JP2016060871A - Resin composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition containing a near infrared absorber excellent in light resistance.SOLUTION: There is provided a resin composition consisting of a near infrared absorber, an oxidant and a resin and the near infrared absorber is obtained by reacting at least copper salt and a phosphonic acid compound represented by the following general formula (1), where Ris a monovalent group represented by -CHCH-Rand Rrepresents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group having 1 to 20 carbon atoms.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition and its use, and more particularly to a resin composition comprising a near-infrared absorber, an oxidizing agent, and a resin, and its use.

  Conventionally, laminated glass has been used in various applications such as vehicles such as automobiles, buildings, and solar cells. As an interlayer film for laminated glass, a polyvinyl butyral resin film, an ionomer resin film, and the like are known.

  By the way, the sun rays include ultraviolet rays, infrared rays and the like in addition to visible rays. Among infrared rays, infrared rays whose wavelengths are close to visible rays are called near infrared rays. Near-infrared rays, also called heat rays, are one of the causes of temperature rise inside vehicles and buildings.

  In order to suppress the temperature rise, it is conceivable to impart heat ray absorbability to laminated glass used in vehicles and buildings while maintaining transparency (visible light transmittance). In order to give heat ray absorbability by utilizing the fact that electrons existing in the d orbital of copper ions selectively absorb near-infrared rays and make transition, a material containing copper ions is used as an interlayer film for laminated glass. It is being used. For example, a copper salt composition containing a phosphonic acid copper salt, a polysiloxane component, a plasticizer, and a dispersant is known (see Patent Document 1). In general, a resin composition obtained by mixing a metal salt and a resin tends to decrease in transparency or yellow when exposed to a high temperature. It has been shown that a resin composition containing a salt composition and a resin can be a near-infrared absorbing film that hardly undergoes yellowing even when exposed to high temperatures and has little decrease in transparency.

  In Patent Document 1, although the yellowness of the laminated glass has been studied, the light resistance, which is another index representing transparency, has not been studied, and high transparency is maintained even after long-term use. There is still room to consider the materials that can be done.

JP 2009-242650 A

  This invention is made | formed in view of the said prior art, and aims at providing the resin composition containing the near-infrared absorber which is excellent in light resistance.

  The present inventors, when a molded product such as an interlayer film for laminated glass formed from a resin composition containing a near-infrared absorber is irradiated with ultraviolet rays over a long period of time, a number of minute It has been found that the phenomenon in which black spots occur, that is, the blackening phenomenon, causes a reduction in visibility in the portion and in a visible light transmittance in the entire molded product. Further, the present inventors have found that the cause of the blackening phenomenon is that copper constituting the near-infrared absorber is reduced from divalent copper ions to monovalent copper ions by ultraviolet rays or the like. I found it.

  Based on the above findings, the present inventors have conducted extensive research to achieve the above object, and as a result, a resin composition comprising a specific near infrared absorber, an oxidizing agent, and a resin can solve the above problems. The present invention was completed.

  That is, the resin composition of the present invention is a resin composition comprising a near-infrared absorber, an oxidizing agent, and a resin, and the near-infrared absorber is represented by at least a copper salt and the following general formula (1). It is obtained by reacting with a phosphonic acid compound.

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

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

The oxidizing agent is preferably an oxidizing agent having a standard oxidation-reduction potential (E ⁰ ) at 25 ° C. exceeding 0.15V.
It is preferable to use 0.00001 to 0.03 mol of oxidizing agent per 1 mol of copper element contained in the near infrared absorber.

  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.

It is preferable to contain 0.05-50 mass parts of near-infrared absorbers per 100 mass parts of said resin.
The interlayer film for laminated glass of the present invention is formed from the resin composition.
The laminated glass of the present invention has the interlayer film for laminated glass.

  The resin composition of the present invention has good light resistance in addition to the near infrared absorption ability.

The resin composition of the present invention is a resin composition comprising a near-infrared absorber, an oxidizing agent, and a resin, and the near-infrared absorber includes at least a copper salt and a phosphonic acid represented by the general formula (1). It is obtained by reacting with a compound.
Hereinafter, the composition will be specifically described. Hereinafter, the resin composition is also referred to as a copper salt fine particle dispersed resin.

[Near infrared absorber]
The near-infrared absorber used in the present invention can be obtained by reacting at least a copper salt with a phosphonic acid compound represented by the following general formula (1).

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

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

R ¹¹ in the general formula (1) is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specifically, as R ¹¹ , 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 Group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like are preferable.

More specifically, examples of the phosphonic acid compound represented by the general formula (1) include ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, heptylphosphonic acid, octylphosphonic acid, Alkylphosphonic acids such as nonylphosphonic acid, decylphosphonic acid, undecylphosphonic acid, dodecylphosphonic acid, tridecylphosphonic acid, tetradecylphosphonic acid, pentadecylphosphonic acid, hexadecylphosphonic acid, heptadecylphosphonic acid, octadecylphosphonic acid Is mentioned.
In addition, about the said phosphonic acid compound, you may use individually by 1 type and may be used in combination of 2 or more type.

