WO2014175231A1

WO2014175231A1 - Resin composition and use thereof

Info

Publication number: WO2014175231A1
Application number: PCT/JP2014/061202
Authority: WO
Inventors: 巨樹岩間; 町田　克一
Original assignee: 株式会社クレハ
Priority date: 2013-04-26
Filing date: 2014-04-21
Publication date: 2014-10-30

Abstract

The purpose of the present invention is to provide a resin composition containing a near-infrared ray absorbent, which has excellent light resistance and heat resistance. The resin composition according to the present invention comprises a near-infrared ray absorbent, a phosphoric acid triester and a resin, wherein the near-infrared ray absorbent comprises microparticles each comprising a phosphonic acid copper salt represented by general formula (1) [wherein R¹ represents a monovalent group represented by the formula -CH₂CH₂-R¹¹; and R¹¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a fluorinated alkyl group having 1 to 20 carbon atoms], and the phosphoric acid triester is a phosphoric acid triester represented by general formula (2) [wherein R's independently represent an alkyl group, an alkenyl group, a phenyl group, or a phenyl group having a substituent].

Description

Resin composition and use thereof

The present invention relates to a resin composition and its use, and more particularly to a resin composition comprising a near-infrared absorber, a phosphoric acid triester, and a resin, and its use.

Conventionally, laminated glass is 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 having a wavelength close to visible light are called near infrared rays. Near-infrared rays are also called heat rays and 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 absorptivity to laminated glass used for vehicles and buildings while maintaining visible light transmittance. For example, a copper salt composition containing a phosphonic acid copper salt, a polysiloxane component, a plasticizer, and a dispersant is known (see, for example, Patent Document 1). In general, when a resin composition obtained by mixing a metal salt with a resin is exposed to a high temperature, the visible light transmittance may be reduced or yellowed. However, Patent Document 1 provides an infrared absorption film in which the resin composition containing the copper salt composition and the resin is excellent in visible light transmission and stability even when exposed to high temperatures. It is disclosed that it is possible.

In the resin composition described in Patent Document 1, yellowing when exposed to a high temperature is suppressed as compared with a resin composition composed only of a phosphonic acid copper salt and a resin, but dehydrates and condenses a silane compound. Since processes are required, there is a problem that the number of processes increases.

In addition, as a resin composition used for laminated glass and the like, it is desired that the resin composition is not colored by sunlight or that the visible light transmittance is not lowered, that is, has light resistance, but the invention disclosed in Patent Document 1 However, no consideration was given to light resistance.

2009-242650

The present invention has been made in view of the above prior art, and an object thereof is to provide a resin composition containing a near-infrared absorber, which is excellent in light resistance and heat resistance.

As a result of intensive studies to achieve the above problems, the present inventors have found that a resin composition comprising a specific near infrared absorber, a specific phosphoric acid triester, and a resin can solve the above problems. The present invention has been completed by finding out what can be done.

That is, the resin composition of the present invention is a resin composition comprising a near-infrared absorber, a phosphate triester, and a resin, and the near-infrared absorber is a phosphonic acid represented by the following general formula (1). It is fine particles made of a copper salt, and the phosphoric acid triester is a phosphoric acid triester represented by the following general formula (2).

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

[In the general formula (2), each R is independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 35 carbon atoms, a phenyl group, or a phenyl group having a substituent, The number is 15 or less. ]
In the general formula (2), each R is preferably independently a phenyl group having a substituent.

It is preferable that the resin composition further contains a phosphorus-based antioxidant.
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 to 50 parts by mass of a near infrared absorber per 100 parts by mass of the resin.
It is preferable to contain 0.05 to 5.0 parts by mass of phosphoric acid triester per 100 parts by mass of the resin.

It is preferable to contain 0.05 to 5.0 parts by mass of a phosphorus-based antioxidant per 100 parts by mass of the 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 excellent light resistance and excellent heat resistance.

Next, the present invention will be specifically described.
The resin composition of the present invention is a resin composition comprising a near-infrared absorber, a phosphate triester, and a resin, and the near-infrared absorber is a copper phosphonate represented by the following general formula (1). It is fine particles made of a salt, and the phosphate triester is a phosphate triester represented by the following general formula (2).

The resin composition of the present invention is also referred to as a copper salt fine particle dispersed resin.
[Near infrared absorber]
The near-infrared absorber used in the present invention is fine particles composed of a phosphonic acid copper salt represented by the following general formula (1).

The fine particles comprising the phosphonic acid copper salt represented by the following general formula (1) may be formed only from the phosphonic acid copper salt represented by the following general formula (1), and represented by the following general formula (1). The phosphonic acid copper salt may be formed from other components.

[In General Formula (1), R ¹ is a monovalent group represented by —CH ₂ CH ₂ —R ¹¹ , and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 carbon atom. Represents -20 fluorinated alkyl groups. ]
R ¹¹ 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 Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like are preferable. In addition, as a phosphonic acid copper salt represented by General formula (1), it may be used individually by 1 type, or 2 or more types may be used.

In the present specification, the “phosphonic acid copper salt represented by the general formula (1)” is also simply referred to as “phosphonic acid copper salt”.
Although there is no limitation in particular as a manufacturing method of the microparticles | fine-particles which consist of a phosphonic acid copper salt used for this invention, For example, it can manufacture with the following method.

As a method for producing fine particles comprising a phosphonic acid copper salt, a step of mixing a phosphonic acid compound represented by the following general formula (4) and a copper salt in a solvent to obtain a reaction mixture (hereinafter also referred to as a reaction step). ), A method having a step of obtaining fine particles composed of a copper phosphonate by removing the solvent in the reaction mixture (hereinafter also referred to as a solvent removal step).

[In General Formula (4), R ¹ is a monovalent group represented by —CH ₂ CH ₂ —R ¹¹ , and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 carbon atom. Represents -20 fluorinated alkyl groups. ]
As the phosphonic acid compound represented by the general formula (4), those in which R ¹¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms are preferable. Examples of the phosphonic acid compound represented by the general formula (4) include ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, heptylphosphonic acid, octylphosphonic acid, nonylphosphonic acid, and decylphosphonic acid. Examples thereof include alkylphosphonic acids such as acid, undecylphosphonic acid, dodecylphosphonic acid, tridecylphosphonic acid, tetradecylphosphonic acid, pentadecylphosphonic acid, hexadecylphosphonic acid, heptadecylphosphonic acid, and octadecylphosphonic acid. In addition, as a phosphonic acid compound represented by General formula (4), it may be used individually by 1 type, or 2 or more types may be used.

As the copper salt, a copper salt capable of supplying divalent copper ions is usually used. The copper salt may be a copper salt other than the phosphonic acid copper salt represented by the general formula (1). 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 in terms of solubility and removal of by-products.
When producing fine particles comprising a phosphonic acid copper salt, a dispersant may be used in the reaction step. Examples of the dispersant include at least one phosphate ester compound selected from a phosphate ester compound represented by the general formula (3a) and a phosphate ester compound represented by the general formula (3b), the phosphoric acid The phosphoric acid in an ester compound, ie, the compound which neutralized the hydroxyl group with the base is mentioned. In addition, as a base used for neutralization, inorganic bases, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, are mentioned.

[In the general formulas (3a) and (3b), R ²¹ , R ²² and R ²³ are monovalent groups represented by — (CH ₂ CH ₂ O) _n R ⁵⁵ , and n is from 2 to 65. R ⁵⁵ is an integer, and R ⁵⁵ 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. ]
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 4 to 35. When n is less than 2, transparency may be insufficient when a laminated glass or the like is produced. On the other hand, when n exceeds 65, the amount of the phosphoric acid ester compound necessary for obtaining laminated glass having sufficient transparency tends to increase, resulting in high costs.

R ⁵⁵ 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. Is more preferable, and 12 to 20 alkyl groups are particularly preferable. When R ⁵⁵ is a group having less than 6 carbon atoms, transparency may be insufficient when a laminated glass or the like is produced. Further, when R ⁵⁵ is a group having more than 25 carbon atoms, the amount of the phosphate ester compound necessary for obtaining a laminated glass having sufficient transparency tends to increase, resulting in high costs. .

When a dispersing agent is used when obtaining fine particles comprising the phosphonic acid copper salt, the phosphoric acid ester compound represented by the general formula (3a) and the phosphoric acid ester compound represented by the general formula (3b) Although at least one is preferably used, it is more preferable to use both the phosphate ester compound represented by the general formula (3a) and the phosphate ester compound represented by the general formula (3b). It is preferable to use the phosphate ester compound represented by the general formula (3a) and the phosphate ester compound represented by the general formula (3b) because they tend to be excellent in transparency and heat resistance of laminated glass and the like. When both the phosphate ester compound represented by the general formula (3a) and the phosphate ester compound represented by the general formula (3b) are used, the phosphate ester compound represented by the general formula (3a) And the ratio of the phosphoric acid ester compound represented by the general formula (3b) is not particularly limited, but is usually 10:90 to 90:10 in molar ratio ((3a) :( 3b)).

