JPWO2014119618A1 - Manufacturing method of near infrared absorber, near infrared absorber and use thereof - Google Patents

Abstract

An object of this invention is to provide the manufacturing method of the near-infrared absorber which can manufacture stably the near-infrared absorber excellent in transparency at the time of using with resin. The manufacturing method of the near-infrared absorber of the invention comprises mixing a phosphonic acid compound represented by the following general formula (1), a phosphoric ester compound dispersant, and a copper salt in a solvent, and a near-infrared absorber. Used in the step A, including a step A for obtaining a reaction mixture containing the step B, a step B for recovering a solvent from the reaction mixture, and a step C using the solvent recovered in the step B as a solvent for the step A. The solvent is an organic solvent having a water content of 0 to 8.0% by mass. In the formula, R 1 is a monovalent group represented by —CH 2 CH 2 —R 11, and R 11 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a fluorinated alkyl group having 1 to 20 carbon atoms.

Description

  The present invention relates to a method for producing a near-infrared absorber, a near-infrared absorber obtained by the production method, and uses thereof.

Metal ions are known to have unique spectral characteristics, such as exhibiting absorption characteristics with respect to light of a specific wavelength, and are applied to optical materials using these characteristics.
As an optical material that can sufficiently exhibit the spectral characteristics peculiar to metal ions, at least one of a predetermined phosphonic acid monoester compound, a predetermined phosphinic acid compound, a predetermined phosphoric acid diester compound, and a predetermined phosphoric acid monoester compound An optical material comprising a compound, a predetermined phosphonic acid compound, and a metal ion such as a copper ion is known (for example, see Patent Document 1).

  In general, copper ions among metal ions are known to have excellent absorption characteristics of light in the near-infrared region (hereinafter also referred to as “near-infrared”), and optical materials containing copper ions are near-infrared absorbers. It was used as.

  For example, it has been proposed to use the near-infrared absorber together with a resin and apply it to a window material or the like. In such a case, in order to ensure sufficient brightness at room temperature while sufficiently absorbing near-infrared rays, it is desired that the visible light transmittance (hereinafter also referred to as transparency) is high.

However, conventionally, the examination of transparency when the near-infrared absorber is used together with a resin has not been sufficient.
As a near-infrared absorber capable of expressing excellent transparency even when a near-infrared absorber is used together with a resin, a specific phosphonic acid compound, a specific phosphate ester compound, and a copper ion Is known (for example, see Patent Document 2).

  Since the near-infrared absorber disclosed in Patent Document 2 has a small particle size, it is disclosed that an optical material using the near-infrared absorber is excellent in transparency and that the optical material is also excellent in heat resistance. Yes.

JP 2002-69305 A JP 2011-99038 A

  In Patent Literature 2, a step of reacting a mixture containing a specific phosphonic acid compound and a specific phosphate ester compound with a copper salt in a first solvent to obtain a reaction mixture, and at least a first mixture from the reaction mixture. The near-infrared absorber is manufactured by the manufacturing method which has the process of removing a solvent, and the mixing process of mixing the reaction mixture from which the 1st solvent was removed with the 2nd solvent.

  In Patent Document 2, in the step of obtaining the reaction mixture, by reacting the specific phosphonic acid compound with a copper salt in the presence of the specific phosphate ester compound, fine particulate copper phosphonate. Manufactures salt.

  In the case where the first solvent is recovered and reused when batch production is performed, or when the recovered solvent is circulated as the first solvent in continuous production, the present invention gradually The particle size of the resulting particulate phosphonic acid copper salt increases, and when the phosphonic acid copper salt having an increased particle size is used together with a resin, the transparency tends to deteriorate or the haze tends to increase. I found out.

  As a result of intensive studies to solve the above problems, the present inventors have reused the solvent used in reacting the phosphonic acid compound and the copper salt under specific conditions, together with the resin. It has been found that a near-infrared absorber having excellent transparency when used can be stably produced, and the present invention has been completed.

  That is, the method for producing a near-infrared absorber of the present invention comprises mixing a phosphonic acid compound represented by the following general formula (1), a phosphoric ester compound dispersant, and a copper salt in a solvent, Step A for obtaining a reaction mixture containing an infrared absorber, Step B for recovering a solvent from the reaction mixture, and Step C using the solvent recovered in Step B as a solvent for Step A, The solvent used in is an organic solvent having a water content of 0 to 8.0% by mass.

［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。］

[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. ]

  Preferably, the organic solvent includes at least one organic solvent selected from methanol, ethanol, isopropyl alcohol, n-butanol, N, N-dimethylformamide, and tetrahydrofuran, and at least selected from methanol and ethanol. More preferably, it contains one organic solvent.

