WO2012077674A1

WO2012077674A1 - Resin composition and uses thereof

Info

Publication number: WO2012077674A1
Application number: PCT/JP2011/078172
Authority: WO
Inventors: 留美佐野; 町田　克一; 岳志島; 彩竹内
Original assignee: 株式会社クレハ
Priority date: 2010-12-07
Filing date: 2011-12-06
Publication date: 2012-06-14
Also published as: JPWO2012077674A1

Abstract

The purpose of the invention is to provide a resin composition of superior near infrared absorption capability obtained from a near infrared absorber and an ionomer resin, and uses of said composition. This resin composition, which is obtained from a near infrared absorber and an ionomer resin, is characterized in that the near infrared absorber is a powder wherein microparticles obtained from a copper phosphonate represented by formula (1) is coated with at least one compound selected from resins (A) and polysiloxanes (B).

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 and an ionomer 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.

In particular, ionomer resins have excellent strength and hardness compared to polyvinyl butyral resins, and are excellent in durability, transparency, and adhesiveness, and therefore can be suitably used as an intermediate film for structural materials such as laminated glass. is there.

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. Patent Document 1 discloses a polyvinyl acetal resin, an ethylene-vinyl acetate copolymer (EVA), a (meth) acrylic resin, a polyester resin, a polyurethane resin, a vinyl chloride resin, and a polyolefin as a resin mixed with a copper salt composition. Resins, polycarbonate resins, norbornene resins and the like are disclosed.

However, it has not yet been sufficiently studied to impart a near-infrared absorbing ability to an ionomer resin that can be suitably used as an interlayer film for laminated glass.

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 having a near-infrared absorbing ability, comprising a near-infrared absorber and an ionomer resin, and a use of the composition. To do.

The inventors of the present invention have intensively studied in order to achieve the above-mentioned problems. In the research, the present inventors have found that when an ionomer resin and a copper salt which is a conventional near infrared absorber are mixed, the resulting resin composition is colored and inferior in near infrared absorption ability. The inventors speculated that this cause is due to ion exchange between the metal ion contained in the ionomer resin and the copper ion contained in the near-infrared absorber.

The present inventors have further researched, and as a near-infrared absorber, by using a powder in which a specific copper salt is coated with at least one selected from a resin and a polysiloxane, a resin excellent in near-infrared absorption ability We have found that it is possible to provide a composition and have completed the present invention.

That is, the resin composition of the present invention is a resin composition comprising a near-infrared absorber and an ionomer resin, and the near-infrared absorber comprises fine particles comprising a phosphonic acid copper salt represented by the following general formula (1). It is a powder coated with at least one selected from resin (A) and polysiloxane (B).

[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 aspect A of the resin composition of the present invention, at least one selected from the resin (A) and the polysiloxane (B) is the resin (A).

It is preferable that the resin (A) is formed using a crosslinking agent as at least a part of the monomer. More preferably, the cross-linking agent is at least one cross-linking agent selected from a polyfunctional aromatic vinyl compound and a polyfunctional (meth) acrylic acid ester.

It is preferable that the resin (A) is formed using a monofunctional monomer as at least a part of the monomer.

In Embodiment B of the resin composition of the present invention, at least one selected from the resin (A) and the polysiloxane (B) is polysiloxane (B).

The polysiloxane (B) is preferably formed from at least one silicon-based compound selected from alkoxysilanes, hydrolysates of alkoxysilanes, and condensates thereof.

It is preferable that the ionomer resin is an ionomer of an ethylene / unsaturated carboxylic acid copolymer.

It is preferable to contain 0.05 to 30 parts by mass of a near-infrared absorber per 100 parts by mass of the ionomer resin.

In the aspect A, the near-infrared absorber is obtained by dispersing fine particles of a phosphonic acid copper salt represented by the general formula (1) in a monomer to obtain a copper salt-containing monomer, and bulk-polymerizing the copper salt-containing monomer. It is preferable to obtain the polymer and pulverize the polymer. It is preferable that the monomer is 0.01 to 20 parts by mass with respect to 1 part by mass of the fine particles made of phosphonic acid copper salt.

In the embodiment B, the near-infrared absorber is at least one selected from fine particles comprising a copper phosphonate represented by the general formula (1), alkoxysilane, a hydrolyzate of alkoxysilane, and a condensate thereof. It is preferably obtained by mixing a seed silicon compound, obtaining polysiloxane (B) from the silicon compound, and pulverizing the reaction product. It is preferable that the silicon-based compound is 0.3 to 20 parts by mass in terms of SiO _{2 with} respect to 1 part by mass of copper in fine particles made of a phosphonic acid copper salt.