Moreover, as a phosphate ester compound represented by the said general formula (3a), it may be used individually by 1 type, or 2 or more types may be used, and the phosphate ester compound represented by the said General formula (3b) May be used alone or in combination of two or more.

As at least one phosphate ester compound selected from the phosphate ester compound represented by the general formula (3a) and the phosphate ester compound represented by the general formula (3b), commercially available phosphoric acid Ester compounds such as DLP-10, DDP-6, DDP-8, DDP-10, TDP-6, TDP-8, TDP-10 (manufactured by Nikko Chemicals Co., Ltd.), Plysurf 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.) and the like can also be used. 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.

When producing fine particles comprising a phosphonic acid copper salt, it is preferable to use 0.5 to 1.5 mol of the phosphonic acid compound represented by the general formula (4) per 1 mol of the copper salt. It is more preferable to use 8 to 1.2 mol. Further, the dispersant is at least one phosphate ester compound selected from a phosphate ester compound represented by the general formula (3a) and a phosphate ester compound represented by the general formula (3b), and / or In the case of phosphoric acid in the phosphoric ester compound, that is, a compound obtained by neutralizing a hydroxyl group with a base, 5 to 100 parts by mass is preferably used per 100 parts by mass of the copper salt, and 10 to 50 parts by mass is preferably used. More preferred.

Examples of the solvent include alcohols such as methanol, ethanol, isopropyl alcohol and n-butanol, tetrahydrofuran (THF), N, N-dimethylformamide (DMF), water and the like. The solvent preferably includes at least one 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 solvent selected from methanol, ethanol, THF, and DMF, and more preferably contains at least one solvent selected from methanol and ethanol. As said solvent, only these solvents may be included and the other solvent may be included. Examples of the solvent include at least one solvent selected from methanol, ethanol, isopropyl alcohol, n-butanol, DMF, and THF (preferably at least one solvent selected from methanol, ethanol, THF, and DMF). More preferably at least one solvent selected from methanol and ethanol), and other solvents are usually contained in an amount of 0 to 50 parts by weight, preferably 0 to 30 parts by weight. Also good. When two or more kinds of solvents are used as the solvent, specific examples thereof include denatured ethanol containing ethanol and a small amount of other solvents. Denatured ethanol usually contains 3 to 50 parts by mass, preferably 3 to 30 parts by mass of other 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 Is carried out 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 (4) reacts with the copper salt, and fine phosphonic acid copper salt that does not dissolve in the solvent is generated by the reaction. At least one phosphate ester compound selected from the phosphate ester compound represented by the general formula (3a) and the phosphate ester compound represented by the general formula (3b) acts as a good 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 between the phosphonic acid compound represented by the general formula (4) and the copper salt, but also, for example, the phosphate ester compound represented by the general formula (3a) and the general formula (3b) 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. Further, a part of the raw material may remain without reacting.

In the method for producing fine particles composed of the copper phosphonate, the fine particles composed of the copper phosphonate are usually obtained by removing at least a part of the solvent from the reaction mixture.

In the solvent removal step, at least a part of the solvent is removed from the reaction mixture. In the solvent removal step, in addition to the solvent, the liquid components in the reaction mixture may be removed together.
As a solvent removal process, the method of removing a solvent as a fraction by distilling a reaction mixture is mentioned.

Distillation is preferably performed under reduced pressure from the viewpoint of preventing thermal deterioration of the reaction mixture.
When performing vacuum distillation, although depending on the type of solvent, the conditions for vacuum distillation are usually 0.01 to 15 kPa. The outflow temperature of the fraction varies depending on the type of solvent and the pressure, but is usually 30 to 150 ° C.

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 phosphonic acid copper salt and removing a supernatant liquid (solvent) is mentioned.

In addition, as a method of removing a solvent, you may carry out combining these methods.
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. A process may be provided.

As the fine particles composed of the copper phosphonate, fine particles composed of a copper phosphonate having an average particle diameter of 1 to 1000 nm are usually used. The average particle size is more preferably 5 to 300 nm in order to ensure dispersibility in the monomer and transparency of the resin composition.

[Phosphoric acid triester]
The phosphate triester used in the present invention is a phosphate triester represented by the following general formula (2).

[In the general formula (2), each R is independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 35 carbon atoms, a phenyl group, or a phenyl group having a substituent, The number is 15 or less. ]
As a phosphoric acid triester used for this invention, 1 type may be used or 2 or more types may be used.

Each R is preferably independently a phenyl group or a phenyl group having a substituent, and more preferably a phenyl group having a substituent.
Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Examples include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group. The alkyl group may have a branched structure.

The alkenyl group having 2 to 35 carbon atoms is preferably an alkenyl group having 4 to 25 carbon atoms. Examples of the alkenyl group include an allyl group, a butenyl group, a hexenyl group, an octenyl group, a decenyl group, and an oleyl group. Note that the alkenyl group may have a branched structure.

The substituent that the phenyl group having the substituent has usually has 15 or less carbon atoms.
The phenyl group having a substituent may be any phenyl group having at least one substituent, and examples thereof include a phenyl group having 1 to 5 substituents, and a phenyl group having 1 to 3 substituents is preferable. A phenyl group having two substituents is more preferable.

In addition, the substituent is preferably present at least at the 1-position or the 3-position of the phenyl group, and preferably at least at the 1-position.
As the substituent, at least one of an alkyl group, an alkoxy group, an oxycarbonylalkyl group, a nitro group, a cyano group, an ester group, a halogen, a phenyl group, a benzyl group, a phenoxy group, and a hydrogen atom is an alkyl group, an alkoxy group, Oxycarbonylalkyl group, nitro group, ester group, cyano group, phenyl group substituted by halogen, etc., at least one hydrogen atom on the benzene ring is alkyl group, alkoxy group, oxycarbonylalkyl group, nitro group, ester group , A benzyl group substituted with a cyano group, halogen, etc., a phenoxy group wherein at least one of the hydrogen atoms is substituted with an alkyl group, alkoxy group, oxycarbonylalkyl group, nitro group, ester group, cyano group, halogen, etc. An alkyl group is preferable.

That is, the substituent is preferably an alkyl group having 15 or less carbon atoms. The alkyl group having 15 or less carbon atoms is more preferably an alkyl group having 1 to 5 carbon atoms, which is advantageous in terms of availability and price, and specifically includes a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Is preferred.

In addition, the alkyl group having 15 or less carbon atoms is preferably a branched alkyl group for the purpose of suppressing hydrolysis of the phosphate ester. Examples of the branched alkyl group include an isopropyl group as the propyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group as the butyl group, and the pentyl group as Examples include 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, and 2,2-dimethylpropyl group.

As the phenyl group having the substituent, for example, groups represented by the following formulas (i), (ii), and (iii) are preferable, and a group represented by (i) is more preferable.

Specific examples of the phosphoric acid triester used in the present invention include phosphoric acid triesters represented by the following formulas (I) to (VII). (I) and (V) are preferred, and (I ) Is more preferable.

Since the resin composition of the present invention contains the phosphoric acid triester, coloring and reduction in visible light transmittance due to irradiation with light such as sunlight are suppressed, and yellowing during heating and the like is suppressed. Can be suppressed, which is preferable.

[resin]
In the present invention, a resin is used. The resin used in the present invention is not particularly limited as long as it can disperse the above-described near-infrared 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 and ethylene-vinyl acetate copolymer, polyvinyl butyral resin (PVB), and ethylene-vinyl acetate copolymer Particularly preferred is at least one resin selected from a coalescence, and most preferred is a polyvinyl butyral resin or an ethylene-vinyl acetate copolymer. When the polyvinyl acetal resin is used, the dispersibility of the above-mentioned near-infrared absorber is excellent. When an optical material is produced using the resin composition of the present invention, the resin of the present invention is excellent in adhesion to glass or the like. It is preferable because the composition is flexible and deformation of the near-infrared absorber due to a change in temperature hardly occurs. Moreover, as polyvinyl acetal resin, it is preferable to use polyvinyl butyral resin (PVB) from the viewpoints of glass adhesion, dispersibility, transparency, heat resistance, light resistance, and the like.