The step B is preferably a step of recovering the solvent as a fraction by distilling the reaction mixture under reduced pressure.
The near-infrared absorber of this invention is obtained by the said manufacturing method.
The resin composition of this invention contains the said near-infrared absorber and 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. A resin is preferable, and a polyvinyl acetal resin or an ethylene-vinyl acetate copolymer is more preferable.

The interlayer film for laminated glass of the present invention is formed from the resin composition.
The laminated glass of the present invention has the interlayer film for laminated glass.

  The manufacturing method of the near-infrared absorber of the present invention includes reusing a solvent used when reacting a phosphonic acid compound and a copper salt, and a solvent used when reacting a phosphonic acid compound and a copper salt. By setting the water content within a specific range, it is possible to stably produce a near infrared absorber that is excellent in transparency when used together with a resin.

Next, the present invention will be specifically described.
The manufacturing method of the near-infrared absorber of this invention mixes the phosphonic acid compound represented by following General formula (1), a phosphate ester compound dispersing agent, and a copper salt in a solvent, and absorbs near-infrared rays. Used in Step A, including Step A for obtaining a reaction mixture containing an agent, Step B for recovering a solvent from the reaction mixture, and Step C using the solvent recovered in Step B as a solvent for Step A The solvent to be used is an organic solvent having a water content of 0 to 8.0% by mass.

［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。］
以下、本発明の近赤外線吸収剤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. ]
Hereinafter, each process of the manufacturing method of the near-infrared absorber of this invention is demonstrated.

[Step A]
In the method for producing a near-infrared absorber of the present invention, first, a phosphonic acid compound represented by the general formula (1), a phosphate ester compound dispersant, and a copper salt are mixed in a solvent, The process A which obtains the reaction mixture containing an infrared absorber is performed.

In the present invention, the “phosphonic acid compound represented by the general formula (1)” is also referred to as “specific phosphonic acid compound”.
The near-infrared absorber 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 the reaction between the specific phosphonic acid compound and the copper salt. The phosphonic acid copper salt is considered to be maintained in a very fine state by the phosphate ester compound 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 phosphate ester compound dispersing agent around it. In addition, it is considered that the phosphate ester compound dispersant is coordinated with a part of the copper ions. For this reason, the copper ion in the near infrared absorber is excellent in stability to heat and the like. For example, when the near infrared absorber is used together with a resin, the resin composition containing the near infrared absorber and the resin is thermoformed. Even when the resin is used, the resin is not affected by copper ions, and is less colored and excellent in 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。］

[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.

  The phosphate ester compound dispersant used in the present invention is not particularly limited as long as it is a phosphate ester compound used as a dispersant. Preferably, the phosphate ester compound represented by the following general formula (2a) And at least 1 sort (s) of phosphate ester compound selected from the phosphate ester compound represented by the following general formula (2b) is used.

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

［式中、Ｒ²¹、Ｒ²²およびＲ²³は、−（ＣＨ₂ＣＨ₂Ｏ）_nＲ⁵で表される１価の基であり、
ｎは２〜６５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。］

[Wherein R ²¹ , R ²² and R ²³ are monovalent groups represented by — (CH ₂ CH ₂ O) _n R ⁵ ,
n is an integer of 2 to 65, 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. ]

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 2 to 65, preferably an integer of 4 to 65, more preferably 4 to 45, and particularly preferably an integer of 6 to 45. When n is less than 2, when the molded product is produced using the near-infrared absorbent of the present invention together with a resin, the transparency of the molded product becomes insufficient. On the other hand, if n exceeds 65, the amount of the phosphoric acid ester compound necessary for obtaining a molded article having sufficient transparency increases, resulting in high costs.

R 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 8 to 20 carbon atoms. Are more preferable, and 12 to 20 alkyl groups are particularly preferable. When R ⁵ is a group having less than 6 carbon atoms, the transparency of the molded article becomes insufficient. Further, if R ⁵ is a group having more than 25 carbon atoms, the amount of the phosphoric acid ester compound necessary for obtaining a molded article having sufficient transparency increases, resulting in high costs.

  When obtaining a near-infrared absorber in the step A, it is preferable to use at least one of a phosphate ester compound represented by the general formula (2a) and a phosphate ester compound represented by the general formula (2b). However, it is more 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 phosphate ester compound represented by the general formula (2a) and the phosphate ester compound represented by the general formula (2b) are used, the molded article tends to be excellent in transparency and heat resistance. 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.

  Further, as the phosphate ester compound dispersant, other phosphate esters can be used. Examples of other phosphate esters include phosphate triesters, and these phosphate triesters may be used alone or together with the specific phosphate ester compound.

  As 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.
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 is present, and further, the phosphate ester compound dispersant is present therearound. It is also considered that there is 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 phosphoric acid ester compound dispersant.

