JP5738031B2 - Method for producing copper salt fine particle dispersed resin, and copper salt fine particle dispersed resin - Google Patents

Description

  The present invention relates to a method for producing a copper salt fine particle dispersed resin and a copper salt fine particle dispersed resin.

  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.

  Further, the heat resistance of conventional optical materials containing near-infrared absorbers containing copper ions 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

  In view of the above-described background art, the present invention produces a copper salt fine particle-dispersed resin capable of suitably producing optical materials of various sizes and capable of obtaining an optical material having excellent heat resistance. It aims to provide a method.

  As a result of intensive studies to solve the above problems, the present inventors have not made an optical material by using a polymerization cell, but dispersed copper salt fine particles in a resin. It has been found that if a resin is used, optical materials of various sizes can be suitably produced, and the copper salt fine particle dispersed resin is excellent in heat resistance.

  In addition, when the present inventors produce a copper salt fine particle dispersed resin, by providing a step of washing a mixture of near-infrared absorbing copper salt fine particles and a dispersant, copper salt fine particle dispersion having better heat resistance The inventors found that a resin was obtained and completed the present invention.

  That is, the method for producing a copper salt fine particle-dispersed resin according to the present invention comprises washing a mixture containing near-infrared absorbing copper salt fine particles having an average particle diameter of 1 nm to 10 μm and a dispersant with a solvent, and then precipitating the copper salt fine particles. Removing the supernatant and obtaining the copper salt fine particles in step A, dispersing the copper salt fine particles obtained in step A in a dispersion medium, obtaining a dispersion, and mixing the dispersion with a resin. And a step C of obtaining a copper salt fine particle-dispersed resin.

The copper salt fine particles preferably have an average particle size of 5 to 1000 nm.
After the step A is washing the mixture containing the copper salt fine particles and the dispersant with a solvent, the copper salt fine particles are settled by centrifugation or natural sedimentation, the supernatant is removed, and the copper salt fine particles are removed. It is preferable that it is a process to obtain.

The step B is preferably a step in which the copper salt fine particles obtained in the step A are dispersed in a dispersion medium in the presence of a dispersant to obtain a dispersion.
The resin is at least one 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. A resin is preferable, and a polyvinyl butyral resin or an ethylene-vinyl acetate copolymer is more preferable.

  At least a part of the copper salt is preferably a copper salt represented by the following general formula (1), and more preferably a copper salt represented by the following general formula (2).

［一般式（１）中、Ｒは、フッ素原子で置換されていてもよいアルキル基、置換基で置換されていてもよいフェニル基、置換基で置換されていてもよいベンジル基、または‐ＯＲ¹基であり、Ｒ¹はフッ素原子で置換されていてもよいアルキル基、置換基で置換されていてもよいフェニル基、置換基で置換されていてもよいベンジル基である。］

[In general formula (1), R represents an alkyl group optionally substituted with a fluorine atom, a phenyl group optionally substituted with a substituent, a benzyl group optionally substituted with a substituent, or -OR. a ¹ group, R ¹ is a fluorine alkyl group which may be substituted with atoms, a phenyl group optionally substituted with a substituent, may be substituted with a substituent a benzyl group. ]

［一般式（２）中、Ｒ²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。］
本発明の銅塩微粒子分散樹脂は、前記製造方法で得られる。

[In General Formula (2), R ² 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 copper salt fine particle-dispersed resin of the present invention is obtained by the above production method.

  The method for producing a copper salt fine particle-dispersed resin of the present invention includes a step of washing a mixture of near-infrared absorbing copper salt fine particles and a dispersant, so that a copper salt fine particle-dispersed resin having excellent heat resistance can be obtained. . The copper salt fine particle-dispersed resin of the present invention can be suitably used as an optical material such as a near-infrared absorbing film by being molded by a known molding method.

Next, the present invention will be specifically described.
The method for producing a copper salt fine particle-dispersed resin of the present invention comprises washing a mixture containing near-infrared absorbing copper salt fine particles having an average particle diameter of 1 nm to 10 μm and a dispersant with a solvent, and then precipitating the copper salt fine particles. The supernatant A is removed to obtain the copper salt fine particles, step A, the copper salt fine particles obtained in the step A are dispersed in a dispersion medium, the dispersion is obtained, and the dispersion is mixed with a resin to obtain copper. It includes a step C of obtaining a salt fine particle dispersed resin.

The method for producing a copper salt fine particle-dispersed resin of the present invention is obtained by the method of the present invention by including a step A in which a mixture containing the copper salt fine particles and a dispersant is washed with a solvent to obtain copper salt fine particles. The copper salt fine particle dispersed resin is excellent in heat resistance.
First, the mixture containing the near-infrared absorbing copper salt fine particles having an average particle diameter of 1 nm to 10 μm and the dispersant used in the production method of the present invention will be described.

[Mixture containing near-infrared absorbing copper salt fine particles having an average particle diameter of 1 nm to 10 μm and a dispersant]
In the production method of the present invention, a mixture containing near-infrared absorbing copper salt fine particles having an average particle diameter of 1 nm to 10 μm and a dispersant is used.

  In the production method of the present invention, by using near-infrared absorbing copper salt fine particles having an average particle diameter of 1 nm to 10 μm, it is possible to obtain a copper salt fine particle-dispersed resin in which the near-infrared absorbing copper salt fine particles exist without being unevenly distributed. it can. The average particle diameter is preferably 5 to 1000 nm, more preferably 5 to 300 nm, from the viewpoint of ease of production and transparency maintenance.

The near-infrared absorbing copper salt fine particles having an average particle diameter of 1 nm to 10 μm are also simply referred to as copper salt fine particles.
The copper salt fine particles are preferably copper salt fine particles that are excellent in heat resistance and hardly cause coloration of the copper salt fine particle dispersed resin. As a copper salt constituting the copper fine particles, at least a part of the copper salt is preferably a copper salt represented by the following general formula (1).