The polyvinyl acetal resin may be a blend of two or more kinds depending on the required physical properties, 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%, with a preferred lower limit being 60% and an upper limit being 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 degree of polymerization and the degree of saponification of the polyvinyl alcohol resin can be measured based on, for example, JISK 6726 “Polyvinyl alcohol test method”.

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.
[Phosphorus antioxidant]
The resin composition of the present invention may further contain a phosphorus-based antioxidant in addition to the near-infrared absorber, the phosphoric acid triester, and the resin.

The phosphorus-based antioxidant has at least one structure represented by the following general formula (A) in the molecule and has a structure represented by the following general formula (B) bonded to a phosphorus atom in the molecule. At least one phosphorus-based antioxidant selected from non-phosphorus-based antioxidants is preferred. As a phosphorus antioxidant, 1 type may be used or 2 or more types may be used.

[In general formula (A), R ² to R ⁴ are each independently an alkyl group having 1 or 2 carbon atoms, and R ⁵ to R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Indicates.
However, when two or more structures represented by the general formula (A) are present in the molecule, R ⁵ to R ⁸ of the structure represented by one general formula (A) are represented by the other general formula (A). Crosslinks with R ⁵ to R ⁸ having the structure shown may be formed. ]

[In General Formula (B), R represents an alkyl group. ]
A phosphorus system having one or more structures represented by the general formula (A) bonded to a phosphorus atom in the molecule and having no structure represented by the general formula (B) bonded to a phosphorus atom in the molecule. The antioxidant is also referred to as a specific phosphorus antioxidant.

The specific phosphorus-based antioxidant preferably has two or more structures represented by the general formula (A) bonded to a phosphorus atom in the molecule. That is, the phosphorus antioxidant has two or more structures represented by the general formula (A) bonded to the phosphorus atom in the molecule and is expressed by the general formula (B) bonded to the phosphorus atom. It is preferable that it is a phosphorus antioxidant which does not have a structure in a molecule | numerator.

The specific phosphorus-based antioxidant has at least one phosphorus atom in the molecule. The phosphorus atom constituting the specific phosphorus-based antioxidant usually has a +3 valence.
In addition, since it is excellent in the transparency of a resin composition when the resin composition of this invention contains phosphorus antioxidant, it is preferable.

As described above, in the general formula (A), R ² to R ⁴ are each independently an alkyl group having 1 or 2 carbon atoms.
In the general formula (A), R ⁵ to R ⁸ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.

When two or more structures represented by the general formula (A) are present in the molecule, R ⁵ to R ⁸ of the structure represented by one general formula (A) are represented by the other general formula (A). Crosslinks with R ⁵ to R ⁸ having a structure as described above may be formed. When R ⁵ to R ⁸ of the structure represented by one general formula (A) form a bridge with R ⁵ to R ⁸ of the structure represented by the other general formula (A), Includes a single bond and an alkylene group having 1 to 4 carbon atoms, and a single bond is preferable.

In the general formula (A), the substituent at the ortho position of the oxygen atom, that is, the group composed of the carbon atom and R ² to R ⁴ is a bulky alkyl group, specifically a tertiary alkyl group. is there. Specifically, R ² to R ⁴ are each independently an alkyl group having 1 or 2 carbon atoms, preferably a methyl group.

In the general formula (A), R ⁶ is preferably an alkyl group having 1 to 7 carbon atoms. R ⁶ is preferably a bulky alkyl group, specifically, preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group, and a t-butyl group. It is particularly preferred.

In the general formula (A), R ⁵ and R ⁷ are preferably each independently a hydrogen atom or an alkyl group having 1 to 2 carbon atoms.
In the general formula (A), R ⁸ is preferably a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R ⁸ is preferably a bulky alkyl group, specifically a tertiary alkyl group, and more preferably a t-butyl group.

The specific phosphorus-based antioxidant is not particularly limited, and for example, a commercially available product can be used. Specific phosphorus-based antioxidants include, for example, IRGAFOS 168 (manufactured by BASF) (the following formula 21), GSY-P101 (manufactured by Sakai Chemical Industry) (the following formula 22), Sumilizer GP (manufactured by Sumitomo Chemical) (the following formula 23) ) Can be used. The phosphorus-based antioxidant represented by the formula 21 is commercially available from Johoku Chemical Industry under the trade name JP-650. As specific phosphorus antioxidant, 1 type may be used or 2 or more types may be used.

The specific phosphorus-based antioxidant preferably has two or more structures represented by the general formula (A) bonded to a phosphorus atom in the molecule as described above, and IRGAFOS 168 is generally bonded to a phosphorus atom. The structure represented by formula (A) has three structures in the molecule, GSY-P101 has four structures represented by the general formula (A) bonded to the phosphorus atom in the molecule, The molecule has two structures represented by the general formula (A) bonded to atoms.

In the above-mentioned Sumilizer GP, R ⁸ having a structure represented by one general formula (A) is bridged with R ⁸ having a structure represented by the other general formula (A) by a single bond.
The specific phosphorus-based antioxidant used in the present invention includes a phosphorus atom having one phosphorus atom in the molecule and three structures represented by the general formula (A) bonded to the phosphorus atom in the molecule. A system antioxidant is most preferable from the viewpoint of suppression of yellowing.

In addition, the specific phosphorus-based antioxidant used in the present invention does not have a structure represented by the general formula (B) bonded to a phosphorus atom in the molecule. In addition, this inventor discovered that yellowing would occur easily when it has this structure. Although the detailed reason for which yellowing is likely to occur is unknown, the present inventors are one of the causes of yellowing that the structure represented by the general formula (B) is hydrolyzed by heating. Presumed to be.

Moreover, as a specific phosphorus antioxidant, it has one or more structures represented by the general formula (A) bonded to the phosphorus atom in the molecule, and is represented by the general formula (B) bonded to the phosphorus atom. As long as it does not have a structure to be formed, other structures are not particularly limited, but a hindered phenol structure may be included in the molecule.

(Resin composition)
As described above, the resin composition of the present invention is a resin composition comprising a near-infrared absorber, a phosphate triester, and a resin.

The resin composition of the present invention is excellent in light resistance and heat resistance. It is preferable that the resin composition of the present invention further contains a phosphorus-based antioxidant. It is preferable to contain a phosphorus-based antioxidant because even if the amount of phosphoric acid triester used is relatively small, the light resistance and heat resistance tend to be excellent, and the transparency of the resin composition tends to be excellent.

The resin composition of the present invention may be a composition comprising a near-infrared absorber, a phosphate triester, and a resin as described above, and preferably contains a phosphorus-based antioxidant, The manufacturing method is not particularly limited. Examples of the method for producing the resin composition of the present invention include resins such as toluene, ethanol / toluene mixed solvent, methanol / toluene mixed solvent, methylene chloride, chloroform and the like, resin triester, near infrared absorber dispersion, Examples thereof include a method of adding an optional phosphorus-based antioxidant, dissolving the resin by stirring, ultrasonic irradiation, etc., obtaining a dispersion, and removing the solvent from the dispersion. The near-infrared absorbent dispersion can be prepared by dispersing the near-infrared absorbent in toluene, methanol, methylene chloride, chloroform, triethylene glycol bis (2-ethylhexanoate) or the like.

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 a 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.

The resin composition of the present invention preferably contains 0.05 to 5.0 parts by mass, more preferably 0.1 to 3.0 parts by mass of the phosphoric acid triester per 100 parts by mass of the resin. preferable. If it is less than 0.05 parts by mass, it may not be possible to sufficiently suppress coloring or a decrease in visible light transmittance. If it is more than 5.0 parts by mass, it may be colored due to decomposition of the phosphate triester. The phosphoric acid triester may precipitate in the resin and the transparency of the resin film may be impaired.

Further, when the resin composition of the present invention contains the phosphorus antioxidant, it is preferable to contain 0.05 to 5.0 parts by mass of the phosphorus antioxidant per 100 parts by mass of the resin. More preferably, the content is 0.1 to 3.0 parts by mass. If it is less than 0.05 parts by mass, it may not be possible to sufficiently color or suppress the decrease in visible light transmittance. If it is more than 5.0 parts by mass, it will be colored due to decomposition of the phosphorus antioxidant. Or the phosphorus-based antioxidant may be precipitated in the resin and the transparency of the resin film may be impaired.

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. Further, since the resin composition of the present invention is also suppressed in coloring during heating, that is, yellowing, it can be suitably used as an intermediate film for structural materials such as laminated glass from this viewpoint. It is.