  As the copper salt, a copper salt capable of supplying divalent copper ions is usually used. The copper salt is not particularly limited as long as it is a copper salt other than the phosphonic acid copper salt represented by the following general formula (1 ′). For example, anhydrous copper acetate, anhydrous copper formate, anhydrous copper stearate A copper salt of an organic acid such as anhydrous copper benzoate, anhydrous copper ethylacetoacetate, anhydrous copper pyrophosphate, anhydrous copper naphthenate, anhydrous copper citrate, hydrated or hydrated copper salt of the organic acid; copper oxide, Examples thereof include copper salts of inorganic acids such as copper chloride, copper sulfate, copper nitrate, and basic copper carbonate; hydrates or hydrates of copper salts of the inorganic acids; copper hydroxide.

As the copper salt, anhydrous copper acetate and copper acetate monohydrate are preferably used in terms of solubility and removal of by-products.
In addition, about the said copper salt, 1 type may be used independently and 2 or more types may be used in combination.

  The near-infrared absorber may be obtained by reacting only a copper salt and a phosphonic acid compound represented by the general formula (1) as raw materials, and represented by the copper salt and the general formula (1). In addition to the phosphonic acid compound, other components may be used as raw materials and obtained by reacting them.

As said other component, the dispersing agent mentioned later is mentioned, for example.
In addition, when only the copper salt and the phosphonic acid compound represented by the general formula (1) are used as raw materials, the near-infrared absorber is a copper salt represented by the following general formula (1 ′), and the general formula (1) In addition to the phosphonic acid compound represented by 1), when other components are used as raw materials, the near-infrared absorber contains a copper salt represented by the following general formula (1 ′).

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

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

Examples of R ¹¹ in the general formula (1 ′) include the same as those exemplified as R ^{11 in the} general formula (1).
Although it does not specifically limit as a manufacturing method of the near-infrared absorber used for this invention, For example, the following method is mentioned.

  That is, as a method for producing a near-infrared absorber, a copper salt and a phosphonic acid compound represented by the above general formula (1) are mixed and reacted in a solvent to obtain a reaction mixture (hereinafter, reaction step). And a step of obtaining a near-infrared absorber as fine particles made of a phosphonic acid copper salt by removing the solvent in the reaction mixture (hereinafter also referred to as a solvent removal step).

  When manufacturing a near-infrared absorber, you may use a dispersing agent in the said reaction process. Examples of the dispersant include at least one phosphate ester compound selected from a phosphate monoester represented by the following general formula (2) and a phosphate diester represented by the general formula (3).

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

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

  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, transparency may be insufficient when a laminated glass or the like is produced. Moreover, when n exceeds the said range, the quantity of a phosphoric acid ester compound required in order to obtain the laminated glass etc. which have sufficient transparency will increase, and there exists a tendency which becomes a cause of high cost.

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

  As the alkyl group having 6 to 35 carbon atoms, specifically, octadecyl group, tridecyl group, dodecyl group, decyl group, octyl group and the like are preferable, and as alkylphenyl group having 6 to 35 carbon atoms, specifically, octadecyl group. A phenyl group, dodecylphenyl group, decylphenyl group, octylphenyl group, styrenated phenyl group and the like are preferable.

  As the dispersant, it is preferable to use at least one of the phosphate ester compound represented by the general formula (2) and the phosphate ester compound represented by the general formula (3). It is more preferable to use both the phosphoric acid ester compound represented by) and the phosphoric acid ester compound represented by the general formula (3). Use of these phosphoric acid ester compounds is preferred because they tend to be excellent in transparency and heat resistance of laminated glass and the like. When both of these phosphate ester compounds are used, the ratio of the phosphate ester compound represented by the general formula (2) and the phosphate ester compound represented by the general formula (3) is not particularly limited. However, the molar ratio ((2) :( 3)) is usually 10:90 to 90:10.

  About the phosphate ester compound represented by the said General formula (2), it may be used individually by 1 type, or may be used in combination of 2 or more types, The phosphate ester compound represented by the said General formula (3) As for, one kind may be used alone, or two or more kinds may be used in combination.

  As the at least one phosphate ester compound selected from the phosphate ester compound represented by the general formula (2) and the phosphate ester compound represented by the general formula (3), commercially available phosphoric acid Ester compounds such as DLP-10, DDP-4, DDP-6, DDP-8, DDP-10, TDP-6, TDP-8, TDP-10 (above, manufactured by Nikko Chemicals Co., Ltd.), Prisurf A212C, plysurf A215C, plysurf AL12H, plysurf AL, plysurf A208F, plysurf A208N, plysurf A208B, plysurf A219B, plysurf A210D (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) may be used. it can. Moreover, the phosphoric acid in these phosphate ester compounds, ie, the compound which neutralized the hydroxyl group with the appropriate 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.

  The commercially available phosphate ester compounds include components other than the phosphate monoester represented by the general formula (2) and the phosphate diester represented by the general formula (3), for example, polyoxyalkylene mono In some cases, alkyl ethers and phosphoric acid triesters represented by the following general formula (4) are contained. In this invention, even if such polyoxyalkylene monoalkyl ether and the said phosphate triester exist in a phosphate ester compound, it can be used without a problem.

