supernatant obtained by standing was removed using a dropper to obtain a precipitate.

Again, 50 g of ethanol was added to the container containing the precipitate and stirred for 10 minutes, and the supernatant obtained by standing was removed using a dropper to obtain a precipitate.
The precipitate was dried under reduced pressure at 50 ° C. to obtain 1.15 g of a solid (near infrared absorber).

  A near-infrared absorber is obtained by adding 20 g of the obtained solid substance, toluene, and 0.10 g of the phosphoric acid ester compound (A) to a glass container, and dispersing the whole glass container in an ultrasonic cleaner for 5 hours. Of toluene (near-infrared absorbent dispersion) was obtained. The near-infrared absorber (copper complex) in this dispersion had an average particle size of 64 nm, and no precipitation was observed even after storage at room temperature for 1 month.

[Comparative Example 1]
The same solution (a1) and solution (b1) as in Example 1 were mixed and reacted by stirring at room temperature for 2 hours.

After the reaction, the solvent and acetic acid by-product were removed at 50 ° C. under reduced pressure to obtain 1.5 g of a solid (near infrared absorber).
The obtained solid and 20 g of toluene were added to a glass container, and the whole glass container was placed in an ultrasonic cleaner for 2 hours to attempt a dispersion treatment, but the particle diameter was 88 nm. In order to further reduce the size, ultrasonic treatment was performed for about 3 hours and dispersion was attempted. However, agar was formed on the way, and a stable dispersion could not be obtained.

[Comparative Example 2]
The same solution (a1) and solution (b1) as in Example 1 were mixed and reacted by stirring at room temperature for 2 hours.

After the reaction, the solvent and acetic acid by-product were removed at 50 ° C. under reduced pressure to obtain 1.5 g of a solid (near infrared absorber).
The obtained solid, 20 g of toluene, and 0.10 g of the phosphoric acid ester compound (A) were added to a glass container, and the whole glass container was placed in an ultrasonic cleaner for 2 hours to attempt a dispersion treatment. It became. In order to further reduce the size, ultrasonic treatment was performed for about 3 hours and dispersion was attempted. However, as in Comparative Example 1, it became agar-like on the way, and a stable dispersion could not be obtained.

Example 3
A solution (a2) obtained by dissolving 1.56 g (7.8 × 10 ⁻³ mol) of copper acetate monohydrate in 80 g of ethanol, and equimolar octylphosphonic acid 1 with respect to copper acetate monohydrate A solution (b2) in which 1.02 g of the same phosphate ester compound (A) used in Example 1 was dissolved in 10 g of ethanol was prepared.

Next, the solution (a2) obtained above and the solution (b2) were mixed and reacted by stirring at room temperature for 2 hours.
After the reaction, the solution was allowed to stand to precipitate, so the transparent portion of the supernatant was removed.

The remaining precipitate was dried under reduced pressure at 50 ° C. to obtain 2.45 g of a solid (near infrared absorber).
Methylene chloride (near-infrared absorber) in which near-infrared absorber is dispersed by adding the obtained solid substance, 30 g of methylene chloride to a glass vessel, and putting the whole glass vessel in an ultrasonic cleaner for 10 hours to perform dispersion treatment. Dispersion) was obtained. The average particle size of the near-infrared absorber (copper complex) in this dispersion was 70 nm, and no precipitation was observed even after storage at room temperature for 1 month.

[Comparative Example 3]
The same solution (a2) and solution (b2) as in Example 3 were mixed and reacted by stirring at room temperature for 2 hours.

After the reaction, the solvent and acetic acid as a by-product were removed at 50 ° C. under reduced pressure to obtain 3.0 g of a solid (near infrared absorber).
The obtained solid and 30 g of methylene chloride were added to a glass container, and the whole glass container was placed in an ultrasonic cleaner for 10 hours to attempt dispersion treatment. However, the particle size was reduced only to 104 nm. When this dispersion was stored at room temperature for 1 month, a precipitate was observed.

Example 4
A solution (a2) obtained by dissolving 1.17 g (5.8 × 10 ⁻³ mol) of copper acetate monohydrate in 55 g of ethanol, and equimolar ethylphosphonic acid 0 with respect to copper acetate monohydrate A solution (b2) in which 0.14 g and 0.15 g of the same phosphate ester compound (A) used in Example 1 was dissolved in 5 g of ethanol was prepared.

Next, the solution (a2) obtained above and the solution (b2) were mixed and reacted by stirring at room temperature for 2 hours.
After the reaction, when the solution was centrifuged (3500 rpm, 10 minutes), a precipitate was formed, and thus the transparent portion of the supernatant was removed.

The remaining precipitate was dried under reduced pressure at 50 ° C. to obtain 1.03 g of a solid (near infrared absorber).
A near-infrared absorber is obtained by adding 20 g of the obtained solid substance, toluene, and 0.10 g of the phosphoric acid ester compound (A) to a glass container, and placing the glass container in an ultrasonic cleaner for 10 hours for dispersion treatment. Of toluene (near-infrared absorbent dispersion) was obtained. The average particle size of the near-infrared absorber (copper complex) in this dispersion was 50 nm, and no precipitation was observed even after storage at room temperature for 1 month.

Claims (6)

At least one selected from a phosphonic acid compound represented by the following general formula (1), a phosphoric acid ester compound represented by the following general formula (2a), and a phosphoric acid ester compound represented by the following general formula (2b) Step A in which a phosphate compound of a seed and a copper salt are mixed in a solvent to obtain a reaction mixture containing a near infrared absorber,
Step B1 for precipitating solids in the reaction mixture and removing the supernatant.
Step C for drying the solid content to obtain a purified near infrared absorber, and
The manufacturing method of the near-infrared absorber dispersion liquid which has the process D which disperse | distributes the said refined near-infrared absorber in a dispersion medium.

[In the formula, R ¹ is a monovalent group represented by ^{_{-CH 2 CH 2 -R 11, R}} 11 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a fluorine having 1 to 20 carbon atoms, Represents an alkyl group. R ²¹ , R ²² and R ²³ are a monovalent group represented by — (CH ₂ CH ₂ O) _n R ⁵ , n is an integer of 4 to 35, and R ⁵ is a carbon number of 6 to 25 alkyl groups or C6-C25 alkylphenyl groups are shown. However, R ²¹ , R ²² and R ²³ may be the same or different. ]   The step B1 in which the solid content in the reaction mixture is settled and the supernatant liquid is removed is a step in which the solid content is settled by allowing the reaction mixture to stand and the supernatant liquid is removed, or the reaction mixture is centrifuged. The manufacturing method of the near-infrared absorber dispersion liquid of Claim 1 which is a process of settling solid content and removing a supernatant liquid. Between Step B1 and Step C, the solid content obtained by removing the supernatant liquid is washed by adding a solvent to the solid content, and then the solid content is settled and the supernatant liquid is removed. Performing step B2 at least once,
The method for producing a near-infrared absorber dispersion according to claim 1 or 2, wherein the step C is a step of obtaining a purified near-infrared absorber by drying the solid content obtained in the step B2. Wherein R ¹¹ is the method of producing the near-infrared absorber dispersion according to any one of claims 1 to 3 is an alkyl group having 1 to 10 carbon hydrogen atom or a carbon. Wherein R ¹¹ is the method of producing the near-infrared absorber dispersion according to any one of claims 1 to 3 is an alkyl group having 2 to 8 carbon atoms.   In the said process D, an ultrasonic treatment is performed, The manufacturing method of the near-infrared absorber dispersion liquid as described in any one of Claims 1-5 characterized by the above-mentioned.