Moreover, various additives may be contained in the resin composition of the present invention. Examples of the additive include a plasticizer, a dispersant, a crosslinking agent, a chelating agent, an antioxidant, an ultraviolet absorber, a light stabilizer, and a color tone correction agent. These additives may be added when manufacturing the resin composition of the present invention, and are added when manufacturing the above-mentioned near-infrared absorber, phosphate triester, resin, and phosphorus antioxidant, respectively. May be.

[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 absorption ability, excellent light resistance, and is suppressed in terms of coloring during heating, that is, yellowing, so that it is a structural material such as an interlayer film for laminated glass It can be suitably used as an intermediate film for use.

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

In a separate container, 1.75 g of PRISURF A219B (Daiichi Kogyo Seiyaku) and 4.82 g of n-butylphosphonic acid were dissolved in 100 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 20 ° C. for 10 hours.

Thereafter, the solvent was distilled off from the reaction solution with an evaporator (water bath 60 ° C.). 100 g of toluene was added to the solid content from which the solvent had been distilled off, and the solvent was distilled off with an evaporator until a constant weight was obtained and the acetic acid odor disappeared. A blue-green solid with a yield of 8.75 g (100% yield) was obtained. To this was added 211 g of toluene, and ultrasonic irradiation was performed for 6 hours to obtain an n-butylphosphonic acid copper salt toluene dispersion (1).

[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) (3GO, plasticizer), 250 ml of toluene, and 5.00 g of polyvinyl butyral (PVB) were added.

To this was added 150 mg of tris (2,4-di-tertiarybutylphenyl) phosphate.
To this was added 3.65 g of the above n-butylphosphonic acid copper salt toluene dispersion (1) (containing 0.583 mmol of copper salt), stirred at 20 ° C. for 10 hours, and then irradiated with ultrasonic waves for 1.5 hours. Was dissolved uniformly.

The dispersion was spread on a Teflon (registered trademark) vat and air-dried at 20 ° C for 12 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 (1)>
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 (1).

<Production of resin sheet (2)>
The resin sheet (1) was further preheated at 200 ° C. and 3 MPa for 1 minute using a 0.8 mm-thick mold and a compression molding machine manufactured by Shindo Metal Industry Co., Ltd., and then at 10 MPa for 5 minutes. The resin sheet (2) was obtained by pressing.

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

The laminated glass (1) was heated in an autoclave under a nitrogen atmosphere at a pressure of 1.5 MPa and 130 ° C. for 0.5 hours to obtain a measurement sample (1) in which slide glasses were disposed on both surfaces of the resin sheet. .

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

<Evaluation of transparency>
The haze of the measurement sample (1) and the measurement sample (2) was measured using Nippon Denshoku NDH-2000 (D65 light source, single beam).

The haze of the measurement sample (1) was 8.7%, and the haze of the measurement sample (2) was 5.2%.
<Evaluation of heat resistance>
The spectra of the measurement samples (1) and (2) were measured by the following methods, respectively.

The spectrum of the measurement sample was measured using a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.) in the wavelength range of 250 to 2500 nm. Tristimulus values (X, Y, Z) were calculated using a C light source.

The measurement sample (1) had a YI (yellowness index) of 4.6, and the measurement sample (2) had a YI of 7.4. The YI value was calculated according to the following formula.
YI = (128X-106Z) / Y
When the difference between the YI of the measurement sample (1) and the YI of the measurement sample (2) (YI of the measurement sample (2) −YI of the measurement sample (1)) is ΔYI, ΔYI was 2.8.

<Evaluation of light resistance>
The light resistance test was conducted by the following method.
Tvis (visible light transmittance) of the measurement sample (2) was determined using a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.).

Next, put the measurement sample (2) in a super xenon weather meter (manufactured by Suga Test Instruments Co., Ltd.), store it for 400 hours under the condition of 180 W / m ² , no rain, and then measure the spectrum. YI and Tvis were determined.

YI after 400 hours was 8.0, and ΔYI was 0.6 (8.0-7.4), where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 81.3%, and the Tvis of the measurement sample (2) before the light resistance test was 85.5%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 4 2%.

[Comparative Example 1]
(Preparation of copper salt fine particle dispersed resin)
PVB resin (c1) (resin composition (c1)) in which copper salt fine particles were dispersed was carried out in the same manner as in Example 1 except that tris (2,4-di-tert-butylphenyl) phosphate was not used. Obtained.

(Evaluation)
<Preparation of resin sheet (c1)>
Resin made in the same manner as in <Preparation of resin sheet (1)> in Example 1 except that PVB resin (1) in which copper salt fine particles are dispersed is replaced with PVB resin (c1) in which copper salt fine particles are dispersed. A sheet (c1) was obtained.

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

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

<Preparation of measurement sample (c2)>
A measurement sample (c2) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (c2).

<Evaluation of transparency>
The haze of the measurement sample (c1) and the measurement sample (c2) was measured by the same method as that described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (c1) was 1.1%, and the haze of the measurement sample (c2) was 1.4%.
<Evaluation of heat resistance>
The spectrum of the measurement sample (c1) and the measurement sample (c2) was measured by the same method as that described in the section <Evaluation of heat resistance> in Example 1.

YI of the measurement sample (c1) was 4.3, and YI of the measurement sample (c2) was 9.4. ΔYI of the measurement sample (c1) and the measurement sample (c2) was 5.1.
<Evaluation of light resistance>
YI and Tvis were obtained in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (c2).

YI after 400 hours was 22.6, and ΔYI was 13.2 (22.6-9.4), where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 24.6%, and the Tvis of the measurement sample (c2) before the light resistance test was 84.1%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 59 .5%.

[Example 2]
(Preparation of copper salt fine particle dispersed resin)
To a 300 ml Erlenmeyer flask, 1.90 g of triethylene glycol bis (2-ethylhexanoate) (3GO, plasticizer), 250 ml of toluene, and 5.00 g of polyvinyl butyral (PVB) were added.

To this, 50 mg of tris (2,4-di-tertiarybutylphenyl) phosphate and 50 mg of tris (2,4-di-tertiarybutylphenyl) phosphate were added.
To this was added 3.65 g of the above n-butylphosphonic acid copper salt toluene dispersion (1) (containing 0.583 mmol of copper salt), stirred at 20 ° C. for 10 hours, and then irradiated with ultrasonic waves for 1.5 hours. Was dissolved uniformly.

The dispersion was spread on a Teflon (registered trademark) vat and air-dried at 20 ° C for 12 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 (2) (resin composition (2)) in which copper salt fine particles were dispersed.

(Evaluation)
<Preparation of resin sheet (3)>
Resin is carried out in the same manner as in <Preparation of resin sheet (1)> in Example 1 except that PVB resin (1) in which copper salt fine particles are dispersed is replaced with PVB resin (2) in which copper salt fine particles are dispersed. Sheet (3) was obtained.

<Preparation of resin sheet (4)>
Except having replaced the resin sheet (1) with the resin sheet (3), it carried out like the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (4).

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

<Preparation of measurement sample (4)>
A measurement sample (4) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (4).

<Evaluation of transparency>
The haze of the measurement sample (3) and the measurement sample (4) was measured by the same method as described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (3) was 1.4%, and the haze of the measurement sample (4) was 2.7%.
<Evaluation of heat resistance>
The spectra of the measurement sample (3) and the measurement sample (4) were measured by the same method as that described in the section <Evaluation of heat resistance> in Example 1.

The YI of the measurement sample (3) was 4.6, and the YI of the measurement sample (4) was 8.6. ΔYI of the measurement sample (3) and the measurement sample (4) was 4.0.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (4).

YI after 400 hours was 9.8, and ΔYI was 1.2 (9.8-8.6), where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 81.8%, and the Tvis of the measurement sample (4) before the light resistance test was 84.3%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 2 .5%.

Example 3
(Preparation of copper salt fine particle dispersed resin)
PVB resin (3) in which copper salt fine particles are dispersed (resin composition (3)) except that the amount of tris (2,4-di-tertiarybutylphenyl) phosphate used is changed from 150 mg to 50 mg. 3)) was obtained.

(Evaluation)
<Preparation of resin sheet (5)>
Resin is carried out in the same manner as in <Preparation of resin sheet (1)> in Example 1 except that PVB resin (1) in which copper salt fine particles are dispersed is replaced with PVB resin (3) in which copper salt fine particles are dispersed. A sheet (5) was obtained.

<Preparation of resin sheet (6)>
Except having replaced the resin sheet (1) with the resin sheet (5), it carried out similarly to the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (6).

<Preparation of measurement sample (5)>
A measurement sample (5) was obtained in the same manner as in <Production of measurement sample (1)> in Example 1 except that the resin sheet (1) was replaced with a resin sheet (5).

<Preparation of measurement sample (6)>
A measurement sample (6) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (6).