［一般式（４）中、Ｒ⁵、Ｒ⁶およびＲ⁷は、−（ＣＨ₂ＣＨ₂Ｏ）_nＲ¹²で表される１価の基であり、ｎは２〜６５の整数であり、Ｒ¹²は、炭素数６〜３５のアルキル基または炭素数６〜３５のアルキルフェニル基を示す。ただし、Ｒ⁵、Ｒ⁶およびＲ⁷は、それぞれ同一でも異なっていてもよい。］

[In General Formula (4), R ⁵ , R ⁶ and R ⁷ are monovalent groups represented by — (CH ₂ CH ₂ O) _n R ¹² , n is an integer of 2 to 65, R ¹² represents an alkyl group having 6 to 35 carbon atoms or an alkylphenyl group having 6 to 35 carbon atoms. However, R ⁵ , R ⁶ and R ⁷ may be the same or different. ]

  When polyoxyalkylene monoalkyl ether is contained, the total amount of the phosphoric acid monoester represented by the general formula (2) and the phosphoric acid diester represented by the general formula (3) is 100 parts by mass. The polyoxyalkylene monoalkyl ether is preferably in the range of 1 to 300 parts by mass.

As the polyoxyalkylene monoalkyl _{ether, HO- (CH 2 CH 2 O} ) n R 12 (n is an integer of 2 to 65, R ¹² is an alkyl group carbon atoms or 6 to 35 carbon atoms 6 -35 alkylphenyl groups). The polyoxyalkylene monoalkyl ether is considered to be derived from a raw material used in producing a phosphate ester compound.

  When the phosphoric acid triester represented by the general formula (4) is contained, the phosphoric acid monoester represented by the general formula (2) and the phosphoric acid diester represented by the general formula (3) It is preferable that the phosphoric acid triester represented by the general formula (4) is 1 to 300 parts by mass with respect to 100 parts by mass in total.

As n and R < ¹² > in General formula (4), the thing similar to n and R < ¹² > in General formula (2) and (3) is preferable.
The phosphonic acid compound used in the reaction step is preferably 0.4 mol or more, more preferably 0.5 to 1.5 mol, and more preferably 0.7 to 1.5 mol per 1 mol of copper in the copper salt. Particularly preferred is 1.2 moles. Within the said range, since the transparency and heat resistance of the molded object obtained from a resin composition are especially excellent, it is preferable.

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

Examples of the solvent used in the reaction step include an organic solvent and water, and an organic solvent is preferable from the viewpoint of satisfactory reaction.
The quantity of the solvent used for reaction is 500-20000 mass parts normally with respect to 100 mass parts of copper salts, Preferably it is 1000-15000 mass parts.

  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.

  The reaction step 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 It is performed for 0.5 to 30 hours, more preferably 0.5 to 20 hours, particularly preferably 1 to 15 hours.

  In the reaction step, the phosphonic acid compound represented by the general formula (1) reacts with the copper salt, and fine phosphonic acid copper salt that does not dissolve in the solvent is generated by the reaction. However, at least one phosphate ester compound selected from the phosphate ester compound represented by the general formula (2) and the phosphate ester compound represented by the general formula (3) is used as a dispersant 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 following general formula (1) and the copper salt, but also, for example, the phosphate compound represented by the general formula (2) and the general formula (3) At least one type of phosphate ester compound selected from the phosphate ester compounds represented by) may react with a part of the copper salt.

In the reaction step, a part of the raw material may remain without reacting.
In the solvent removal step, fine particles comprising copper phosphonate are obtained by removing at least a part of the solvent from the reaction mixture.
In the solvent removal step, in the solvent removal step, in addition to the solvent, 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, and 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.

  As another method for removing the solvent, the reaction mixture is allowed to stand to precipitate fine particles composed of copper phosphonate, and the supernatant (solvent) is removed, or the reaction mixture is centrifuged. By this, the method of precipitating the microparticles | fine-particles which consist of a phosphonic acid copper salt, and removing a supernatant liquid (solvent) is mentioned.

  As a method for removing the solvent, for example, the solid content is settled by allowing the reaction mixture to stand, and the supernatant liquid (solvent) is removed, and the solid content is precipitated by centrifuging the reaction mixture to obtain the supernatant. Examples thereof include a method of removing the liquid (solvent) and a method of removing the solvent by distillation.

  Distillation is preferably performed under reduced pressure from the viewpoint of preventing thermal deterioration of the reaction mixture. That is, the solvent removal step is preferably a step of removing 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.

As a method for removing the solvent, these methods may be combined.
In addition, after the solvent removal step, for the purpose of removing impurities contained in the phosphonic acid copper salt fine particles, the phosphonic acid copper salt fine particles are dispersed in the dispersion medium, and then the dispersion medium is removed. You may provide the process to do.

  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.

  The average particle diameter of the fine particles comprising the phosphonic acid copper salt is usually 1 to 1000 nm, and preferably 5 to 300 nm from the viewpoint of ensuring dispersibility in the monomer and transparency of the resin composition.

[Oxidant]
The oxidizing agent used in the present invention is not particularly limited as long as it can suppress the reduction reaction of copper contained in the above-mentioned near infrared absorber. As the oxidizing agent used in the present invention, an oxidizing agent having a standard oxidation-reduction potential (E ⁰ ) at 25 ° C. of more than 0.15V is preferable, an oxidizing agent of more than 0.15V and not more than 2.1V is more preferable. An oxidant that exceeds .15 V and is 1.8 V or less is particularly preferable, and an oxidant that is 0.2 V or more and 1.8 V or less is most preferable.