  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 mol of the phosphate ester compound dispersant. If it is less than 5 mol, the near-infrared absorption characteristics of the molded article 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 the transparency and heat resistance of a molded object are especially excellent, it is preferable.

  In step A, as described above, the specific phosphonic acid compound, the phosphate ester compound dispersant, and the copper salt are mixed in a solvent to obtain a reaction mixture containing a near-infrared absorber. The following reactions are considered to occur.

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

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

  In addition, in the manufacturing method of the near-infrared absorber of this invention, the organic solvent with a moisture content of 0-8.0 mass% is used as a solvent used at the process A. By using an organic solvent having a water content within the above range, the particle diameter of the obtained near-infrared absorber can be controlled to 10 to 150 nm, and a resin composition containing near-infrared fine particles and a resin is used. Even when a molded body is obtained, it is possible to produce a near-infrared absorber having low haze and excellent transparency.

  The water content is preferably 0 to 4.0% by mass and preferably 0 to 2.5% by mass when the organic solvent is ethanol or denatured ethanol from the viewpoint of preventing aggregation of near-infrared absorber particles. % Is more preferable, and when the organic solvent is methanol, it is preferably 0 to 8.0% by mass, and more preferably 0 to 5.0% by mass.

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

Step A is usually 0 to 80 ° C., preferably 10 to 60 ° C., more preferably room temperature to 60 ° C., particularly preferably 20 to 40 ° C., usually 0.5 to 60 hours, preferably Is carried out for 0.5 to 30 hours, more preferably 0.5 to 20 hours, particularly preferably 1 to 15 hours.
By this reaction, a reaction mixture containing a near infrared absorber is obtained. In addition to the near infrared absorber, the reaction mixture may contain a solvent, a by-product depending on the raw material used, an unreacted raw material, and the like.

[Step B]
In the manufacturing method of the near-infrared absorber of this invention, the process B which collect | recovers a solvent from the reaction mixture obtained at the above-mentioned process A is performed.

  As a method for recovering the solvent from the reaction mixture obtained in step A, for example, a method in which the solid content in the reaction mixture is precipitated and the solvent is recovered as a supernatant, and the solvent is recovered as a fraction by distillation of the reaction mixture. The method of doing is mentioned.

Examples of the method for precipitating the solid content include a method for precipitating the solid content by allowing the reaction mixture to stand, and a method for precipitating the solid content by centrifuging the reaction mixture.
As a method of recovering the solvent, a method of recovering the solvent as a fraction by distilling the reaction mixture is preferable from the viewpoint that a general apparatus can be used.

  Distillation is preferably performed under reduced pressure from the viewpoint of preventing thermal deterioration of the reaction mixture. That is, step B is preferably a step of recovering the solvent as a fraction by distilling the reaction mixture under reduced pressure.

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

[Step C]
In the manufacturing method of the near-infrared absorber of this invention, the process C which uses the solvent collect | recovered at the above-mentioned process B as a solvent of the process A is performed.

  The solvent recovered in step B is not particularly limited as a specific method for use in step A. The recovered solvent may be reused in the next batch production, or in continuous production. You may reuse as a solvent.

The manufacturing method of the near-infrared absorber of the present invention is an excellent manufacturing method from the viewpoint of resource reduction and cost reduction because the solvent can be used repeatedly.
In addition, when a solvent is repeatedly used, there exists a tendency for the water content of the solvent collect | recovered at the process B to become high gradually. When the water content of the solvent recovered in step B exceeds the above range, or when it is desired to reduce the water content of the solvent, replace part or all of the recovered solvent with a new organic solvent having a low water content. In order to reduce the water content of the solvent recovered in the step B, a treatment such as distillation or addition of a dehydrating agent may be performed before use in the step A.

  A near-infrared absorber can be manufactured by the above-mentioned method. In the production method of the present invention, after performing Step A, Step B for recovering the solvent from the reaction mixture obtained in Step A is performed, and the reaction mixture from which the solvent obtained in Step B is recovered is the aforementioned. It is a near-infrared absorber containing the phosphonic acid copper salt. The reaction mixture from which the solvent has been recovered may be used as it is as a near-infrared absorber, or may be used as a near-infrared absorber after further steps.

As another step, for example, for the purpose of purifying the near-infrared absorber, a step of dispersing the reaction mixture from which the solvent has been recovered in a dispersion medium and removing the dispersion medium may be performed.
In addition, the reaction mixture from which the solvent has been recovered may be dispersed in a dispersion medium and used as a near-infrared absorber dispersion for each application.