［一般式（１）中、Ｒは、フッ素原子で置換されていてもよいアルキル基、置換基で置換されていてもよいフェニル基、置換基で置換されていてもよいベンジル基、または‐ＯＲ¹基であり、Ｒ¹はフッ素原子で置換されていてもよいアルキル基、置換基で置換されていてもよいフェニル基、置換基で置換されていてもよいベンジル基である。］

[In general formula (1), R represents an alkyl group optionally substituted with a fluorine atom, a phenyl group optionally substituted with a substituent, a benzyl group optionally substituted with a substituent, or -OR. a ¹ group, R ¹ is a fluorine alkyl group which may be substituted with atoms, a phenyl group optionally substituted with a substituent, may be substituted with a substituent a benzyl group. ]

Examples of the alkyl group which may be substituted with the fluorine atom include R ² in the general formula (2) described later. Examples of the alkyl group that may be substituted with a fluorine atom other than R ² include a perfluoroethyl group, a perfluoropropyl group, a perfluoro-n-butyl group, a perfluorohexyl group, a perfluorooctyl group, and perfluorodecyl. Groups and the like.

  Examples of the phenyl group which may be substituted with the substituent include a phenyl group, a linear or branched alkylphenyl group having 1 to 20 carbon atoms, and a linear or branched alkoxy group having 1 to 20 carbon atoms. Alkoxyphenyl group, aminophenyl group, thiophenyl group, hydroxyphenyl group, nitrophenyl group, cyanophenyl group, linear or branched alkoxycarbonylphenyl group having 1 to 20 carbon atoms, acylphenyl group, carboxyl A phenyl group etc. are mentioned. These substituents may be substituted at any position of the ortho position, meta position, and para position of the phosphorus atom, and may be substituted at two or more positions. Moreover, at least a part of hydrogen atoms of the phenyl group which may be substituted with these substituents may be substituted with fluorine atoms.

  Examples of the benzyl group that may be substituted with the substituent include a benzyl group, a linear or branched alkylbenzyl group having 1 to 20 carbon atoms, and a linear or branched alkoxy group having 1 to 20 carbon atoms. Alkoxybenzyl group, aminobenzyl group, thiobenzyl group, hydroxybenzyl group, nitrobenzyl group, cyanobenzyl group, linear or branched alkoxycarbonylbenzyl group having 1 to 20 carbon atoms, acylbenzyl group, carboxyl A benzyl group etc. are mentioned. These substituents may be substituted at any position of the ortho-position, meta-position and para-position of the methylene group bonded to the phosphorus atom, or may be substituted at two or more positions. Moreover, the group by which at least one part of the hydrogen atom which the benzyl group which may be substituted by these substituents has was substituted by the fluorine atom may be sufficient.

  As the copper salt represented by the general formula (1), it is preferable that R is an alkyl group which may be substituted with a fluorine atom because of excellent near-infrared absorption characteristics. In addition, it is more preferable that at least a part of the copper salt is an alkylphosphonic acid copper salt represented by the following general formula (2) because the near-infrared absorption characteristics are particularly excellent.

［一般式（２）中、Ｒ²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 (2), R ² 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 is a 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, etc. .

The method for producing the copper salt fine particles used in the present invention is not particularly limited, but usually, the copper salt fine particles are produced in the presence of a dispersant to obtain a mixture containing the copper salt fine particles and the dispersant.
In addition, as an example of the manufacturing method of copper salt microparticles | fine-particles, when using the alkylphosphonic acid copper salt represented by the said General formula (2) as a copper salt, it can manufacture with the following method.

  As a method for producing copper salt fine particles in which the copper salt is a copper salt represented by the general formula (2), for example, in a solvent, a phosphonic acid compound represented by the following general formula (3) and a copper salt, Usually, a step of mixing in the presence of a dispersant to obtain a reaction mixture (hereinafter also referred to as a reaction step), a step of obtaining copper salt fine particles by removing a solvent in the reaction mixture (hereinafter also referred to as a solvent removal step) The method which has this is mentioned. In the solvent removal step, when a dispersant is used in the reaction step, a mixture containing copper salt fine particles and a dispersant is obtained.

［一般式（３）中、Ｒ²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 (3), R ² 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. ]

As the R ¹¹ can be, for example, are the same as those for R ¹¹ in the formula (2). In addition, as a phosphonic acid compound represented by General formula (3), it may be used individually by 1 type, or 2 or more types may be used.

  As the copper salt, a copper salt capable of supplying divalent copper ions is usually used. The copper salt may be a copper salt other than the alkylphosphonic acid copper salt represented by the general formula (2), for example, anhydrous copper acetate, anhydrous copper formate, anhydrous copper stearate, anhydrous copper benzoate, anhydrous acetoacetate Copper salt of organic acid such as copper acetate, anhydrous ethyl acetoacetate, anhydrous copper methacrylate, anhydrous copper pyrophosphate, anhydrous copper naphthenate, anhydrous copper citrate, hydrate or hydrate of copper salt of organic acid; oxidation Copper salt of copper, copper chloride, copper sulfate, copper nitrate, copper phosphate, basic copper sulfate, basic copper carbonate, etc., inorganic acid copper salt, hydrate or hydrate of copper salt of inorganic acid; Can be 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.
When producing near-infrared absorbing copper salt fine particles in which the copper salt is an alkylphosphonic acid copper salt represented by the general formula (2), a dispersant is usually used. Use of a dispersant is preferable because the dispersibility of the alkylphosphonic acid copper salt represented by the general formula (2) is improved. Examples of the dispersant include at least one phosphate ester compound selected from a phosphate ester compound represented by the general formula (4a) and a phosphate ester compound represented by the general formula (4b). As at least one phosphate ester compound selected from the phosphate ester compound represented by the general formula (4a) and the phosphate ester compound represented by the general formula (4b), for example, NIKKOL DOP-8NV, NIKKOL DLP-10, NIKKOL DDP-6, NIKKOL DDP-8, NIKKOL DDP-10, NIKKOL TDP-6, NIKKOL TDP-8, NIKKOL TDP-10 (manufactured by Nikko Chemicals Co., Ltd.), Prisurf A219B Commercial products such as Surf A217E and Prisurf A210G (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) can also be used. Moreover, the neutralized product of the phosphate ester compound obtained by neutralizing phosphoric acid (P-OH) in these compounds with a suitable base can also be used. Examples of the base used for neutralization include inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, and calcium hydroxide, triethylamine, diisopropylethylamine, triisobutylamine, pyridine, 4 -Tertiary amines such as dimethylaminopyridine.