When the standard oxidation-reduction potential (E ⁰ ) at 25 ° C. of the oxidizing agent exceeds 0.15 V, the standard oxidation-reduction potential (E ⁰ ) of at least one ion constituting the oxidizing agent exceeds 0.15 V. Means that.

Here, the standard oxidation-reduction potential (E ⁰ ) will be described. When the n-valent metal ion M ^{n +} is in equilibrium with the metal M as shown in the formula (1) in the aqueous solution, the equilibrium potential (E) of the formula (1) is Nernst represented by the formula (2). Is given by
M ^{n +} + ne ⁻ → M (1)
E = E ⁰ + RT / nF ln [M ^{n +} ] (2)
[In the formula (2), E ⁰ is a standard redox potential, F is a Faraday constant, R is a gas constant, T is an absolute temperature, and [M ^{n +} ] is an activity of a metal ion. ]

The standard oxidation-reduction potential is also called a unipolar potential, and is a measure of the ease with which electrons are exchanged by pairing with a standard hydrogen electrode. The potential of various metals and metal ion system when E ⁰ of this standard hydrogen electrode is ⁰ V is the standard oxidation-reduction potential (E ⁰ ).

The oxidizing agent that can be used in the present invention is usually a liquid or solid oxidizing agent, and specific examples thereof include potassium permanganate (KMnO ₄ ), iron (III) nitrate (Fe (NO _{3 3} ), hydrogen peroxide (H ₂ O ₂ ), sodium perchlorate (NaClO ₄ ), sodium dichromate (Na ₂ Cr ₂ O ₇ ), manganese dioxide (MnO ₂ ), sodium nitrate (NaNO ₃ ), Silver nitrate (AgNO ₃ ), copper nitrate (Cu (NO ₃ ) ₂ ), nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ), bromine (Br ₂ ), iodine (I ₂ ), and hydrates thereof Of these, potassium permanganate, iron (III) nitrate, copper nitrate, nitric acid, and hydrates thereof are preferable because they are inexpensive and easily available.

When a conventional resin composition containing a copper-based near-infrared absorber is used as an interlayer film for laminated glass for a long period of time, the copper contained in the near-infrared absorber changes from a divalent copper ion to a monovalent copper ion. It is thought that a reductive reaction that changes gradually occurs. Laminated glass is required to maintain a high visible light transmittance for a long period of time. However, due to such a reduction reaction of copper, a blackening phenomenon gradually occurs, and the visible light transmittance is lowered. The standard redox potential (E ⁰ ) of the copper (II) -copper (I) ion system is +0.15 V as shown below.

  By containing the oxidizing agent in the resin composition of the present invention, the reduction reaction of copper in the near-infrared absorbing agent can be effectively suppressed. That is, by using the resin composition of the present invention for an interlayer film for laminated glass, high visible light transmittance can be maintained for a long period without causing blackening. In other words, the resin composition of the present invention is excellent in light resistance.

Examples of the oxidizing agent are potassium permanganate (KMnO ₄ ) and iron (III) nitrate (Fe (NO ₃ ) ₃ ).
For potassium permanganate (KMnO ₄ ), manganese may exist in oxidation states such as +2, +3, +4, +6, and +7, but typically a reaction represented by the following half-reaction equation occurs.

The standard redox potential (E ⁰ ) of the permanganate ion-manganese (II) ion system is +1.51 V, which is a larger positive standard redox potential than the copper (II) ion-copper (I) ion system. Have Thus, potassium permanganate can oxidize copper (I) ions to copper (II) ions.
In iron (III) nitrate (Fe (NO ₃ ) ₃ ), typically, a reaction represented by the following half-reaction equation occurs.

Iron (III) ions - iron (II) standard oxidation-reduction potential of the ionic (E ⁰⁾ is + 0.75 V, nitrate ions - standard oxidation-reduction potential of nitric oxide system (E ⁰⁾ is + 0.96 V, Both systems have a large positive standard redox potential compared to the copper (II) ion-copper (I) ion system. Therefore, iron (III) nitrate can oxidize copper (I) ions to copper (II) ions.
About the said oxidizing agent, 1 type may be used independently and 2 or more types may be used in combination.

[resin]
Although it will not specifically limit as resin used for this invention if the above-mentioned near-infrared absorber can be disperse | distributed, For example, the following resin 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. At least one type of resin is preferable because it can disperse the near-infrared absorber well and is excellent in visible light transmittance.

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

  Polyvinyl acetal resin is excellent in dispersibility with the above-mentioned near infrared absorber. For this reason, since the intermediate film for laminated glasses using the resin composition containing polyvinyl acetal resin is excellent in adhesiveness with glass, it is preferable. Moreover, since the resin composition containing a polyvinyl acetal resin is flexible, when the laminated glass is placed under various temperature conditions, it is preferable because the deformation of the interlayer film for laminated glass due to temperature change is small. As the polyvinyl acetal resin, it is particularly 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 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. As for the viscosity average polymerization degree of the said polyvinyl alcohol resin, a preferable minimum is 200 and an upper limit is 3000, a more preferable minimum is 500 and an upper limit is 2200. If it is less than 200, the penetration resistance of the resulting laminated glass may be lowered. On the other hand, when 3000 is exceeded, the moldability of a resin composition may worsen, the rigidity of a resin composition may become large too much, and workability may worsen. The viscosity average polymerization degree and saponification degree of the polyvinyl alcohol resin can be measured based on, for example, JIS K 6726 “Testing method for polyvinyl alcohol”.