<Evaluation of transparency>
The haze of the measurement sample (5) and the measurement sample (6) was measured by the same method as described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (5) was 1.6%, and the haze of the measurement sample (6) was 1.9%.
<Evaluation of heat resistance>
Spectroscopy of the measurement sample (5) and the measurement sample (6) was measured by the same method as that described in the section <Evaluation of heat resistance> in Example 1.

YI of the measurement sample (5) was 4.8, and YI of the measurement sample (6) was 7.8. ΔYI of the measurement sample (5) and the measurement sample (6) was 3.0.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (6).

YI after 400 hours was 14.6, and ΔYI was 6.8 (14.6-7.8) when the difference from YI before the light resistance test was ΔYI.
The Tvis after 400 hours was 63.8%, and the Tvis of the measurement sample (6) before the light resistance test was 85.3%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 21 .5%.

Example 4
(Preparation of copper salt fine particle dispersed resin)
The amount of tris (2,4-di-tertiarybutylphenyl) phosphite was changed from 50 mg to 100 mg, and the amount of tris (2,4-di-tertiarybutylphenyl) phosphate was changed from 50 mg to 100 mg. Was performed in the same manner as in Example 2 to obtain a PVB resin (4) (resin composition (4)) in which copper salt fine particles were dispersed.

(Evaluation)
<Preparation of resin sheet (7)>
Resin is carried out in the same manner as in <Preparation of resin sheet (1)> in Example 1 except that PVB resin (1) in which copper salt fine particles are dispersed is replaced with PVB resin (4) in which copper salt fine particles are dispersed. A sheet (7) was obtained.

<Production of resin sheet (8)>
Except having replaced the resin sheet (1) with the resin sheet (7), it carried out like the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (8).

<Preparation of measurement sample (7)>
A measurement sample (7) was obtained in the same manner as in <Production of measurement sample (1)> in Example 1 except that the resin sheet (1) was replaced with a resin sheet (7).

<Preparation of measurement sample (8)>
A measurement sample (8) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (8).

<Evaluation of transparency>
The haze of the measurement sample (7) and the measurement sample (8) was measured by the same method as described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (7) was 6.8%, and the haze of the measurement sample (8) was 6.4%.
<Evaluation of heat resistance>
Spectroscopy of the measurement sample (7) and the measurement sample (8) was measured by the same method as described in the section <Evaluation of heat resistance> in Example 1.

YI of the measurement sample (7) was 5.0, and YI of the measurement sample (8) was 7.9. ΔYI of the measurement sample (7) and the measurement sample (8) was 2.9.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (8).

YI after 400 hours was 8.3, and ΔYI was 0.4 (8.3-7.9), where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 81.6%, and the Tvis of the measurement sample (8) before the light resistance test was 84.2%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 2 It was 6%.

Example 5
(Preparation of copper salt fine particle dispersed resin)
PVB resin (5) (resin composition) in which copper salt fine particles were dispersed was carried out in the same manner as in Example 1 except that 150 mg of tris (2,4-di-tert-butylphenyl) phosphate was replaced with 24.7 mg of triphenyl phosphate. (5)) was obtained.

(Evaluation)
<Preparation of resin sheet (9)>
Resin is carried out in the same manner as in <Production of resin sheet (1)> in Example 1, except that PVB resin (1) in which copper salt fine particles are dispersed is replaced with PVB resin (5) in which copper salt fine particles are dispersed. Sheet (9) was obtained.

<Preparation of resin sheet (10)>
Except having replaced the resin sheet (1) with the resin sheet (9), it carried out similarly to the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (10).

<Preparation of measurement sample (9)>
A measurement sample (9) was obtained in the same manner as in <Production of measurement sample (1)> in Example 1 except that the resin sheet (1) was replaced with a resin sheet (9).

<Preparation of measurement sample (10)>
A measurement sample (10) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (10).

<Evaluation of transparency>
The haze of the measurement sample (9) and the measurement sample (10) was measured by the same method as that described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (9) was 1.8%, and the haze of the measurement sample (10) was 1.8%.
<Evaluation of heat resistance>
The spectrum of the measurement sample (9) and the measurement sample (10) was measured by the same method as that described in the section <Evaluation of heat resistance> in Example 1.

YI of the measurement sample (9) was 5.7, and YI of the measurement sample (10) was 7.5. ΔYI of the measurement sample (9) and the measurement sample (10) was 1.8.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (10).

YI after 400 hours was 18.1, and ΔYI was 10.6 (18.1-7.5), where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 37.3%, and the Tvis of the measurement sample (10) before the light resistance test was 85.6%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 48 3%.

Example 6
(Preparation of copper salt fine particle dispersed resin)
PVB resin (6) in which copper salt fine particles are dispersed (resin composition (except for the resin composition)), except that 150 mg of tris (2,4-di-tert-butylphenyl) phosphate is replaced with 40.4 mg of tributyl phosphate. 6)) was obtained.

(Evaluation)
<Preparation of resin sheet (11)>
Resin is carried out in the same manner as in <Production of resin sheet (1)> in Example 1, except that PVB resin (1) in which copper salt fine particles are dispersed is replaced with PVB resin (6) in which copper salt fine particles are dispersed. A sheet (11) was obtained.

<Preparation of resin sheet (12)>
Except having replaced the resin sheet (1) with the resin sheet (11), it carried out similarly to the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (12).

<Preparation of measurement sample (11)>
A measurement sample (11) was obtained in the same manner as in <Production of measurement sample (1)> in Example 1 except that the resin sheet (1) was replaced with a resin sheet (11).

<Preparation of measurement sample (12)>
A measurement sample (12) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (12).

<Evaluation of transparency>
The haze of the measurement sample (11) and the measurement sample (12) was measured by the same method as described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (11) was 2.2%, and the haze of the measurement sample (12) was 2.1%.
<Evaluation of heat resistance>
Spectroscopy of the measurement sample (11) and the measurement sample (12) was measured by the same method as that described in the section <Evaluation of heat resistance> in Example 1.

YI of the measurement sample (11) was 5.7, and YI of the measurement sample (12) was 8.4. ΔYI of the measurement sample (11) and the measurement sample (12) was 2.7.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (12).

YI after 400 hours was 15.8, and ΔYI was 7.4 (15.8-8.4), where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 30.1%, and the Tvis of the measurement sample (12) before the light resistance test was 84.4%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 54 3%.

Example 7
(Preparation of copper salt fine particle dispersed resin)
PVB resin in which copper salt fine particles are dispersed (7), except that 150 mg of tris (2,4-di-tert-butylphenyl) phosphate is replaced with 32.9 mg of tris (2-ethylhexyl) phosphate. (Resin composition (7)) was obtained.

(Evaluation)
<Preparation of resin sheet (13)>
Resin is carried out in the same manner as in <Preparation of resin sheet (1)> in Example 1, except that PVB resin (1) in which copper salt fine particles are dispersed is replaced with PVB resin (7) in which copper salt fine particles are dispersed. A sheet (13) was obtained.

<Preparation of resin sheet (14)>
Except having replaced the resin sheet (1) with the resin sheet (13), it carried out like the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (14).

<Preparation of measurement sample (13)>
A measurement sample (13) was obtained in the same manner as in <Production of measurement sample (1)> in Example 1 except that the resin sheet (1) was replaced with a resin sheet (13).

<Preparation of measurement sample (14)>
A measurement sample (14) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (14).

<Evaluation of transparency>
The haze of the measurement sample (13) and the measurement sample (14) was measured by the same method as that described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (13) was 2.6%, and the haze of the measurement sample (14) was 2.0%.
<Evaluation of heat resistance>
Spectroscopy of the measurement sample (13) and the measurement sample (14) was measured by the same method as that described in the section <Evaluation of heat resistance> in Example 1.

The YI of the measurement sample (13) was 6.0, and the YI of the measurement sample (14) was 6.7. ΔYI of the measurement sample (13) and the measurement sample (14) was 0.7.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (14).

YI after 400 hours was 9.9, and ΔYI was 3.2 (9.9-6.7), where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 29.6%, and the Tvis of the measurement sample (14) before the light resistance test was 85.8%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 56 2%.

[Production Example 2]
(Preparation of copper salt dispersion)
To a 500 ml eggplant flask, 3.557 g (17.82 mmol) of copper acetate monohydrate and 178 g of ethanol were added and stirred at 20 ° C. for 1 hour to obtain a solution (solution A).

In a separate container, 0.711 g of Prisurf A219B (Daiichi Kogyo Seiyaku) and 2.436 g of n-butylphosphonic acid were dissolved in 25 g of ethanol to obtain a solution (liquid B).
B liquid was dripped over 3 hours with respect to A liquid. The reaction was stirred at 20 ° C. for 20 hours.