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

[Near infrared absorber]
The near-infrared absorber of this invention is obtained by the manufacturing method of the above-mentioned near-infrared absorber.
Since the near-infrared absorber of the present invention is obtained by the above production method and is excellent in transparency when used together with a resin, the resin composition comprising the near-infrared absorber and the resin can be used for various kinds of interlayer films for laminated glass, etc. It is possible to manufacture a molded object suitably.
Moreover, the average particle diameter of the near-infrared absorber of this invention becomes like this. Preferably it is 10-150 nm, More preferably, it is 20-140 nm.

[Resin composition]
The resin composition of this invention contains the above-mentioned near-infrared absorber and resin.
Examples of the method for producing the resin composition include a method of obtaining a resin composition by mixing a near-infrared absorber powder and a resin, and dispersing the obtained near-infrared absorber in the aforementioned dispersion medium. The liquid and the resin are mixed, and the dispersion medium is removed from the obtained mixture, thereby obtaining a resin composition, the dispersion liquid and the resin solution are mixed, and the dispersion medium and The method of obtaining a resin composition by removing a solvent is mentioned.

When removing the dispersion medium or removing the dispersion medium and the solvent, the removal method is not particularly limited, but is usually performed by drying such as drying under normal pressure or vacuum drying.
In addition, when obtaining the molded object which consists of this resin composition, you may obtain a molded object by performing manufacture and shaping | molding of this resin composition simultaneously, and after manufacturing this resin composition as a pellet etc., desired A molded body may be obtained by molding into a shape of, and after obtaining the resin composition as a master batch such as pellets, the master batch and the resin are used to perform various processes such as extrusion molding, cast molding, injection molding, etc. A molded body such as an interlayer film for laminated glass may be obtained by a molding method.

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

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

  Depending on the required physical properties, the polyvinyl acetal resin may be a blend of two or more types, or may be a polyvinyl acetal resin obtained by acetalizing a combination of 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. When it exceeds 3000, the moldability of the resin composition may be deteriorated, and the rigidity of the resin composition is excessively increased, resulting in poor processability. 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 excellent dispersibility of the above-mentioned near-infrared absorber and glass adhesion, dispersibility, transparency, heat resistance, light resistance, and the like.
The resin solution can be obtained by dissolving the aforementioned resin in a solvent. The solvent is not particularly limited as long as it can dissolve the resin, and examples thereof include toluene, ethanol, methanol, methylene chloride, chloroform and the like. As the solvent, one kind may be used alone, or two or more kinds may be used.

  Moreover, the resin composition of this invention may contain a plasticizer. The plasticizer is not particularly limited. For example, triethylene glycol bis (2-ethylhexanoate), triethylene glycol bis (2-ethylbutyrate), tetraethylene glycol bis (2-ethylhexanoate), Examples include tetraethylene glycol diheptanoate, dihexyl adipate, tributoxyethyl phosphate, and isodecylphenyl phosphate.

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

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

  The near-infrared absorber contained in the resin composition of the present invention is excellent in transparency when used with a resin, and is an intermediate for structural materials such as laminated glass because coloring during heating, that is, yellowing is suppressed. It can be suitably used as a membrane.

  Moreover, various additives may be contained in the resin composition of the present invention. Examples of the additive include a dispersant, an antioxidant, an ultraviolet absorber, and a light stabilizer. These additives may be added when manufacturing the resin composition of the present invention, or may be added when manufacturing the near-infrared absorber and the resin, respectively.

[Use of resin composition]
The resin composition of the present invention is usually used for applications where it is desired to absorb near infrared rays.
The resin film formed from the resin composition of the present invention has excellent near-infrared absorptivity and is suitable as an intermediate film for structural materials such as an interlayer film for laminated glass because coloring during heating, that is, yellowing is suppressed. Can be used.

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

EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.
[Test Example 1]
(Synthesis of copper phosphonate complex (1))
In a 200 ml eggplant flask, 1.164 g (5.83 mmol) of copper acetate monohydrate, 35 g of ethanol (water content 0.07% by mass), Prisurf A219B (Daiichi Kogyo Seiyaku Co., Ltd.), which is a phosphate ester compound, 0 .50 g was added (Liquid A).

In a separate container, a solution (solution B) was prepared by dissolving 0.789 g of n-butylphosphonic acid in 20 g of the ethanol (water content 0.07% by mass).
The water content in ethanol was measured using a trace moisture measuring device AQ-2200 (manufactured by Hiranuma Sangyo).

B liquid was dripped with respect to A liquid in about 5 minutes. This reaction solution was stirred at 20 ° C. for 14 hours to obtain a reaction mixture containing a phosphonic acid copper complex (1) which is a near infrared absorber.
Subsequently, the solvent was distilled off from the reaction mixture by performing the following solvent recovery operation.