  The aldehyde is not particularly limited, and examples thereof include aldehydes having 1 to 10 carbon atoms. Specific examples include n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyl aldehyde, n- Examples include hexyl aldehyde, n-octyl aldehyde, n-nonyl aldehyde, n-decyl aldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Of these, n-butyraldehyde, n-hexylaldehyde, n-valeraldehyde and the like are preferable, and butyraldehyde having 4 carbon atoms is more preferable.

  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 a preferable lower limit is 60% and an upper limit is 75%.

The polyvinyl acetal resin may be a blend of two or more types depending on the required physical properties.
When an ethylene-vinyl acetate copolymer is used, the above-mentioned near-infrared absorber is excellent in dispersibility, and the resulting resin composition is excellent in glass adhesion, dispersibility, transparency, heat resistance, light resistance, etc. preferable.

(Resin composition)
The resin composition of the present invention is composed of a near-infrared absorber, an oxidizing agent, and a resin, and is a resin composition having excellent light resistance.

  It does not specifically limit as a manufacturing method of the resin composition of this invention. As a method for producing the resin composition, for example, after adding a resin, a near-infrared absorber dispersion, and an oxidizing agent to a solvent such as toluene, ethanol / toluene mixed solvent, methanol / toluene mixed solvent, methylene chloride, chloroform, and the like. And a method of dissolving the resin by stirring, ultrasonic irradiation, etc., obtaining a dispersion, and removing the solvent from the dispersion. As another method, after adding the resin to a solvent such as toluene, ethanol / toluene mixed solvent, methanol / toluene mixed solvent, methylene chloride, chloroform, etc., the resin is dissolved by stirring, ultrasonic irradiation, etc. Next, after adding the near-infrared absorbent dispersion and the oxidizing agent to the solution in which the resin is dissolved, stirring, ultrasonic irradiation, etc. are performed to obtain a dispersion, and the solvent is removed from the dispersion. . Further, as another method, after adding the resin to a solvent such as toluene, ethanol / toluene mixed solvent, methanol / toluene mixed solvent, methylene chloride, chloroform, etc., a solution in which the resin is dissolved by stirring, ultrasonic irradiation, etc. And after adding the near-infrared absorbent dispersion and the oxidizing agent to a solvent such as toluene, methanol, ethanol / toluene mixed solvent, methanol / toluene mixed solvent, methylene chloride, chloroform, and the like, by stirring, ultrasonic irradiation, etc. Then, each of the dispersed dispersions is adjusted, and the dispersion is added to the solution, or the solution is added to the dispersion, and if necessary, stirring and ultrasonic irradiation are performed. After mixing the two, the solvent is removed. The method of doing is mentioned.

  Further, for example, by using copper nitrate as a copper salt, a near-infrared absorbent dispersion containing an oxidizing agent is prepared by a method such that nitric acid as an oxidizing agent is contained in the near-infrared absorbent dispersion, A resin composition may be obtained from a near-infrared absorbent dispersion containing an oxidizing agent and a resin.

In addition, the said near-infrared absorber dispersion liquid can be prepared by disperse | distributing a near-infrared absorber in toluene, methanol, a methylene chloride, chloroform, etc.
The resin composition of the present invention preferably contains 0.05 to 50 parts by mass, more preferably 0.1 to 25 parts by mass of the near infrared absorber per 100 parts by mass of the resin. If the amount is less than 0.05 parts by mass, sufficient near infrared absorption characteristics may not be obtained. If the amount is more than 50 parts by mass, the transparency and adhesiveness of the resin may be significantly reduced.

  In the resin composition of the present invention, it is preferable to use 0.00001 to 0.03 mol of an oxidizing agent, and more preferably 0.0001 to 0.015 mol, per 1 mol of copper element contained in the near infrared absorber. preferable.

  If the content of the oxidizing agent relative to 1 mol of copper contained in the near-infrared absorbing agent is more than 0.03 mol, the resin composition itself is colored by the color of the oxidizing agent itself, resulting in Tvis (visible light transmittance). May have an effect. On the other hand, if the content of the oxidizing agent relative to 1 mol of copper contained in the near-infrared absorber is less than 0.00001 mol, the copper reduction reaction may not be sufficiently suppressed.

  The resin composition of the present invention preferably contains 0.0001 to 0.1 part by mass of the oxidizing agent, more preferably 0.0005 to 0.05 part by mass, per 100 parts by mass of the resin. Within the said range, since transparency of resin and adhesiveness with glass are kept favorable, it is preferable.

  The resin composition of the present invention has excellent near-infrared absorptivity and is suitable as an intermediate film for structural materials such as laminated glass because coloring when irradiated with light and reduction in visible light transmittance are suppressed. Can be used.

  The resin composition of the present invention may contain various additives as necessary. Examples of the additive include plasticizers, other dispersants, cross-linking agents, chelating agents, antioxidants, ultraviolet absorbers, light stabilizers, color tone correction agents, pH adjusting agents, and the like. These additives may be added when manufacturing the resin composition of the present invention, or may be added when manufacturing the above-mentioned near-infrared absorber, oxidizing agent, and resin, respectively.