［一般式（４ａ）および（４ｂ）中、Ｒ²¹、Ｒ²²およびＲ²³は、−（ＣＨ₂ＣＨ₂Ｏ）_nＲ⁵で表される１価の基であり、ｎは４〜４５の整数であり、Ｒ⁵は、炭素数６〜２５のアルキル基または炭素数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 general formulas (4a) and (4b), R ²¹ , R ²² and R ²³ are monovalent groups represented by — (CH ₂ CH ₂ O) _n R ⁵ , and n is 4 to 45. It is an integer and R ⁵ represents an alkyl group having 6 to 25 carbon atoms or an alkylphenyl group having 6 to 25 carbon atoms. However, R ²¹ , R ²² and R ²³ may be the same or different. ]

  The n is more preferably an integer of 6 to 30. When n is less than 4, transparency may be insufficient when an optical material such as a near-infrared absorbing film is produced. On the other hand, when n exceeds 45, the amount of the phosphoric acid ester compound necessary for obtaining an optical material such as a near-infrared absorbing film having sufficient transparency increases, which tends to cause 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 preferably an alkyl group having 10 to 20 carbon atoms. Is more preferable. When R ⁵ is a group having less than 6 carbon atoms, transparency may be insufficient when an optical material such as a near infrared absorbing film is produced. Further, if R ⁵ is a group having more than 25 carbon atoms, the amount of the phosphoric acid ester compound necessary for obtaining an optical material such as a near-infrared absorbing film having sufficient transparency increases, resulting in high costs. Tend to be.

  When obtaining the copper salt fine particles used in the present invention, at least one of the phosphate ester compound represented by the general formula (4a), the phosphate ester compound represented by the general formula (4b), or a neutralized product thereof However, it is more preferable to use both of the phosphate ester compound represented by the general formula (4a) and the phosphate ester compound represented by the general formula (4b) or a neutralized product thereof. . When the phosphate ester compound represented by the general formula (4a) and the phosphate ester compound represented by the general formula (4b) or a neutralized product thereof are used, the transparency of an optical material such as a near-infrared absorbing film, It tends to be excellent in heat resistance, which is preferable. When both the phosphate ester compound represented by the general formula (4a) and the phosphate ester compound represented by the general formula (4b) or a neutralized product thereof are used, they are represented by the general formula (4a). The ratio of the phosphoric acid ester compound and the phosphoric acid ester compound represented by the general formula (4b) is not particularly limited, but is usually 10:90 to 90: in a molar ratio ((4a) :( 4b)). 10.

  Moreover, as a phosphate ester compound represented by the said general formula (4a), 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 (4b) May be used alone or in combination of two or more.

  In addition, when manufacturing copper salt microparticles | fine-particles, it is preferable to use 0.9-1.1 mol of phosphonic acid compounds represented by General formula (3) per 1 mol of said copper salts. Further, the dispersant is at least one phosphate ester compound selected from the phosphate ester compound represented by the general formula (4a) and the phosphate ester compound represented by the general formula (4b), or a neutralized product thereof. In this case, 0.005 to 0.5 mol is preferably used per 1 mol of the copper salt.

  Examples of the solvent include alcohols such as methanol, ethanol, and isopropanol, tetrahydrofuran (THF), dimethylformamide (DMF), toluene, xylene, methylene chloride, chloroform, water, and the like. Toluene, THF or DMF is preferred. The reaction step is preferably performed at a temperature of 5 to 60 ° C, more preferably 10 to 40 ° C, preferably 0.5 to 50 hours, more preferably 1 to 30 hours.

  In the reaction step, the phosphonic acid compound represented by the general formula (3) reacts with the copper salt, and the reaction causes the phosphonic acid represented by the fine particle general formula (2) not dissolved in the solvent. Copper salt is formed. At least one phosphate ester compound selected from the phosphate ester compound represented by the general formula (4a) and the phosphate ester compound represented by the general formula (4b) or a neutralized product thereof is good during the reaction. Therefore, the phosphonic acid copper salt can maintain high dispersibility and suppress aggregation.

  In the reaction step, not only the reaction of the phosphonic acid compound represented by the general formula (3) and the copper salt, but also the phosphate ester compound represented by the general formula (4a) and the general formula (4b), for example. ) At least one phosphate ester compound selected from the phosphate ester compounds represented by (1) or a neutralized product thereof may react with a part of the copper salt. Further, a part of the raw material may remain without reacting.

In the method for producing copper salt fine particles, usually, copper salt fine particles are obtained by removing at least a part of the solvent from the reaction mixture.
In the solvent removal step, at least a part of the solvent is removed from the reaction mixture. In the solvent removal step, in addition to the solvent, the liquid components in the reaction mixture may be removed together.

  In the solvent removal step, at least a part of the solvent is usually removed by heating the reaction mixture, but the heating condition is usually room temperature to 70 ° C, preferably 40 to 60 ° C. The solvent removal step may be performed under normal pressure or under reduced pressure. When the solvent removal step is performed under reduced pressure, heating may not be performed or the heating temperature may be low.

  When copper salt fine particles are produced using the dispersant, the copper salt fine particles are obtained as a mixture containing copper salt fine particles and a dispersant. In addition, a part of solvent, a by-product, etc. may be contained in this mixture.

  The mixture containing the near-infrared absorbing copper salt fine particles and the dispersant used in the production method of the present invention can be prepared, for example, by the above-mentioned method, and the mixture is usually based on 100 parts by mass of the copper salt fine particles. And 1 to 300 parts by mass of a dispersant.

  In addition, after performing the solvent removal step, the near-infrared absorbing copper salt fine particles were dispersed in a dispersion medium for the purpose of azeotropic removal of volatile impurities contained in the near-infrared absorbing copper salt fine particles. A step of removing the dispersion medium may be provided later.