  30 g of toluene was added to the reaction mixture from which the solvent had been distilled off (remainder), and the mixture was distilled off with an evaporator until a constant weight was obtained. Thus, a 1.66 g (100% yield) blue-green solid (phosphonic acid copper complex (1 ))was gotten.

  30 g of toluene was added to the blue-green solid, and ultrasonic irradiation was performed for 3 hours to prepare a copper phosphonate complex toluene dispersion (1). The average particle size of the toluene dispersion (1) was measured and found to be 52 nm. The particle size of the copper complex was measured using a particle size measuring device ELS-Z2 (manufactured by Otsuka Electronics Co., Ltd.), a quartz cell having a cell length of 10 mm as a cell, toluene as a solvent for concentration adjustment, a temperature of 25 ° C., and a concentration of 0. It carried out on the conditions of 1-0.6 mol / L.

<Solvent recovery operation>
The reaction mixture was subjected to simple distillation under reduced pressure (pressure 1 to 4 kPa, temperature 50 to 70 ° C.) to recover the solvent.

(Preparation of copper salt fine particle dispersed resin (1))
To a 500 ml beaker, 2.43 g of triethylene glycol bis (2-ethylhexanoate), 300 ml of methylene chloride and 6.38 g of polyvinyl butyral (PVB) were added. 4.05 g (containing 0.746 mmol of copper complex) of the phosphonic acid copper complex toluene dispersion (1) was added thereto, and the mixture was stirred at 20 ° C. for 14 hours to uniformly dissolve PVB. This dispersion was spread on a Teflon (registered trademark) vat and air-dried at 20 ° C. for 12 hours. Furthermore, it vacuum-dried at 70 degreeC for 4 hours, the solvent was removed completely, and PVB resin (1) in which the copper complex fine particles were disperse | distributed was obtained.

(Preparation of resin sheet (1))
After the PVB resin (1) in which the copper complex fine particles are dispersed is preheated at 120 ° C. and 3 MPa for 1 minute using a 0.8 mm thick formwork and a compression molding machine manufactured by Shinfuji Metal Industry Co., Ltd. , And pressed at 15 MPa for 3 minutes to obtain a resin sheet (1).

(Preparation of haze 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) is heated in an autoclave in a nitrogen atmosphere at a pressure of 1.5 MPa and 130 ° C. for 0.5 hours to obtain a haze measurement sample (1) in which slide glasses are arranged on both surfaces of the resin sheet. It was.
When the haze of the said haze measurement sample (1) was measured using Nippon Denshoku Industries NDH-2000 (D65 light source, single beam), the haze was 1.2.

(Synthesis of copper phosphonate complex (2))
Ethanol (water content 0.6% by mass) recovered by the solvent recovery operation in the synthesis of the copper phosphonate complex (1) (the operation of recovering after use for the synthesis of the copper phosphonate complex) Except that the ethanol was changed once), the same procedure as in the synthesis of the copper phosphonate complex (1) was performed to prepare a phosphonate copper complex toluene dispersion (2). The average particle size of the toluene dispersion (2) was measured and found to be 60 nm.

(Preparation of copper salt fine particle dispersed resin (2), resin sheet (2), haze measurement sample (2))
Preparation of copper salt fine particle dispersion resin (1), preparation of resin sheet (1), haze measurement sample, except that copper phosphonate complex toluene dispersion (1) is replaced with copper phosphonate complex toluene dispersion (2) It carried out similarly to preparation of (1), and obtained the copper salt fine particle dispersion resin (2), the resin sheet (2), and the haze measurement sample (2).
The haze of the haze measurement sample (2) was 1.2.

(Synthesis of copper phosphonate complex (3))
Ethanol (water content 1.1% by mass) recovered by the solvent recovery operation in the synthesis of the copper phosphonate complex (2) as the solvent at the time of copper complex synthesis (operation to recover after use for the synthesis of the copper phosphonate complex) Except that the ethanol was changed twice), the same procedure as in the synthesis of the copper phosphonate complex (1) was performed to prepare a phosphonate copper complex toluene dispersion (3). The average particle size of the toluene dispersion (3) was measured and found to be 65 nm.

(Preparation of copper salt fine particle dispersed resin (3), resin sheet (3), haze measurement sample (3))
Preparation of copper salt fine particle dispersion resin (1), preparation of resin sheet (1), haze measurement sample, except that copper phosphonate complex toluene dispersion (1) is replaced with copper phosphonate complex toluene dispersion (3) It carried out similarly to preparation of (1), and obtained the copper salt fine particle dispersion resin (3), the resin sheet (3), and the haze measurement sample (3).
The haze of the haze measurement sample (3) was 1.1.