When an extremely strong acid such as nitric acid or sulfuric acid is used as the oxidizing agent, it is preferable that a pH adjuster is contained in the composition. Examples of the pH adjuster include sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium butoxide and the like.
When using a pH adjuster, it is preferable to use in the range of 0.01-0.95 mol per mol of oxidizing agent.

[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 is suitably used as an intermediate film for structural materials such as an intermediate film for laminated glass because it has excellent light resistance in addition to excellent near infrared absorption ability.

  The laminated glass of the present invention has the interlayer film for laminated glass. 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.
The phosphoric acid ester compounds used in Production Example 1 and Example 6 below are phosphoric acid monoesters represented by the general formula (2), phosphoric acid diesters represented by the general formula (3), and polyoxy It is a mixture of an alkylene monoalkyl ether (C ₁₂ H ₂₅ (OCH ₂ CH ₂ ) _n OH) and a phosphoric acid triester represented by the general formula (4), in the formulas (2) to (4) R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ , and polyoxyalkylene monoalkyl ether n is 20, and R ¹² is an alkyl group having 12 carbon atoms. In addition, the abundance ratio (molar ratio) of the monoester, the diester, and the polyoxyalkylene monoalkyl ether in the phosphate compound is approximately 1: 1: 1. Further, the phosphate ester compound contains a small amount (about 5% by mass) of phosphate triester.

[Production Example 1]
(Preparation of copper salt dispersion)
To a 1 L eggplant flask, 14.0 g (70.13 mmol) of copper acetate monohydrate and 490 g of methanol were added and stirred at 25 ° C. for 1 hour to obtain a solution (solution A).

In a separate container, 2.8 g of a phosphoric ester compound and 9.59 g of n-butylphosphonic acid were dissolved in 96 g of methanol to obtain a solution (liquid B).
B liquid was dripped over 3 hours with respect to A liquid. The reaction was stirred at 25 ° C. for 20 hours.

Thereafter, the solvent was distilled off from the reaction solution with an evaporator. 100 g of toluene was added to the solid content from which the solvent had been distilled off, and the solvent was removed by an evaporator until the acetic acid odor disappeared and became a constant weight.
A thin light blue solid (copper salt, near infrared absorber) with a yield of 16.7 g (yield 100%) was obtained. Toluene 140g was added to this, ultrasonic irradiation was performed for 6 hours, and n-butylphosphonic acid copper salt toluene dispersion liquid (copper salt dispersion liquid (1)) was prepared.

[Example 1]
(Preparation of copper salt fine particle dispersed resin)
To a 300 mL Erlenmeyer flask, 1.90 g of triethylene glycol bis (2-ethylhexanoate), 100 g of toluene, 40 g of ethanol, and 5.0 g of polyvinyl butyral (PVB) were added. To this, 1.30 g of copper salt dispersion liquid (1) prepared in Production Example 1 (containing 0.583 mmol of copper salt) was added.

Add 0.01 mL of a solution of 43.4 mg of iron (III) nitrate nonahydrate ([Fe (H ₂ O) ₆ ] (NO ₃ ) ₃ · 3H ₂ O]) dissolved in 10 mL of methanol. did. After stirring for 10 hours at 25 ° C., ultrasonic irradiation was performed for 1 hour to uniformly dissolve PVB. This dispersion was spread on a Teflon (registered trademark) vat and air-dried at 25 ° C. for 20 hours. Furthermore, vacuum drying was performed at 40 ° C. for 5 hours and at 70 ° C. for 3.5 hours to completely remove the solvent, thereby obtaining a PVB resin (1) (resin composition (1)) in which copper salt fine particles were dispersed.

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

  The resin sheet was further preheated at 200 ° C. and 3 MPa for 1 minute using a mold having a thickness of 0.8 mm and a compression molding machine manufactured by Shindo Metal Industry Co., Ltd., and then pressed at 10 MPa for 5 minutes. A resin sheet (1) was obtained.

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. .

<Evaluation of light resistance>
The light resistance test was conducted by the following method.
Tvis (visible light transmittance) of the measurement sample (1) was determined using a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.).

Next, the measurement sample (1) is put into a super xenon weather meter (manufactured by Suga Test Instruments Co., Ltd.), and the intensity of the irradiated light is 180 W / m ² and stored for 150 hours under the conditions of no rain, and then the spectrum is measured. Tvis (visible light transmittance) was determined.
The Tvis of the measurement sample (1) before the light resistance test was 82.6%, the Tvis after 150 hours was 78.7%, and the difference in Tvis before and after the test ΔTvis was 3.9%.

[Example 2]
(Preparation of copper salt fine particle dispersed resin)
Add 43.4 mg of iron (III) nitrate nonahydrate ([Fe (H ₂ O) ₆ ] (NO ₃ ) ₃ · 3H ₂ O]) dissolved in 10 mL of methanol to 0.01 mL Except having changed to 0.03 mL, it carried out similarly to Example 1, and obtained PVB resin (2) (resin composition (2)) in which the copper salt fine particles were disperse | distributed.