Thereafter, the solvent was distilled off from the reaction solution with an evaporator (water bath 60 ° C.). 50 g of toluene was added to the solid content from which the solvent had been distilled off, and the solvent was distilled off with an evaporator until a constant weight was reached and there was no odor of acetic acid. A blue-green solid with a yield of 4.27 g (yield 100%) was obtained. To this was added 83 g of toluene, and ultrasonic irradiation was performed for 3 hours to obtain an n-butylphosphonic acid copper salt toluene dispersion (2).

Example 8
(Preparation of copper salt fine particle dispersed resin)
Add 1.90 g of triethylene glycol bis (2-ethylhexanoate) (3GO, plasticizer), 100 g of toluene, 40 g of ethanol, and 5.00 g of polyvinyl butyral (PVB) to a 300 ml Erlenmeyer flask and stir at 20 ° C. for 10 hours. And completely dissolved (solution C).

To 3.131 g of the above n-butylphosphonic acid copper salt toluene dispersion (2) (containing 0.583 mmol of copper salt) was added 30.1 mg of Nikkor TOP-0V (manufactured by Nikko Chemicals Corporation, trioleyl phosphate). The mixture was stirred at 20 ° C for 1 hour (D liquid).

The D liquid was added to the C liquid in about 1 minute and irradiated with ultrasonic waves for 1 hour. This dispersion was spread on a Teflon (registered trademark) vat and air-dried at 20 ° C. for 12 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 (8) (resin composition (8)) in which copper salt fine particles were dispersed.

(Evaluation)
<Production of resin sheet (15)>
Resin is carried out in the same manner as in <Preparation of resin sheet (1)> in Example 1 except that PVB resin (1) in which copper salt fine particles are dispersed is replaced with PVB resin (8) in which copper salt fine particles are dispersed. A sheet (15) was obtained.

<Preparation of resin sheet (16)>
Except having replaced the resin sheet (1) with the resin sheet (15), it carried out similarly to the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (16).

<Preparation of measurement sample (15)>
A measurement sample (15) was obtained in the same manner as in <Production of measurement sample (1)> in Example 1 except that the resin sheet (1) was replaced with a resin sheet (15).

<Preparation of measurement sample (16)>
A measurement sample (16) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (16).

<Evaluation of transparency>
The haze of the measurement sample (15) and the measurement sample (16) was measured by the same method as described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (15) was 1.6%, and the haze of the measurement sample (16) was 1.0%.
<Evaluation of heat resistance>
Spectroscopy of the measurement sample (15) and the measurement sample (16) was measured by the same method as that described in the section <Evaluation of heat resistance> in Example 1.

YI of the measurement sample (15) was 2.3, and YI of the measurement sample (16) was 4.1. ΔYI of the measurement sample (15) and the measurement sample (16) was 1.8.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (16).

The YI after 400 hours was 9.7. If the difference from the YI before the light resistance test was ΔYI, the ΔYI was 5.6 (9.7-4.1).
The Tvis after 400 hours was 65.1%, and the Tvis of the measurement sample (16) before the light resistance test was 88.0%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 22 9%.

[Comparative Example 2]
(Preparation of copper salt fine particle dispersed resin)
A PVB resin (c2) (resin composition (c2)) in which copper salt fine particles were dispersed was obtained in the same manner as in Example 8 except that Nikkor TOP-0V was not used.

(Evaluation)
<Preparation of resin sheet (c3)>
Except that the PVB resin (1) in which the copper salt fine particles are dispersed is replaced with the PVB resin (c2) in which the copper salt fine particles are dispersed, the same procedure as in <Preparation of the resin sheet (1)> in Example 1 is carried out. A sheet (c3) was obtained.

<Production of resin sheet (c4)>
Except having replaced the resin sheet (1) with the resin sheet (c3), it carried out similarly to the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (c4).

<Preparation of measurement sample (c3)>
A measurement sample (c3) was obtained in the same manner as in <Production of measurement sample (1)> in Example 1 except that the resin sheet (1) was replaced with a resin sheet (c3).

<Preparation of measurement sample (c4)>
A measurement sample (c4) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (c4).

<Evaluation of transparency>
The haze of the measurement sample (c3) and the measurement sample (c4) was measured by the same method as that described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (c3) was 1.1%, and the haze of the measurement sample (c4) was 0.9%.
<Evaluation of heat resistance>
Spectroscopy of the measurement sample (c3) and the measurement sample (c4) was measured by the same method as described in the section <Evaluation of heat resistance> in Example 1.

YI of the measurement sample (c3) was 1.9, and YI of the measurement sample (c4) was 5.0. ΔYI of the measurement sample (c3) and the measurement sample (c4) was 3.1.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (c4).

YI after 400 hours was 44.1, and ΔYI was 39.1 (44.1-5.0), where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 24.2%, and the Tvis of the measurement sample (c4) before the light resistance test was 87.5%. Therefore, when the difference in Tvis before and after the test is ΔTvis, ΔTvis is 63 3%.

Example 9
(Preparation of copper salt fine particle dispersed resin)
Performed in the same manner as in Example 8 except that 30.1 mg of Nikkor TOP-0V (manufactured by Nikko Chemicals Co., Ltd., trioleyl phosphate) was replaced with 3.9 mg of tris (2,4-di-tert-butylphenyl) phosphate. A PVB resin (9) (resin composition (9)) in which copper salt fine particles were dispersed was obtained.

(Evaluation)
<Preparation of resin sheet (17)>
Resin is carried out in the same manner as in <Preparation of resin sheet (1)> in Example 1, except that PVB resin (1) in which copper salt fine particles are dispersed is replaced with PVB resin (9) in which copper salt fine particles are dispersed. A sheet (17) was obtained.

<Preparation of resin sheet (18)>
Except having replaced the resin sheet (1) with the resin sheet (17), it carried out similarly to the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (18).

<Preparation of measurement sample (17)>
A measurement sample (17) was obtained in the same manner as in <Production of measurement sample (1)> in Example 1 except that the resin sheet (1) was replaced with a resin sheet (17).

<Preparation of measurement sample (18)>
A measurement sample (18) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (18).

<Evaluation of transparency>
The haze of the measurement sample (17) and the measurement sample (18) was measured by the same method as described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (17) was 1.5%, and the haze of the measurement sample (18) was 1.1%.
<Evaluation of heat resistance>
Spectroscopy of the measurement sample (17) and the measurement sample (18) was measured by the same method as that described in the section <Evaluation of heat resistance> in Example 1.

YI of the measurement sample (17) was 2.2, and YI of the measurement sample (18) was 4.1. ΔYI of the measurement sample (17) and the measurement sample (18) was 1.9.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (18).

YI after 400 hours was 12.9, and ΔYI was 8.8 (12.9-4.1), where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 41.7%, and the Tvis of the measurement sample (18) before the light resistance test was 87.3%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 45 It was 6%.

Example 10
(Preparation of copper salt fine particle dispersed resin)
Performed in the same manner as in Example 8 except that 30.1 mg of Nikkor TOP-0V (manufactured by Nikko Chemicals Co., Ltd., trioleyl phosphate) was replaced with 11.8 mg of tris (2,4-di-tert-butylphenyl) phosphate. A PVB resin (10) (resin composition (10)) in which copper salt fine particles were dispersed was obtained.

(Evaluation)
<Preparation of resin sheet (19)>
Resin is carried out in the same manner as in <Production of resin sheet (1)> in Example 1 except that PVB resin (1) in which copper salt fine particles are dispersed is replaced with PVB resin (10) in which copper salt fine particles are dispersed. A sheet (19) was obtained.

<Preparation of resin sheet (20)>
Except having replaced the resin sheet (1) with the resin sheet (19), it carried out like the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (20).

<Preparation of measurement sample (19)>
A measurement sample (19) was obtained in the same manner as in <Production of measurement sample (1)> in Example 1 except that the resin sheet (1) was replaced with a resin sheet (19).

<Preparation of measurement sample (20)>
A measurement sample (20) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (20).

<Evaluation of transparency>
The haze of the measurement sample (19) and the measurement sample (20) was measured by the same method as described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (19) was 1.9%, and the haze of the measurement sample (20) was 1.8%.
<Evaluation of heat resistance>
Spectroscopy of the measurement sample (19) and the measurement sample (20) was measured by the same method as described in the section <Evaluation of heat resistance> in Example 1.

YI of the measurement sample (19) was 2.4, and YI of the measurement sample (20) was 4.7. ΔYI of the measurement sample (19) and the measurement sample (20) was 2.3.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (20).