(Synthesis of copper phosphonate complex (4))
The ethanol recovered by the solvent recovery operation in the synthesis of the copper phosphonate complex (3) was used for the synthesis of the copper phosphonate complex as the solvent at the time of copper complex synthesis. 2.1 mass%) The same procedure as in the synthesis of the copper phosphonate complex (1) was carried out except that the ethanol was recovered four times after use for the synthesis of the copper phosphonate complex. A copper complex toluene dispersion (4) was prepared. The average particle diameter of the toluene dispersion (4) was measured and found to be 68 nm.

(Preparation of copper salt fine particle dispersed resin (4), resin sheet (4), haze measurement sample (4))
Except for replacing the phosphonate copper complex toluene dispersion (1) with the phosphonate copper complex toluene dispersion (4), preparation of the copper salt fine particle dispersion resin (1), preparation of the resin sheet (1), haze measurement sample It carried out similarly to preparation of (1), and obtained the copper salt fine particle dispersion resin (4), the resin sheet (4), and the haze measurement sample (4).
The haze of the haze measurement sample (4) was 0.9.

(Synthesis of copper phosphonate complex (5))
The ethanol recovered by the solvent recovery operation in the synthesis of the copper phosphonate complex (4) was used for the synthesis of the copper phosphonate complex as the solvent at the time of copper complex synthesis. The amount of phosphonic acid was changed to 3.1% by mass) (except for the ethanol that was recovered six times after use for the synthesis of the copper phosphonate complex). A copper complex toluene dispersion (5) was prepared. The average particle size of the toluene dispersion (5) was measured and found to be 131 nm.

(Preparation of copper salt fine particle dispersed resin (5), resin sheet (5), haze measurement sample (5))
Preparation of copper salt fine particle dispersion resin (1), preparation of resin sheet (1), haze measurement sample, except that phosphonic acid copper complex toluene dispersion (1) is replaced with phosphonic acid copper complex toluene dispersion (5) It carried out similarly to preparation of (1), and obtained the copper salt fine particle dispersion resin (5), the resin sheet (5), and the haze measurement sample (5).
The haze of the haze measurement sample (5) was 2.8.

[Test Example 2]
(Synthesis of copper phosphonate complex (6))
To a 200 ml eggplant flask, 1.164 g (5.83 mmol) of copper acetate monohydrate and 35 g of methanol (water content 0.007% by mass) were added (solution A).

  In another container, 0.291 g of Prisurf A219B (Daiichi Kogyo Seiyaku Co., Ltd.), a phosphate ester compound, and 0.801 g of n-butylphosphonic acid are dissolved in 30 g of the methanol (water content 0.007% by mass). A solution (liquid B) was prepared.

In addition, the water content in methanol was measured using a trace moisture measuring apparatus AQ-2200 (manufactured by Hiranuma Sangyo).
Liquid B was added dropwise to liquid A in about 1.5 hours. This reaction solution was stirred at 20 ° C. for 12 hours to obtain a reaction mixture containing a phosphonic acid copper complex (6) which is a near infrared absorber.

Subsequently, the solvent was distilled off from the reaction mixture by performing the following solvent recovery operation.
30 g of toluene was added to the reaction mixture from which the solvent had been distilled off (remainder), and the mixture was distilled off with an evaporator until a constant weight was obtained, whereby a 1.45 g (100% yield) pale pale white solid (copper phosphonate complex ( 6)) was obtained.

  30 g of toluene was added to the bluish white solid and ultrasonic irradiation was performed for 5 hours to prepare a copper phosphonate complex toluene dispersion (6). It was 55 nm when the average particle diameter of the toluene dispersion liquid (6) was measured.

<Solvent recovery operation>
The reaction mixture was distilled under reduced pressure (pressure 1 to 4 kPa, temperature 40 to 60 ° C.) to recover the solvent.

(Preparation of copper salt fine particle dispersed resin (6))
To a 300 ml Erlenmeyer flask, 1.90 g of triethylene glycol bis (2-ethylhexanoate), 250 ml of toluene, and 5.00 g of polyvinyl butyral (PVB) were added. To this was added 3.15 g of the phosphonic acid copper complex toluene dispersion (6) (containing 0.583 mmol of copper complex), stirred at 20 ° C. for 12 hours, and subjected to ultrasonic irradiation for 2 hours to dissolve PVB uniformly. It was. This dispersion was spread on a Teflon (registered trademark) vat and air-dried at 20 ° C. for 12 hours. Furthermore, it vacuum-dried at 40 degreeC for 5 hours, and 70 degreeC for 4 hours, the solvent was removed completely, and the PVB resin (6) in which the copper complex fine particle disperse | distributed was obtained.

(Preparation of resin sheet (6) and haze measurement sample (6))
The resin sheet (1) is replaced with the resin sheet (6), except that the resin sheet (1) is prepared in the same manner as the preparation of the haze measurement sample (1). )
The haze of the haze measurement sample (6) was 0.9.