(Evaluation)
<Preparation of resin sheet and measurement sample>
A measurement sample (2) was obtained in the same manner as in the production of the resin sheet of Example 1, except that the PVB resin (1) in which the copper salt fine particles were dispersed was replaced with the PVB resin (2) in which the copper salt fine particles were dispersed. ) Was produced.

<Evaluation of light resistance>
Using the measurement sample (2), a light resistance test was conducted in the same manner as the method shown in Example 1.
Tvis of the measurement sample (2) before the light resistance test was 82.8%, Tvis after 150 hours was 78.0%, and ΔTvis was 4.8%.

Example 3
(Preparation of copper salt fine particle dispersed resin)
Add 43.4 mg of iron (III) nitrate nonahydrate ([Fe (H ₂ O) ₆ ] (NO ₃ ) ₃ · 3H ₂ O]) dissolved in 10 mL of methanol to 0.01 mL Except having changed to 0.10 mL, it carried out similarly to Example 1, and obtained PVB resin (3) (resin composition (3)) in which the copper salt fine particles were disperse | distributed.

(Evaluation)
<Preparation of resin sheet and measurement sample>
A measurement sample (3) was obtained in the same manner as in the production of the resin sheet of Example 1, except that the PVB resin (1) in which the copper salt fine particles were dispersed was replaced with the PVB resin (3) in which the copper salt fine particles were dispersed. ) Was produced.

<Evaluation of light resistance>
Using the measurement sample (3), a light resistance test was performed in the same manner as the method shown in Example 1.
Tvis of the measurement sample (3) before the light resistance test was 82.9%, Tvis after 150 hours was 77.4%, and ΔTvis was 5.5%.

Example 4
(Preparation of copper salt fine particle dispersed resin)
To a 300 mL Erlenmeyer flask, 1.9 g of triethylene glycol bis (2-ethylhexanoate), 250 mL of methylene chloride, and 5.0 g of polyvinyl butyral (PVB) were added. To this, 1.30 g of the copper salt dispersion (1) (containing 0.583 mmol of copper salt) was added.

  To this, 0.01 mL of a solution prepared by dissolving 38.6 mg of potassium permanganate in 10 mL of acetone was added. After stirring for 10 hours at 25 ° C., ultrasonic irradiation was performed for 1 hour to uniformly dissolve PVB. This dispersion was spread on a Teflon (registered trademark) vat and air-dried at 25 ° C. for 20 hours. Further, vacuum drying was performed at 40 ° C. for 5 hours and at 70 ° C. for 3.5 hours to completely remove the solvent, thereby obtaining a PVB resin (4) (resin composition (4)) in which copper salt fine particles were dispersed.

(Evaluation)
<Preparation of resin sheet and measurement sample>
A measurement sample (4) was obtained in the same manner as in the production of the resin sheet of Example 1, except that the PVB resin (1) in which the copper salt fine particles were dispersed was replaced with the PVB resin (4) in which the copper salt fine particles were dispersed. ) Was produced.

<Evaluation of light resistance>
Using the measurement sample (4), a light resistance test was conducted in the same manner as the method shown in Example 1.
Tvis of the measurement sample (4) before the light resistance test was 79.9%, Tvis after 150 hours was 56.2%, and ΔTvis was 23.7%.

Example 5
(Preparation of copper salt fine particle dispersed resin)
To a 300 mL Erlenmeyer flask, 1.9 g of triethylene glycol bis (2-ethylhexanoate), 250 mL of methylene chloride, and 5.0 g of polyvinyl butyral (PVB) were added. To this, 1.30 g of the copper salt dispersion (1) (containing 0.583 mmol of copper salt) was added.

  To this, 0.1 mL of a solution obtained by dissolving 38.6 mg of potassium permanganate in 10 mL of acetone was added. After stirring for 10 hours at 25 ° C., ultrasonic irradiation was performed for 1 hour to uniformly dissolve PVB. This dispersion was spread on a Teflon (registered trademark) vat and air-dried at 25 ° C. for 20 hours. Furthermore, vacuum drying was performed at 40 ° C. for 5 hours and at 70 ° C. for 3.5 hours to completely remove the solvent, thereby obtaining a PVB resin (5) (resin composition (5)) in which copper salt fine particles were dispersed.

(Evaluation)
<Preparation of resin sheet and measurement sample>
A measurement sample (5) was obtained in the same manner as in the production of the resin sheet of Example 1, except that the PVB resin (1) in which the copper salt fine particles were dispersed was replaced with the PVB resin (5) in which the copper salt fine particles were dispersed. ) Was produced.

<Evaluation of light resistance>
Using the measurement sample (5), a light resistance test was performed in the same manner as the method shown in Example 1.
Tvis of the measurement sample (5) before the light resistance test was 80.5%, Tvis after 150 hours was 70.3%, and ΔTvis was 10.2%.

[Comparative Example 1]
(Preparation of copper salt fine particle dispersed resin)
Example except that 43.4 mg of iron (III) nitrate nonahydrate ([Fe (H ₂ O) ₆ ] (NO ₃ ) ₃ · 3H ₂ O]) in 10 mL of methanol was not added. In the same manner as in Example 1, a PVB resin (c1) (resin composition (c1)) in which n-butylphosphonic acid copper salt fine particles were dispersed was prepared.