Examples of the dispersion medium include toluene, xylene, tetrahydrofuran (THF), dimethylformamide (DMF), methylene chloride, chloroform and the like.
Next, the resin used in the production method of the present invention will be described.

[resin]
In the present invention, a resin is used. The resin used in the present invention is not particularly limited as long as it can disperse the above-described near-infrared absorbing copper salt fine particles. 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 kind of resin can disperse near-infrared absorbing copper salt fine particles satisfactorily 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 and ethylene-vinyl acetate copolymer, polyvinyl butyral resin (PVB), and ethylene-vinyl acetate copolymer Particularly preferred is at least one resin selected from a coalescence, and most preferred is a polyvinyl butyral resin or an ethylene-vinyl acetate copolymer. When the polyvinyl acetal resin is used, it is excellent in dispersibility of the above-mentioned near-infrared absorbing copper salt fine particles, and when producing an optical material using the copper salt fine particle-dispersed resin obtained by the production method of the present invention, to glass or the like. The copper salt fine particle-dispersed resin is preferable because it is flexible and the copper salt fine particle-dispersed resin is not easily deformed due to temperature change. 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 molecular weight, molecular weight distribution, and degree of acetalization of the polyvinyl acetal resin are not particularly limited, but the degree of acetalization is generally 40 to 85%, and the preferred lower limit is 60% and the upper limit is 75%.

  The polyvinyl acetal resin can be obtained by acetalizing a polyvinyl alcohol resin with an aldehyde. The polyvinyl alcohol resin is generally obtained by saponifying polyvinyl acetate, and a polyvinyl alcohol resin having a saponification degree of 80 to 99.8 mol% is generally used. The preferable lower limit of the viscosity average polymerization degree of the polyvinyl alcohol resin is 200, and the upper limit is 3000. If it is less than 200, the penetration resistance of the resulting laminated glass may be lowered. If it exceeds 3000, the moldability of the copper salt fine particle dispersed resin may be deteriorated, and the rigidity of the copper salt fine particle dispersed resin becomes too large, resulting in poor workability. A more preferred lower limit is 500 and an upper limit is 2200. The viscosity average polymerization degree and saponification degree of the polyvinyl alcohol resin can be measured based on, for example, JISK 6726 “Testing method for polyvinyl alcohol”.

  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 glass dispersibility, dispersibility, transparency, heat resistance, light resistance, and the like because of excellent dispersibility of the above-mentioned near-infrared absorbing copper salt fine particles.

  The method for producing a copper salt fine particle-dispersed resin according to the present invention includes the step of washing a mixture containing near-infrared absorbing copper salt fine particles having an average particle diameter of 1 nm to 10 μm and a dispersant as described above with a solvent, and then the copper salt fine particles. The step A for obtaining the copper salt fine particles by removing the supernatant, the step B for obtaining the dispersion by dispersing the copper salt fine particles obtained in the step A in a dispersion medium, Step C is mixed to obtain a copper salt fine particle dispersed resin. Hereafter, each process in the manufacturing method of this invention is demonstrated.

[Step A]
In the method for producing a copper salt fine particle-dispersed resin of the present invention, first, after washing a mixture containing near-infrared absorbing copper salt fine particles having an average particle diameter of 1 nm to 10 μm and a dispersant with a solvent, the copper salt fine particles are precipitated. And removing the supernatant and performing step A to obtain the copper salt fine particles.

  In step A, first, the mixture containing the copper salt fine particles and the dispersant is washed with a solvent. Washing is usually performed by mixing the mixture and a solvent and stirring. Moreover, in order to grind | pulverize the lump of the aggregated copper salt, you may irradiate an ultrasonic wave with respect to the liquid which mixed the said mixture and solvent. By this washing, it is possible to dissolve the dispersant in the mixture and the subcomponents soluble in the solvent that are considered to be present in the mixture in the solvent. The amount ratio of the mixture to the solvent when washing is not particularly limited, but is preferably an amount that can be suitably washed by stirring and the like, specifically, with respect to 100 parts by mass of the mixture. The solvent is preferably 300 to 30000 parts by mass, and more preferably 500 to 10000 parts by mass. Stirring may be performed by putting a stirring bar into the dispersion and stirring with a magnetic stirrer or with a test tube mixer. The stirring speed is usually 10 rpm to 1000 rpm, and the stirring time is usually 1 minute to 1 hour. Moreover, when irradiating an ultrasonic wave, what is necessary is just to irradiate time sufficient for the lump of the agglomerated copper salt to be about 1 mm or less visually, and specifically, it is 1 minute-3 hours normally.

  The solvent is not particularly limited as long as it can dissolve the dispersant, and examples thereof include methanol, ethanol, isopropanol, tetrahydrofuran (THF), dimethylformamide (DMF), water, and the like, and methanol, ethanol, and the like are preferable. The solvent may be a mixed solvent composed of a plurality of components.

  In step A, after washing, the copper salt fine particles are allowed to settle. As a method of settling, for example, when washing is carried out by stirring, a method of allowing the mixture to settle naturally by stopping stirring and standing, or a method of settling by centrifugation are exemplified.

  As a method of settling, natural settling is preferable from the viewpoint of cost. However, when the particle diameter of the copper salt fine particles is small, natural sedimentation may be difficult or may be required for a long time for natural sedimentation. In such a case, it is preferable to precipitate the copper salt fine particles by performing centrifugation. As rotation conditions for the centrifugation, the rotation is usually performed at 500 rpm to 10,000 rpm. The centrifugation time is usually 1 minute to 3 hours.

  In Step A, after the copper salt fine particles are settled, the supernatant is removed to obtain copper salt fine particles. 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 A, the washing, sedimentation, and removal of the supernatant liquid are performed, whereby the copper salt fine particles from which the dispersant in the mixture and the secondary components soluble in the solvent are removed can be obtained. Further, for the purpose of increasing the purity of the copper salt fine particles, it is preferable to repeatedly perform the washing, sedimentation, and removal of the supernatant. Repeated washing, sedimentation, and removal of the supernatant are preferable because the heat resistance of the copper salt fine particle dispersed resin tends to be further improved. In addition, although it does not specifically limit as the frequency | count in the case of performing repeatedly, It is preferable to repeat in the range which the heat resistance of the copper salt fine particle dispersion resin obtained by the manufacturing method of this invention fully improves, for example, 1-3 times. Repeating once means that after washing, sedimentation, and removal of the supernatant liquid, a solvent is added again to the obtained copper salt fine particles to perform washing, sedimentation, and removal of the supernatant liquid.