(Synthesis of copper phosphonate complex (7))
Methanol (water content 0.08% by mass) recovered by the solvent recovery operation in the synthesis of the copper phosphonate complex (6) as the solvent at the time of copper complex synthesis (operation to recover after use for the synthesis of the copper phosphonate complex) Except that the methanol was replaced once), the same procedure as in the synthesis of the copper phosphonate complex (6) was performed to prepare a phosphonate copper complex toluene dispersion (7). The average particle size of the toluene dispersion (7) was measured and found to be 62 nm.

(Preparation of copper salt fine particle dispersed resin (7), resin sheet (7), haze measurement sample (7))
Except for replacing the phosphonate copper complex toluene dispersion (6) with the phosphonate copper complex toluene dispersion (7), preparation of the copper salt fine particle dispersion resin (6), preparation of the resin sheet (6), haze measurement sample It carried out similarly to preparation of (6), and obtained the copper salt fine particle dispersion resin (7), the resin sheet (7), and the haze measurement sample (7).
The haze of the haze measurement sample (7) was 1.2.

(Synthesis of copper phosphonate complex (8))
Methanol (water content 0.19% by mass) recovered by the solvent recovery operation in the synthesis of the copper phosphonate complex (7) as the solvent at the time of copper complex synthesis (operation to recover after use for the synthesis of the copper phosphonate complex) Except that the methanol was replaced twice), the same procedure as in the synthesis of the copper phosphonate complex (6) was performed to prepare a phosphonate copper complex toluene dispersion (8). The average particle size of the toluene dispersion (8) was measured and found to be 68 nm.

(Preparation of copper salt fine particle dispersed resin (8), resin sheet (8), haze measurement sample (8))
Preparation of copper salt fine particle dispersion resin (6), preparation of resin sheet (6), haze measurement sample, except that copper phosphonate complex toluene dispersion (6) is replaced with copper phosphonate complex toluene dispersion (8) It carried out similarly to preparation of (6), and obtained the copper salt fine particle dispersion resin (8), the resin sheet (8), and the haze measurement sample (8).
The haze of the haze measurement sample (8) was 1.1.

(Synthesis of copper phosphonate complex (9))
The methanol recovered by the solvent recovery operation in the synthesis of the copper phosphonate complex (8) as the solvent at the time of copper complex synthesis was further used for the synthesis of the copper phosphonate complex, and the methanol (containing water) recovered by the solvent recovery operation. 0.5 mass%) (phosphorus acid complex was synthesized in the same manner as in the synthesis of copper phosphonate complex (6)) except that the methanol was recovered four times after use for the synthesis of copper phosphonate complex. A copper complex toluene dispersion (9) was prepared. The average particle diameter of the toluene dispersion (9) was measured and found to be 72 nm.

(Preparation of copper salt fine particle dispersed resin (9), resin sheet (9), haze measurement sample (9))
Preparation of copper salt fine particle dispersion resin (6), preparation of resin sheet (6), haze measurement sample, except that phosphonic acid copper complex toluene dispersion (6) is replaced with phosphonic acid copper complex toluene dispersion (9) It carried out similarly to preparation of (6), and obtained the copper salt fine particle dispersion resin (9), the resin sheet (9), and the haze measurement sample (9).
The haze of the haze measurement sample (9) was 1.4.

(Synthesis of copper phosphonate complex (10))
The methanol recovered by the solvent recovery operation in the synthesis of the copper phosphonate complex (9) was used for the synthesis of the copper phosphonate complex 5 times, and the methanol ( Except that the moisture content was 3.1% by mass) (methanol that had been recovered 10 times after use for the synthesis of the phosphonate copper complex), the same procedure as in the synthesis of the phosphonate copper complex (6) was carried out. A phosphonic acid copper complex toluene dispersion (10) was prepared. It was 88 nm when the average particle diameter of the toluene dispersion liquid (10) was measured.

(Preparation of copper salt fine particle dispersed resin (10), resin sheet (10), haze measurement sample (10))
Preparation of copper salt fine particle dispersion resin (6), preparation of resin sheet (6), haze measurement sample, except that copper phosphonate complex toluene dispersion (6) is replaced with copper phosphonate complex toluene dispersion (10) It carried out similarly to preparation of (6), and obtained the copper salt fine particle dispersion resin (10), the resin sheet (10), and the haze measurement sample (10).
The haze of the haze measurement sample (10) was 2.8.