(Evaluation)
<Preparation of resin sheet and measurement sample>
A measurement sample (c1) was obtained in the same manner as in the production of the resin sheet of Example 1, except that the PVB resin (1) in which the copper salt fine particles were dispersed was replaced with the PVB resin (c1) in which the copper salt fine particles were dispersed. ) Was produced.

<Evaluation of light resistance>
Using the measurement sample (c1), a light resistance test was performed in the same manner as the method shown in Example 1. The Tvis of the measurement sample (c1) before the light resistance test was 86.3%, the Tvis after 150 hours was 44.0%, and ΔTvis was 42.3%.

Example 6
(Preparation of copper salt dispersion)
To a 100 mL eggplant flask, 297 mg (1.49 mmol) of copper acetate monohydrate, 4.0 mg of copper nitrate trihydrate and 15 g of ethanol were added and stirred at 25 ° C. for 1 hour to obtain a solution (solution C).

In a separate container, 60 mg of a phosphoric ester compound and 207 mg of n-butylphosphonic acid were dissolved in 3 g of ethanol to obtain a solution (solution D).
D liquid was dripped over 1 hour with respect to C liquid. The reaction was stirred at 25 ° C. for 20 hours.

Thereafter, the solvent was distilled off from the reaction solution with an evaporator. Toluene (10 g) was added to the solid content from which the solvent was distilled off, and the mixture was distilled off with an evaporator until the acetic acid odor disappeared and became a constant weight.
A light blue solid (copper salt (near infrared absorber) and nitric acid (oxidant)) with a yield of 361 mg was obtained. To this was added 3.0 g of toluene, ultrasonic irradiation was performed for 1 hour, and an n-butylphosphonic acid copper salt toluene dispersion (copper salt dispersion (2)) containing nitric acid was prepared.

(Preparation of copper salt fine particle dispersed resin)
To a 300 mL Erlenmeyer flask, 1.90 g of triethylene glycol bis (2-ethylhexanoate), 100 g of toluene, 40 g of ethanol, and 5.0 g of polyvinyl butyral (PVB) were added. To this, 1.32 g (containing 0.583 mmol of copper salt) of the copper salt dispersion (2) was added.

  After stirring for 10 hours at 25 ° C., ultrasonic irradiation was performed for 1 hour to uniformly dissolve PVB. This dispersion was spread on a Teflon (registered trademark) vat and air-dried at 25 ° C. for 20 hours. Further, vacuum drying was performed at 40 ° C. for 5 hours and at 70 ° C. for 3.5 hours to completely remove the solvent, thereby obtaining a PVB resin (resin composition (6)) in which copper salt fine particles were dispersed.

(Evaluation)
<Preparation of resin sheet and measurement sample>
A measurement sample (6) was obtained in the same manner as in the production of the resin sheet of Example 1, except that the PVB resin (1) in which the copper salt fine particles were dispersed was replaced with the PVB resin (6) in which the copper salt fine particles were dispersed. ) Was produced.

(Evaluation)
Tvis of the measurement sample (6) before the light resistance test was 85.6%, Tvis after 150 hours was 82.4%, and ΔTvis was 3.2%.

Example 7
(Preparation of copper salt fine particle dispersed resin)
After adding 1.32 g of copper salt dispersion (2) (containing 0.583 mmol of copper salt), 0.1 mL of a solution obtained by dissolving 12.5 mg of sodium ethoxide in 12.5 mL of methanol was added. PVB resin (resin composition (7)) in which copper salt fine particles were dispersed was obtained in the same manner as in Example 6.

(Evaluation)
<Preparation of resin sheet and measurement sample>
A measurement sample (7) was obtained in the same manner as in the production of the resin sheet of Example 1, except that the PVB resin (1) in which the copper salt fine particles were dispersed was replaced with the PVB resin (7) in which the copper salt fine particles were dispersed. ) Was produced.

(Evaluation)
Tvis of the measurement sample (7) before the light resistance test was 83.7%, Tvis after 150 hours was 81.9%, and ΔTvis was 1.8%.

Claims (8)

A resin composition comprising a near-infrared absorber, an oxidizing agent, and a resin;
A resin composition characterized in that the near-infrared absorber is obtained by reacting at least a copper salt with a phosphonic acid compound represented by the following general formula (1).

[In General Formula (1), R ¹ is a monovalent group represented by —CH ₂ CH ₂ —R ¹¹ , and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 carbon atom. -20 fluorinated alkyl groups. ] The resin composition according to claim 1, wherein the oxidizing agent is an oxidizing agent having a standard oxidation-reduction potential (E ⁰ ) at 25 ° C exceeding 0.15V.   The resin composition according to claim 1 or 2, wherein 0.00001 to 0.03 mol of an oxidizing agent is used per 1 mol of copper element contained in the near infrared absorber.   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 resin composition as described in any one of Claims 1-3.   The resin composition according to claim 4, wherein the resin is a polyvinyl butyral resin or an ethylene-vinyl acetate copolymer.   The resin composition as described in any one of Claims 1-5 which contains 0.05-50 mass parts of near-infrared absorbers per 100 mass parts of said resin.   The intermediate film for laminated glasses formed from the resin composition as described in any one of Claims 1-6.   A laminated glass having the interlayer film for laminated glass according to claim 7.