  The reason why the copper salt fine particle-dispersed resin obtained by the production method of the present invention is excellent in heat resistance is not clear, but by performing Step A, the present inventors have removed subcomponents soluble in the solvent. It was speculated that this contributed to the improvement of the heat resistance of the copper salt fine particle dispersed resin.

  Further, the step of dispersing the copper salt fine particles obtained in step A in the solvent or the like again between step A and step B described later, and then distilling off the solvent under reduced pressure to obtain the copper salt fine particles. It may be provided. Providing this step is preferable from the viewpoint of preventing aggregation of the copper salt fine particles.

[Step B]
In the method for producing a copper salt fine particle-dispersed resin of the present invention, after performing the step A, the step B is performed in which the copper salt fine particles obtained in the step A are dispersed in a dispersion medium to obtain a dispersion.

  In step B, the copper salt fine particles obtained in step A are 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 copper salt fine particles in the dispersion medium is not particularly limited. By adding the copper salt fine particles to the dispersion medium and irradiating with ultrasonic waves, the copper salt fine particles are added to the dispersion medium and stirred. Examples thereof include a method of dispersing, a method of adding copper salt fine particles to a dispersion medium, and pulverizing and dispersing with a ball mill.

  Although there is no limitation in particular as the quantity of the dispersion medium used at the process B, From a viewpoint of the size of manufacturing equipment, when a copper salt fine particle shall be 100 mass parts normally, 300-30000 mass parts of dispersion media are used.

  In Step B, it is preferable to disperse the copper salt fine particles in a dispersion medium in the presence of a dispersant to obtain a dispersion. As the dispersant used in Step B, the dispersant described in the section of the mixture containing the copper salt fine particles and the dispersant can be used. Moreover, as a dispersing agent, the same dispersing agent as the dispersing agent used when synthesize | combining the mixture containing copper salt microparticles | fine-particles and a dispersing agent may be used, and a different thing may be used.

Although there is no limitation in particular as the quantity of the dispersing agent used at the process B, Usually, 1-300 mass parts will be used if a copper salt microparticle is 100 mass parts.
Moreover, in this process B, you may add another additive to a solvent. Examples of other additives include plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, dehydrating agents, adhesive force adjusting agents, silane coupling agents, and pigments.

[Step C]
In the method for producing a copper salt fine particle-dispersed resin of the present invention, after performing Step B, Step C is performed in which the dispersion obtained in Step B is mixed with a resin to obtain a copper salt fine particle dispersed resin.

In Step C, the dispersion liquid is mixed with a resin to obtain a copper salt fine particle dispersed resin. Usually, in Step C, at least a part of the dispersion medium is removed.
The amount of the copper salt fine particles dispersed in the copper salt fine particle dispersed resin obtained by the production method of the present invention is not particularly limited, but the copper salt fine particles are usually 0.1 to 15% by mass, preferably 0. 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

  A specific embodiment of Step C is not particularly limited, but for example, a step of obtaining a copper salt fine particle dispersed resin by mixing at least a part of the dispersion medium with the dispersion liquid (hereinafter referred to as Step C). -1)), the dispersion is mixed with a small amount of resin, and at least a part of the dispersion medium is removed to obtain a master batch of the copper salt fine particle dispersed resin, and then the master batch is kneaded with the resin. Thus, a step of obtaining a copper salt fine particle-dispersed resin (hereinafter also referred to as step C-2) and the like can be mentioned.

  When performing Step C-1 as Step C, Step C-1-1 for obtaining a mixture of the dispersion and the resin by mixing the dispersion and the resin, at least the dispersion medium in the mixture Part C-1-2 is obtained by removing a part and obtaining a copper salt fine particle-dispersed resin.

Step C-1-1 is usually performed by adding a resin to the dispersion and mixing.
The amount of the copper salt fine particles used in the step C-1-1 is not particularly limited, but the amount of the copper salt fine particles dispersed in the copper salt fine particle dispersed resin obtained in the step C-1-2 is usually 0.00. 1 to 15% by mass, preferably 0.1 to 10% by mass, more preferably 0.5 to 5.0% by mass. The amount of the resin used in the step is not particularly limited, but the amount of the resin contained in the copper salt fine particle-dispersed resin obtained in step C-1-2 is usually 50 to 99% by mass, preferably 60. It is used in an amount of ˜99 mass%, more preferably 65 to 95 mass%.

  Moreover, in process C-1-1, you may mix another additive with a dispersion liquid and resin. Examples of other additives include plasticizers (eg, 3GO (triethylene glycol bis (2-ethylhexanoate)), etc. Further, methylene chloride, chloroform, A solvent such as an ethanol / toluene mixed solvent may be added.

  In Step C-1-1, since the near-infrared absorbing copper salt fine particles are mixed in the resin in the state of the dispersion, the near-infrared absorbing copper salt fine particles are more uniform in the resin than in the case of directly mixing the near-infrared absorbing copper salt fine particles with the resin. Can be dispersed.

In the step C-1-2, at least a part of the dispersion medium in the mixture of the dispersion liquid and the resin obtained in the step C-1-1 may be removed.
The method for removing the dispersion medium is not particularly limited, and although it varies depending on the boiling point of the dispersion medium, methods such as heat drying, vacuum drying, and heat vacuum drying are used. In drying, from the viewpoint of suppressing deterioration of the resin, the temperature is preferably room temperature to 100 ° C. even when heating.

A copper salt fine particle-dispersed resin can be obtained by the step C-1-2.
When performing Step C-2 as Step C, Step C-2-1 for obtaining a mixture of the dispersion and the resin by mixing the dispersion and resin, and at least the dispersion medium in the mixture A step C-2-2 for obtaining a master batch by removing a part, and a step C-2-3 for obtaining a copper salt fine particle-dispersed resin by kneading the master batch and a resin are performed.