(Synthesis of copper phosphonate complex (11))
The methanol recovered by the solvent recovery operation in the synthesis of the copper phosphonate complex (10) was used for the synthesis of the copper phosphonate complex four times, and the methanol ( Except that the water content was 5.1% by mass) (methanol that was recovered after use 15 times for the synthesis of the copper phosphonate complex), the same procedure as in the synthesis of the copper phosphonate complex (6) was performed. A phosphonic acid copper complex toluene dispersion (11) was prepared. The average particle size of the toluene dispersion (11) was measured and found to be 111 nm.

(Preparation of copper salt fine particle dispersed resin (11), resin sheet (11), haze measurement sample (11))
Except for replacing the phosphonate copper complex toluene dispersion (6) with the phosphonate copper complex toluene dispersion (11), preparation of the copper salt fine particle dispersion resin (6), preparation of the resin sheet (6), haze measurement sample It carried out similarly to preparation of (6), and obtained the copper salt fine particle dispersion resin (11), the resin sheet (11), and the haze measurement sample (11).
The haze of the haze measurement sample (11) was 3.8.

(Synthesis of copper phosphonate complex (12))
The methanol recovered by the solvent recovery operation in the synthesis of the copper phosphonate complex (11) was used for the synthesis of the copper phosphonate complex four times, and the methanol ( Except that the water content was 7.1 mass%) (methanol that was recovered 20 times after use for the synthesis of the copper phosphonate complex), the same procedure as in the synthesis of the copper phosphonate complex (6) was performed, A phosphonic acid copper complex toluene dispersion (12) was prepared. It was 113 nm when the average particle diameter of the toluene dispersion liquid (12) was measured.

(Preparation of copper salt fine particle dispersed resin (12), resin sheet (12), haze measurement sample (12))
Preparation of copper salt fine particle dispersed resin (6), preparation of resin sheet (6), haze measurement sample, except that copper phosphonate complex toluene dispersion (6) was replaced with copper phosphonate complex toluene dispersion (12) It carried out similarly to preparation of (6), and obtained the copper salt fine particle dispersion resin (12), the resin sheet (12), and the haze measurement sample (12).
The haze of the haze measurement sample (12) was 3.6.

(Synthesis of copper phosphonate complex (c1))
The methanol recovered by the solvent recovery operation in the synthesis of the copper phosphonate complex (12) was used for the synthesis of the copper phosphonate complex four times, and the methanol ( Except that the moisture content was changed to 10.1% by mass) (methanol that was recovered 25 times after use for the synthesis of the copper phosphonate complex), the same procedure as in the synthesis of the copper phosphonate complex (6) was performed. A phosphonic acid copper complex toluene dispersion (c1) was prepared. It was 236 nm when the average particle diameter of the toluene dispersion liquid (c1) was measured.

(Preparation of copper salt fine particle dispersed resin (c1), resin sheet (c1), haze measurement sample (c1))
Preparation of copper salt fine particle dispersion resin (6), preparation of resin sheet (6), haze measurement sample, except that copper phosphonate complex toluene dispersion (6) was replaced with copper phosphonate complex toluene dispersion (c1) It carried out similarly to preparation of (6), and obtained the copper salt fine particle dispersion resin (c1), the resin sheet (c1), and the haze measurement sample (c1).

The haze of the haze measurement sample (c1) was 22.5.
The synthesis of the copper phosphonate complex (c1) corresponds to a comparative example because the methanol used has a high water content.

Claims (10)

Step A in which a phosphonic acid compound represented by the following general formula (1), a phosphate ester compound dispersant, and a copper salt are mixed in a solvent to obtain a reaction mixture containing a near-infrared absorber.
Step B for recovering the solvent from the reaction mixture, and Step C using the solvent recovered in Step B as the solvent for Step A,
The manufacturing method of the near-infrared absorber whose solvent used at the said process A is an organic solvent with a moisture content of 0-8.0 mass%.

[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. ]   The near-infrared ray according to claim 1, wherein the organic solvent includes at least one organic solvent selected from methanol, ethanol, isopropyl alcohol, n-butanol, N, N-dimethylformamide, and tetrahydrofuran. Production method of absorbent.   The method for producing a near-infrared absorber according to claim 1, wherein the organic solvent includes at least one organic solvent selected from methanol and ethanol.   The manufacturing method of the near-infrared absorber as described in any one of Claims 1-3 whose said process B is a process of collect | recovering a solvent as a fraction by distilling a reaction mixture under reduced pressure.   The near-infrared absorber obtained by the manufacturing method as described in any one of Claims 1-4.   The resin composition containing the near-infrared absorber of Claim 5, and 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. The resin composition according to claim 6, which is a resin.   The resin composition according to claim 6, wherein the resin is a polyvinyl acetal resin or an ethylene-vinyl acetate copolymer.   The intermediate film for laminated glasses formed from the resin composition as described in any one of Claims 6-8.   A laminated glass having the interlayer film for laminated glass according to claim 9.