YI after 400 hours was 19.3, and ΔYI was 14.6 (19.3-4.7) where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 34.8%, and the Tvis of the measurement sample (20) before the light resistance test was 88.3%. Therefore, if the difference in Tvis before and after the test is ΔTvis, ΔTvis is 53 .5%.

Example 11
Performed in the same manner as in Example 8 except that 30.1 mg of Nikkor TOP-0V (manufactured by Nikko Chemicals Co., Ltd., trioleyl phosphate) was replaced with 23.5 mg of tris (2,4-di-tert-butylphenyl) phosphate. A PVB resin (11) (resin composition (11)) in which copper salt fine particles were dispersed was obtained.

(Evaluation)
<Production of resin sheet (21)>
Resin is carried out in the same manner as in <Production of resin sheet (1)> in Example 1, except that PVB resin (1) in which copper salt fine particles are dispersed is replaced with PVB resin (11) in which copper salt fine particles are dispersed. A sheet (21) was obtained.

<Production of resin sheet (22)>
Except having replaced the resin sheet (1) with the resin sheet (21), it carried out like the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (22).

<Preparation of measurement sample (21)>
A measurement sample (21) was obtained in the same manner as in <Production of measurement sample (1)> in Example 1 except that the resin sheet (1) was replaced with a resin sheet (21).

<Preparation of measurement sample (22)>
A measurement sample (22) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (22).

<Evaluation of transparency>
The haze of the measurement sample (21) and the measurement sample (22) was measured by the same method as described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (21) was 1.6%, and the haze of the measurement sample (22) was 1.2%.
<Evaluation of heat resistance>
Spectroscopy of the measurement sample (21) and the measurement sample (22) was measured by the same method as that described in the section <Evaluation of heat resistance> in Example 1.

YI of the measurement sample (21) was 2.3, and YI of the measurement sample (22) was 4.2. ΔYI of the measurement sample (21) and the measurement sample (22) was 1.9.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (22).

YI after 400 hours was 14.1, and ΔYI was 9.9 (14.1-4.2), where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 39.9%, and the Tvis of the measurement sample (22) before the light resistance test was 87.8%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 47 9%.

Example 12
(Preparation of copper salt fine particle dispersed resin)
A PVB resin in which copper salt fine particles are dispersed is carried out in the same manner as in Example 8 except that the amount of Nikkor TOP-0V (manufactured by Nikko Chemicals Co., Ltd., trioleyl phosphate) is changed from 30.1 mg to 5.0 mg. 12) (Resin composition (12)) was obtained.

(Evaluation)
<Preparation of resin sheet (23)>
Except that the PVB resin (1) in which the copper salt fine particles are dispersed is replaced with the PVB resin (12) in which the copper salt fine particles are dispersed, the same procedure as in <Preparation of resin sheet (1)> in Example 1 is carried out. A sheet (23) was obtained.

<Production of resin sheet (24)>
Except having replaced the resin sheet (1) with the resin sheet (23), it carried out similarly to the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (24).

<Preparation of measurement sample (23)>
A measurement sample (23) was obtained in the same manner as in <Production of measurement sample (1)> in Example 1 except that the resin sheet (1) was replaced with a resin sheet (23).

<Preparation of measurement sample (24)>
A measurement sample (24) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (24).

<Evaluation of transparency>
The haze of the measurement sample (23) and the measurement sample (24) was measured by the same method as that described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (23) was 1.5%, and the haze of the measurement sample (24) was 1.0%.
<Evaluation of heat resistance>
The spectra of the measurement sample (23) and the measurement sample (24) were measured by the same method as that described in the section <Evaluation of heat resistance> in Example 1.

YI of the measurement sample (23) was 2.3, and YI of the measurement sample (24) was 4.7. ΔYI of the measurement sample (23) and the measurement sample (24) was 2.4.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (24).

YI after 400 hours was 31.3, and ΔYI was 26.6 (31.3-4.7), where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 32.5%, and the Tvis of the measurement sample (24) before the light resistance test was 87.4%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 54 9%.

Example 13
(Preparation of copper salt fine particle dispersed resin)
A PVB resin in which copper salt fine particles were dispersed was carried out in the same manner as in Example 8 except that the amount of Nikkor TOP-0V (manufactured by Nikko Chemicals Co., Ltd., trioleyl phosphate) was changed from 30.1 mg to 15.1 mg. 13) (Resin composition (13)) was obtained.

(Evaluation)
<Production of resin sheet (25)>
Resin is carried out in the same manner as in <Preparation of resin sheet (1)> in Example 1 except that PVB resin (1) in which copper salt fine particles are dispersed is replaced with PVB resin (13) in which copper salt fine particles are dispersed. A sheet (25) was obtained.

<Production of resin sheet (26)>
Except having replaced the resin sheet (1) with the resin sheet (25), it carried out similarly to the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (26).

<Preparation of measurement sample (25)>
A measurement sample (25) was obtained in the same manner as in <Production of measurement sample (1)> in Example 1 except that the resin sheet (1) was replaced with a resin sheet (25).

<Preparation of measurement sample (26)>
A measurement sample (26) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (26).

<Evaluation of transparency>
The haze of the measurement sample (25) and the measurement sample (26) was measured by the same method as described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (25) was 1.7%, and the haze of the measurement sample (26) was 1.2%.
<Evaluation of heat resistance>
Spectroscopy of the measurement sample (25) and the measurement sample (26) was measured by the same method as described in the section <Evaluation of heat resistance> in Example 1.

YI of the measurement sample (25) was 2.7, and YI of the measurement sample (26) was 5.7. ΔYI of the measurement sample (25) and the measurement sample (26) was 3.0.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (26).

YI after 400 hours was 30.4, and ΔYI was 24.7 (30.4−5.7), where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 35.1%, and the Tvis of the measurement sample (26) before the light resistance test was 86.7%. Therefore, if the difference in Tvis before and after the test is ΔTvis, ΔTvis is 51 It was 6%.

Example 14
(Preparation of copper salt fine particle dispersed resin)
PVB resin in which copper salt fine particles are dispersed (14) (Resin composition (14)) was obtained.

(Evaluation)
<Preparation of resin sheet (27)>
Except that the PVB resin (1) in which the copper salt fine particles are dispersed is replaced with the PVB resin (14) in which the copper salt fine particles are dispersed, the same procedure as in <Preparation of resin sheet (1)> in Example 1 is performed. A sheet (27) was obtained.

<Production of resin sheet (28)>
Except having replaced the resin sheet (1) with the resin sheet (27), it carried out similarly to the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (28).

<Preparation of measurement sample (27)>
A measurement sample (27) was obtained in the same manner as in <Production of measurement sample (1)> in Example 1 except that the resin sheet (1) was replaced with a resin sheet (27).

<Preparation of measurement sample (28)>
A measurement sample (28) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (28).

<Evaluation of transparency>
The haze of the measurement sample (27) and the measurement sample (28) was measured by the same method as described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (27) was 2.2%, and the haze of the measurement sample (28) was 1.4%.
<Evaluation of heat resistance>
Spectroscopy of the measurement sample (27) and the measurement sample (28) was measured by the same method as that described in the section <Evaluation of heat resistance> in Example 1.

YI of the measurement sample (27) was 3.0, and YI of the measurement sample (28) was 4.5. ΔYI of the measurement sample (27) and the measurement sample (28) was 1.5.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (28).

YI after 400 hours was 14.8, and ΔYI was 10.3 (14.8-4.5), where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 45.6%, and the Tvis of the measurement sample (28) before the light resistance test was 88.1%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 42 .5%.

Example 15
(Preparation of copper salt fine particle dispersed resin)
The same procedure as in Example 8 was conducted except that 30.1 mg of Nikkor TOP-0V (manufactured by Nikko Chemicals Co., Ltd., trioleyl phosphate) was replaced with 7.6 mg of tris (2-ethylhexyl) phosphate, and copper salt fine particles were dispersed. PVB resin (15) (resin composition (15)) was obtained.

(Evaluation)
<Production of resin sheet (29)>
Resin is carried out in the same manner as in <Preparation of resin sheet (1)> in Example 1 except that PVB resin (1) in which copper salt fine particles are dispersed is replaced with PVB resin (15) in which copper salt fine particles are dispersed. A sheet (29) was obtained.

<Preparation of resin sheet (30)>
Except having replaced the resin sheet (1) with the resin sheet (29), it carried out similarly to the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (30).

<Preparation of measurement sample (29)>
A measurement sample (29) was obtained in the same manner as in <Production of measurement sample (1)> in Example 1 except that the resin sheet (1) was replaced with a resin sheet (29).