Step C-2-1 is usually performed by adding a resin to the dispersion and mixing.
The amount of resin used in Step C-2-1 is usually within a range where a master batch in which 1 to 30% by mass of copper salt fine particles are dispersed is obtained in Step C-2-2 for obtaining a master batch described later. Good. The master batch contains copper salt fine particles and a resin, and further contains additives such as a dispersant. The amount of the resin used may be 1 to 30% by mass of the copper salt fine particles when the entire masterbatch is 100% by mass, and is not particularly limited, but the entire masterbatch is 100% by mass. When used, the resin is usually used in the range of 30 to 95% by mass, and preferably in the range of 50 to 90% by mass.

  Moreover, in this process C-2-1, you may mix another additive with a dispersion liquid and resin. Examples of other additives include plasticizers (eg, 3GO (triethylene glycol bis (2-ethylhexanoate)), etc. Further, methylene chloride, chloroform, A solvent such as an ethanol / toluene mixed solvent may be added.

  In the step C-2-1, since the mixture is mixed with the resin in a dispersion state, the near-infrared absorbing copper salt fine particles are mixed in the resin as compared with the case where the near-infrared absorbing copper salt fine particles are directly mixed with the resin. It can be uniformly dispersed.

  In the step C-2-2, following the step C-2-1 described above, a master batch is obtained by removing at least a part of the dispersion medium in the mixture. In the master batch, usually 1 to 30% by mass of copper salt fine particles are dispersed.

  In Step C-2-2, the dispersion medium in the mixture may be removed. As a specific example, the mixture may be formed into a desired shape by a cast molding method, and then the dispersion medium may be removed to obtain a master batch. The medium may be removed.

  As a method for removing the dispersion medium, although it depends on the boiling point of the dispersion medium, a method such as heat drying, vacuum drying, or heat vacuum drying is used. In drying, from the viewpoint of suppressing deterioration of the resin, the temperature is preferably room temperature to 100 ° C. even when heating.

  By this step, a master batch in which copper salt fine particles are usually dispersed by 1 to 30% by mass can be obtained. The master batch may contain the additives used in the step of obtaining the above-mentioned dispersion, step C-2-1, and the like. The master batch obtained in this step can uniformly disperse the copper salt fine particles in the resin as compared with the master batch obtained by directly kneading the copper salt fine particles with the resin.

  In the step C-2-3, the master batch obtained in the step C-2-2 and the resin are kneaded to obtain a copper salt fine particle dispersed resin. The copper salt fine particle-dispersed resin obtained in this step is preferably a copper salt fine particle-dispersed resin formed from a resin and copper salt fine particles in which 0.1 to 15% by mass of copper salt fine particles are dispersed.

By this step C-2-3, a copper salt fine particle-dispersed resin adjusted to a desired copper salt fine particle content when used in various applications can be obtained.
As the resin used in Step C-2-3, the same resin as that used in Step C-2-1 or a different resin may be used, but the compatibility, dispersibility, and transparency of the resin may be used. From the viewpoint of safety, usually the same resin is used.

  Kneading is usually performed by kneading the master batch and the resin using a kneader. As the kneader, for example, a single screw extruder, a twin screw extruder, a Banbury mixer, a roll mill, a kneader, or the like is used.

The kneading is usually performed at a temperature of 150 to 240 ° C.
Moreover, you may use an additive in this process C-2-3. Examples of the additive include a plasticizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a dehydrating agent, an adhesive force adjusting agent, a silane coupling agent, and a pigment.

  The amount of resin used in Step C-2-3 is 0.1 to 15% by mass, preferably 0.1 to 10% by mass, more preferably 0.5 to 5.0% by mass of copper salt fine particles. It is only necessary to obtain a copper salt fine particle dispersed resin. The copper salt fine particle-dispersed resin contains copper salt fine particles and a resin, and further contains additives such as a dispersant. The amount of resin used is not particularly limited as long as the total amount of the copper salt fine particle-dispersed resin is 100% by mass, and the copper salt fine particle may be 0.1 to 15% by mass. Usually, the resin is used in an amount of 50 to 3000 parts by mass, preferably 100 to 1500 parts by mass with respect to parts by mass.

  Since the copper salt fine particle dispersed resin obtained by the production method of the present invention is obtained by the production method having the step A, it has excellent heat resistance. Further, since the copper salt fine particle dispersed resin can be molded by various molding methods such as extrusion molding, cast molding, and injection molding, it is possible to suitably manufacture optical materials of various sizes.

  Examples of the optical material formed from the copper salt fine particle-dispersed resin of the present invention include a near-infrared absorbing film for display, a visibility correction filter disposed in a light receiving part such as a photodiode, and the like.

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

[Example 1]
(Preparation of copper salt dispersion)
To a 200 ml eggplant flask, 1.16 g (5.83 mmol) of copper acetate monohydrate and 34.9 g of ethanol were added and stirred at 20 ° C. for complete dissolution. To this, 0.5 g of sodium neutralized product of Prisurf A219B (Daiichi Kogyo Kagaku) was added and stirred at 20 ° C. for 2.5 hours to obtain a solution (liquid A). A solution (liquid B) was prepared by dissolving 449 mg (4.08 mmol) of ethylphosphonic acid and 389 mg (1.75 mmol) of 1-decylphosphonic acid in 11.6 g of ethanol. B liquid was dripped with respect to A liquid in about 5 minutes. After stirring this reaction liquid at 20 degreeC for 10 hours, the solvent was distilled off by the evaporator (water bath 60 degreeC) and it was made to dry. 30 g of toluene was added to this, and it was distilled off with an evaporator until it became a constant weight and the acetic acid odor disappeared. The yield was 1.69 g (yield 100%). Toluene 20g was added to this, and the ultrasonic wave was irradiated for 10 hours, the copper salt was disperse | distributed, and the toluene dispersion liquid was obtained.