<Preparation of measurement sample (30)>
A measurement sample (30) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (30).

<Evaluation of transparency>
The haze of the measurement sample (29) and the measurement sample (30) was measured by the same method as described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (29) was 2.3%, and the haze of the measurement sample (30) was 1.5%.
<Evaluation of heat resistance>
Spectroscopy of the measurement sample (29) and the measurement sample (30) was measured by the same method as that described in the section <Evaluation of heat resistance> in Example 1.

YI of the measurement sample (29) was 3.0, and YI of the measurement sample (30) was 4.5. ΔYI of the measurement sample (29) and the measurement sample (30) was 1.5.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (30).

YI after 400 hours was 15.7, and ΔYI was 11.2 (15.7-4.5), where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 42.3%, and the Tvis of the measurement sample (30) before the light resistance test was 88.1%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 45 8%.

Example 16
(Preparation of copper salt fine particle dispersed resin)
PVB resin (16) in which copper salt fine particles were dispersed was carried out in the same manner as in Example 8 except that 30.1 mg of Nikkor TOP-0V (manufactured by Nikko Chemicals Co., Ltd., trioleyl phosphate) was replaced with 5.7 mg of triphenyl phosphate. ) (Resin composition (16)) was obtained.

(Evaluation)
<Preparation of resin sheet (31)>
Resin is carried out in the same manner as in <Preparation of resin sheet (1)> in Example 1 except that PVB resin (1) in which copper salt fine particles are dispersed is replaced with PVB resin (16) in which copper salt fine particles are dispersed. A sheet (31) was obtained.

<Production of resin sheet (32)>
Except having replaced the resin sheet (1) with the resin sheet (31), it carried out like the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (32).

<Preparation of measurement sample (31)>
A measurement sample (31) was obtained in the same manner as in <Production of measurement sample (1)> in Example 1 except that the resin sheet (1) was replaced with a resin sheet (31).

<Preparation of measurement sample (32)>
A measurement sample (32) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (32).

<Evaluation of transparency>
The haze of the measurement sample (31) and the measurement sample (32) was measured by the same method as described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (31) was 3.5%, and the haze of the measurement sample (32) was 2.0%.
<Evaluation of heat resistance>
Spectroscopy of the measurement sample (31) and the measurement sample (32) was measured by the same method as that described in the section <Evaluation of heat resistance> in Example 1.

YI of the measurement sample (31) was 3.4, and YI of the measurement sample (32) was 5.1. ΔYI of the measurement sample (31) and the measurement sample (32) was 1.7.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (32).

YI after 400 hours was 26.5, and ΔYI was 21.4 (26.5-5.1) where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 32.8%, and the Tvis of the measurement sample (32) before the light resistance test was 87.6%. Therefore, when the difference in Tvis before and after the test is ΔTvis, ΔTvis is 54 8%.

Example 17
(Preparation of copper salt fine particle dispersed resin)
The same procedure was performed as in Example 8 except that 30.1 mg of Nikkor TOP-0V (manufactured by Nikko Chemicals Co., Ltd., trioleyl phosphate) was replaced with 6.5 mg of tri-o-cresyl phosphate, and copper salt fine particles were dispersed. PVB resin (17) (resin composition (17)) was obtained.

(Evaluation)
<Production of resin sheet (33)>
Resin is carried out in the same manner as in <Preparation of resin sheet (1)> in Example 1, except that PVB resin (1) in which copper salt fine particles are dispersed is replaced with PVB resin (17) in which copper salt fine particles are dispersed. A sheet (33) was obtained.

<Preparation of resin sheet (34)>
Except having replaced the resin sheet (1) with the resin sheet (33), it carried out similarly to the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (34).

<Preparation of measurement sample (33)>
A measurement sample (33) was obtained in the same manner as in <Production of measurement sample (1)> in Example 1 except that the resin sheet (1) was replaced with a resin sheet (33).

<Preparation of measurement sample (34)>
A measurement sample (34) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (34).

<Evaluation of transparency>
The haze of the measurement sample (33) and the measurement sample (34) was measured by the same method as described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (33) was 3.1%, and the haze of the measurement sample (34) was 2.1%.
<Evaluation of heat resistance>
Spectroscopy of the measurement sample (33) and the measurement sample (34) was measured by the same method as described in the section <Evaluation of heat resistance> in Example 1.

YI of the measurement sample (33) was 2.8, and YI of the measurement sample (34) was 4.9. ΔYI of the measurement sample (33) and the measurement sample (34) was 2.1.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (34).

YI after 400 hours was 17.3, and ΔYI was 12.4 (17.3-4.9), where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 42.1%, and the Tvis of the measurement sample (34) before the light resistance test was 87.5%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 45 4%.

Example 18
(Preparation of copper salt fine particle dispersed resin)
The same procedure was carried out as in Example 8 except that 30.1 mg of Nikkor TOP-0V (manufactured by Nikko Chemicals Co., Ltd., trioleyl phosphate) was replaced with 6.4 mg of tri-p-cresyl phosphate. PVB resin (18) (resin composition (18)) was obtained.

(Evaluation)
<Production of resin sheet (35)>
Resin is carried out in the same manner as in <Production of resin sheet (1)> in Example 1, except that PVB resin (1) in which copper salt fine particles are dispersed is replaced with PVB resin (18) in which copper salt fine particles are dispersed. A sheet (35) was obtained.

<Production of resin sheet (36)>
Except having replaced the resin sheet (1) with the resin sheet (35), it carried out like the <Preparation of the resin sheet (2)> term of Example 1, and obtained the resin sheet (36).

<Preparation of measurement sample (35)>
A measurement sample (35) was obtained in the same manner as in <Production of measurement sample (1)> in Example 1 except that the resin sheet (1) was replaced with a resin sheet (35).

<Preparation of measurement sample (36)>
A measurement sample (36) was obtained in the same manner as in <Production of measurement sample (2)> in Example 1 except that the resin sheet (2) was replaced with a resin sheet (36).

<Evaluation of transparency>
The haze of the measurement sample (35) and the measurement sample (36) was measured by the same method as that described in the section <Evaluation of transparency> in Example 1.

The haze of the measurement sample (35) was 3.0%, and the haze of the measurement sample (36) was 1.5%.
<Evaluation of heat resistance>
Spectroscopy of the measurement sample (35) and the measurement sample (36) was measured by the same method as described in the section <Evaluation of heat resistance> in Example 1.

YI of the measurement sample (35) was 2.7, and YI of the measurement sample (36) was 4.2. ΔYI of the measurement sample (35) and the measurement sample (36) was 1.5.
<Evaluation of light resistance>
YI and Tvis were determined in the same manner as in the section <Evaluation of light resistance> in Example 1 except that the measurement sample (2) was replaced with the measurement sample (36).

YI after 400 hours was 15.8, and ΔYI was 11.6 (15.8-4.2), where ΔYI was the difference from YI before the light resistance test.
The Tvis after 400 hours was 45.3%, and the Tvis of the measurement sample (36) before the light resistance test was 88.3%. Therefore, assuming that the difference in Tvis before and after the test is ΔTvis, ΔTvis is 43 0.0%.

Claims

A resin composition comprising a near infrared absorber, a phosphoric acid triester, and a resin;
The near-infrared absorber is fine particles composed of a phosphonic acid copper salt represented by the following general formula (1):
The phosphoric acid triester is a phosphoric acid triester represented by the following general formula (2).

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

[In the general formula (2), each R is independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 35 carbon atoms, a phenyl group, or a phenyl group having a substituent, The number is 15 or less. ]
The resin composition according to claim 1, wherein, in the general formula (2), each R is independently a phenyl group having a substituent.
The resin composition according to claim 1 or 2, wherein the resin composition further contains a phosphorus-based antioxidant.
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 any one of claims 1 to 3, which is a resin.
The resin composition according to any one of claims 1 to 3, wherein the resin is a polyvinyl butyral resin or an ethylene-vinyl acetate copolymer.
The resin composition according to any one of claims 1 to 5, comprising 0.05 to 50 parts by mass of a near infrared absorber per 100 parts by mass of the resin.
The resin composition according to any one of claims 1 to 6, which contains 0.05 to 5.0 parts by mass of a phosphoric acid triester per 100 parts by mass of the resin.
The resin composition according to claim 3, comprising 0.05 to 5.0 parts by mass of a phosphorus-based antioxidant per 100 parts by mass of the resin.
An interlayer film for laminated glass formed from the resin composition according to any one of claims 1 to 8.
Laminated glass having the interlayer film for laminated glass according to claim 9.