(Copper salt washing, supernatant removal, redispersion operation (step A and step B))
In an eggplant flask, 2.82 g of the above toluene dispersion was taken, and toluene was distilled off with an evaporator. Ethanol 10g was added to this, ultrasonic irradiation, stirring, etc. were performed, and it was made not to form a lump. The dispersion was stirred for 1 hour to wash the solid. The dispersion was transferred to a test tube and stirred with a test tube mixer, and then centrifuged with a centrifuge (3000 rpm, 10 minutes). The supernatant was removed with a Pasteur pipette. 10 g of ethanol was added to the test tube, and the mixture was stirred with a test tube mixer, and then centrifuged with a centrifuge (3000 rpm, 10 minutes). The supernatant was removed with a Pasteur pipette. The obtained precipitate was suspended in ethanol, transferred to an eggplant flask, and concentrated with an evaporator to obtain 170 mg of a light blue solid. To this, 39 mg of Prisurf A219B sodium neutralized product and 10 g of toluene were added, and ultrasonic waves were applied for 4.5 hours to disperse the copper salt.

(Preparation of copper salt fine particle dispersed resin (step C))
In a 500 ml beaker, 2.43 g of triethylene glycol bis (2-ethylhexanoate), 300 ml of methylene chloride, 10.21 g of the toluene dispersion after the above copper salt washing, supernatant removal, and redispersion operations, polyvinyl butyral (PVB 6.38 g was added and stirred for 0.5 hour, and then the solution was spread on a Teflon vat and air-dried at 20 ° C. for 12 hours. The obtained resin was vacuum-dried at 50 ° C. for 3 hours to obtain a PVB resin in which copper salt fine particles were dispersed.

(Evaluation)
The PVB resin 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 mold and a compression molding machine manufactured by Shinto Metal Industries Co., Ltd., and then at 15 MPa. The resin sheet (1) was obtained by pressing for 3 minutes.

<Preparation of measurement sample (1)>
Both surfaces of the resin sheet (1) were sandwiched between slide glasses (thickness 1.2 to 1.5 mm), and a laminated glass (1) was formed on a 70 ° C. plate.

  The laminated glass (1) 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 (1) in which slide glasses were disposed on both surfaces of the resin sheet. .

<Preparation of measurement sample (2)>
The resin sheet (1) was further preheated at 200 ° C. and 3 MPa for 1 minute using a 0.8 mm thick formwork and a compression molding machine manufactured by Shindo Metal Industry Co., Ltd., and then at 10 MPa for 15 minutes. The resin sheet (2) was obtained by pressing.

  Except that the resin sheet (1) was replaced with the resin sheet (2), the measurement was performed in the same manner as the measurement sample (1) to obtain a measurement sample (2) in which slide glasses were disposed on both surfaces of the resin sheet. .

<Evaluation of heat resistance>
The spectra of the measurement samples (1) and (2) were measured by the following methods, respectively.
The spectrum of the measurement sample was measured using a spectrophotometer (U-4000 type, 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 (1) had a YI (yellowness index) of 3.4, and the measurement sample (2) had a YI of 5.6. The YI value was calculated according to the following formula.

YI = (128X−106Z) / Y
When the difference between the YI of the measurement sample (1) and the YI of the measurement sample (2) (YI of the measurement sample (2) −YI of the measurement sample (1)) is ΔYI, ΔYI was 2.2.
The measurement sample (2) was stored in a constant temperature oven at 100 ° C. for 400 hours. After 400 hours had passed, the sample was taken out and the spectrum was measured to obtain YI. As a result, YI was 8.0.

[Comparative Example 1]
(Preparation of copper salt fine particle dispersed resin)
In a 500 ml beaker, 2.43 g of triethylene glycol bis (2-ethylhexanoate), 300 ml of methylene chloride, 2.82 g of a toluene dispersion obtained in the same manner as in the preparation of the copper salt dispersion of Example 1 After adding 6.38 g of polyvinyl butyral (PVB, manufactured by Solusia) and stirring for 0.5 hour, the solution was spread on a Teflon vat and air-dried at 20 ° C. for 12 hours. The obtained resin was vacuum-dried at 50 ° C. for 3 hours to obtain a PVB resin in which copper salt fine particles were dispersed.

(Evaluation)
The PVB resin in which the copper salt fine particles dispersed in the section of Comparative Example 1, Preparation of the copper salt fine particle dispersed resin was used as the PVB resin in which the copper salt fine particles used in the production of the resin sheet (1) of Example 1 were dispersed. A resin sheet (c1) was obtained by pressing under the same conditions (120 ° C., 15 MPa) as in Example 1 except that the above was replaced.

<Preparation of measurement sample (c1)>
A measurement sample (c1) was obtained in the same manner as in the preparation of the measurement sample (1) in Example 1, except that the resin sheet (1) was replaced with the resin sheet (c1).

<Preparation of measurement sample (c2)>
Except having replaced the resin sheet (1) with the resin sheet (c1), it carried out similarly to the preparation of the measurement sample (2) of Example 1, and obtained the measurement sample (c2).

<Evaluation of heat resistance>
Spectroscopy of the measurement sample (c1) and the measurement sample (c2) was measured in the same manner as the method described in Example 1. The measurement sample (c1) had a YI of 2.8, and the measurement sample (c2) had a YI of 7.1. ΔYI of the measurement sample (c1) and the measurement sample (c2) was 4.3.

  The measurement sample (c2) was stored in a constant temperature oven at 100 ° C. for 400 hours. After 400 hours had passed, the sample was taken out and measured for spectroscopy to obtain YI. The YI was 12.1.

[Example 2]
(Preparation of copper salt dispersion)
To a 1 L eggplant flask, 4.656 g (23.32 mmol) of copper acetate monohydrate and 140 g of ethanol were added and stirred at 20 ° C. to completely dissolve. To this, 4.0 g of sodium neutralized product of PRISURF A219B (Daiichi Kogyo Kagaku) was added and stirred at 20 ° C. for 2 hours to obtain a solution (liquid A). A solution (liquid B) was prepared by dissolving 1.80 g (16.32 mmol) of ethylphosphonic acid and 1.56 g (7.0 mmol) of 1-decylphosphonic acid in 46 g of ethanol. B liquid was dripped with respect to A liquid in about 20 minutes. After stirring this reaction liquid at 20 degreeC for 10 hours, the solvent was distilled off by the evaporator (water bath 60 degreeC) and it was made to dry. 80 g of toluene was added to this, and it was distilled off with an evaporator until it became a constant weight and the acetic acid odor disappeared. The yield was 8.2 g (yield 100%). Toluene 80g was added to this, and the ultrasonic wave was irradiated for 20 hours, the copper salt was disperse | distributed, and the toluene dispersion liquid was obtained.

(Copper salt washing, supernatant removal, redispersion operation (step A and step B))
In a 50 ml eggplant flask, 2.82 g of the above toluene dispersion was taken, and toluene was distilled off with an evaporator. Ethanol 10g was added to this, ultrasonic irradiation, stirring, etc. were performed, and it was made not to form a lump. The dispersion was stirred for 1 hour to wash the solid. The dispersion was transferred to a test tube and stirred with a test tube mixer, and then centrifuged with a centrifuge (3000 rpm, 1 hour). The supernatant was removed with a Pasteur pipette. Further, 10 g of ethanol was added to the test tube, and the mixture was stirred with a test tube mixer, and then centrifuged with a centrifuge (3000 rpm, 30 minutes). The supernatant was removed with a Pasteur pipette. Further, 10 g of ethanol was added to the test tube, and the mixture was stirred with a test tube mixer, and then centrifuged with a centrifuge (3000 rpm, 30 minutes). The supernatant was removed with a Pasteur pipette. The obtained precipitate was suspended in ethanol, transferred to an eggplant flask, and concentrated with an evaporator to obtain 240 mg of a light blue solid. To this, 44 mg of plysurf A219B cesium neutralized product and 10 g of toluene were added, and ultrasonic waves were applied for 6 hours to disperse the copper salt.

(Preparation of copper salt fine particle dispersed resin (step C))
In a 500 ml beaker, 2.43 g of triethylene glycol bis (2-ethylhexanoate), 300 ml of methylene chloride, 10.28 g of toluene dispersion after the above copper salt washing, supernatant removal and redispersion operations, polyvinyl butyral (PVB 6.38 g) was added and stirred at 20 ° C. for 2.5 hours. The solution was spread on a Teflon vat and air-dried at 20 ° C. for 12 hours. The obtained resin was vacuum-dried at 50 ° C. for 3.5 hours to obtain a PVB resin in which copper salt fine particles were dispersed.

(Evaluation)
The PVB resin in which the copper salt fine particles dispersed in Example 2, the preparation of the copper salt fine particle dispersed resin was used as the PVB resin in which the copper salt fine particles used in the production of the resin sheet (1) of Example 1 were dispersed. A resin sheet (2) was obtained by pressing under the same conditions (120 ° C., 15 MPa) as in Example 1 except that the above was replaced.

<Preparation of measurement sample (3)>
A measurement sample (3) was obtained in the same manner as in Example 1 except that the resin sheet (1) was replaced with the resin sheet (2).

<Preparation of measurement sample (4)>
Except having replaced the resin sheet (1) with the resin sheet (2), it carried out similarly to the preparation of the measurement sample (2) of Example 1, and obtained the measurement sample (4).

<Evaluation of heat resistance>
Spectroscopy of the measurement sample (3) and the measurement sample (4) was measured in the same manner as the method described in Example 1. YI of the measurement sample (3) was 5.6. YI of the measurement sample (4) was 9.3. ΔYI of measurement sample (3) and measurement sample (4) was 3.7.

  The measurement sample (4) was stored in a constant temperature oven at 100 ° C. for 400 hours. After 400 hours had passed, the sample was taken out and measured for spectroscopy to obtain YI. As a result, YI was 10.9.

Claims (7)

A step of washing a mixture containing near-infrared absorbing copper salt fine particles having an average particle diameter of 1 nm to 10 μm and a dispersant with a solvent, and then precipitating the copper salt fine particles, removing a supernatant, and obtaining the copper salt fine particles A,
Step B in which the copper salt fine particles obtained in Step A are dispersed in a dispersion medium to obtain a dispersion.
The dispersion was mixed with the resin, it saw including a step C to obtain a copper salt fine particle dispersed resin,
At least a part of the near-infrared absorbing copper salt fine particles is an alkylphosphonic acid copper salt represented by the following general formula (2):
A step of mixing the phosphonic acid compound represented by the following general formula (3) with a copper salt in the presence of a dispersant to obtain a reaction mixture, wherein the mixture containing the near-infrared absorbing copper salt fine particles and the dispersant is: A method for producing a copper salt fine particle-dispersed resin obtained by a method comprising a step of obtaining a mixture containing near-infrared absorbing copper salt fine particles and a dispersant by removing a solvent in the reaction mixture .

[In General Formula (2), R ² 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 General Formula (3), R ² 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 copper salt fine particle-dispersed resin according to claim 1, wherein the copper salt fine particles have an average particle diameter of 5 to 1000 nm.   After the step A is washing the mixture containing the copper salt fine particles and the dispersant with a solvent, the copper salt fine particles are settled by centrifugation or natural sedimentation, the supernatant is removed, and the copper salt fine particles are removed. The method for producing a copper salt fine particle-dispersed resin according to claim 1 or 2, which is a step of obtaining.   The copper according to any one of claims 1 to 3, wherein the step B is a step of dispersing the copper salt fine particles obtained in the step A in a dispersion medium in the presence of a dispersant to obtain a dispersion. Manufacturing method of salt fine particle dispersed resin.   The resin is at least one 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 resin, The manufacturing method of the copper salt fine particle dispersion resin as described in any one of Claims 1-4.   The method for producing a copper salt fine particle-dispersed resin according to any one of claims 1 to 4, wherein the resin is a polyvinyl butyral resin or an ethylene-vinyl acetate copolymer. Copper salt fine particle dispersion resin obtained by the manufacturing method as described in any one of Claims 1-6 .