In other words, the resin composition of the aspect B is a resin composition comprising a near-infrared absorber and an ionomer resin, and the near-infrared absorber is a fine particle comprising a phosphonic acid copper salt represented by the following general formula (1) And at least one silicon-based compound selected from alkoxysilane, a hydrolyzate of alkoxysilane, and a condensate thereof, to obtain polysiloxane (B) from the silicon-based compound, It is a powdery near-infrared absorber obtained by pulverization.

[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. ]
The resin film of the present invention and the interlayer film for laminated glass are 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 comprises a near infrared absorber and an ionomer resin, and is excellent in near infrared absorption ability. Moreover, the resin film formed from this resin composition can be suitably used as an interlayer film for laminated glass.

The TEM photograph of the resin-coated copper salt powder (2) of Example A2 is shown. The spectral transmittance of the sheet | seat formed from the resin composition of the comparative example 1 is shown. The spectral transmittance of the sheet | seat formed from the resin composition of Example A1 is shown. The spectral transmittance of the sheet | seat formed from the resin composition of Example A2 is shown. The spectral transmittance of the sheet | seat formed from the resin composition of Example A3 is shown. The spectral transmittance of the sheet | seat formed from the resin composition of Example A4 is shown. The spectral transmittance of the sheet | seat formed from the resin composition of the comparative example 1 and Example B1 is shown. The spectral transmittance of the sheet | seat formed from the resin composition of the comparative example 1 and Example B2 is shown. The spectral transmittance of the sheet | seat formed from the resin composition of the comparative example 1 and Example B3 is shown. The spectral transmittance of the sheet | seat formed from the resin composition of the comparative example 1 and Example B4 is shown.

Next, the present invention will be specifically described.

The resin composition of the present invention is a resin composition comprising a near-infrared absorber and an ionomer resin, and the near-infrared absorber is a resin comprising fine particles comprising a phosphonic acid copper salt represented by the general formula (1) described later. It is a powder coated with at least one selected from (A) and polysiloxane (B).

The phosphonic acid copper salt represented by the general formula (1) is also referred to as a specific phosphonic acid copper salt.

The near-infrared absorber may be a powder in which fine particles made of the specific copper phosphonate salt are coated with the resin (A) and the polysiloxane (B), but preferably the resin (A) or the polysiloxane (B). It is a coated powder.

In the resin composition of the present invention, an embodiment in which a powder in which fine particles composed of the specific phosphonic acid copper salt are coated with the resin (A) is used as the near infrared absorber is also referred to as an embodiment A. Further, in the resin composition of the present invention, an embodiment in which a powder in which fine particles made of the specific copper phosphonate salt are coated with polysiloxane (B) is used as the near infrared absorber is also referred to as an embodiment B.

[Near-infrared absorber]
The near-infrared absorber used in the present invention is a powder in which fine particles comprising a phosphonic acid copper salt represented by the following general formula (1) are coated with at least one selected from a resin (A) and a polysiloxane (B) It is.

Examples of the near-infrared absorber include a powder in which fine particles composed of a phosphonic acid copper salt represented by the following general formula (1) are coated with a resin (A), or a phosphonic acid copper salt represented by the following general formula (1). A powder in which the fine particles are coated with polysiloxane (B) is preferable.

The fine particles comprising the phosphonic acid copper salt represented by the following general formula (1) constituting the near infrared absorber may be formed only from the phosphonic acid copper salt represented by the following general formula (1), You may form from the phosphonic acid copper salt represented by following General formula (1), and another component.

[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”.

In addition, when the copper salt containing a fluorine atom is used as the said phosphonic acid copper salt, there exists a tendency for the dispersibility of the microparticles | fine-particles which consist of a phosphonic acid copper salt with respect to resin (A) to improve. For this reason, for example, when a group having a fluorine atom is used as R ¹¹ of the phosphonic acid copper salt, uneven distribution occurs even when a dispersant described later is not used or when the amount of the dispersant used is small. The fine particles comprising the phosphonic acid copper salt can be dispersed in the resin (A) without any problem.

The method for producing fine particles comprising a phosphonic acid copper salt used in the present invention is not particularly limited, and for example, it can be produced by the following method.

As a method for producing fine particles comprising a phosphonic acid copper salt, a phosphonic acid compound represented by the following general formula (2) and a copper salt are preferably mixed in a solvent in a solvent to obtain a reaction mixture. Examples thereof include a method having a step (hereinafter also referred to as a reaction step) and a step of obtaining fine particles composed of a phosphonic acid copper salt by removing a solvent in the reaction mixture (hereinafter also referred to as a solvent removal step).

[In General Formula (2), 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 (2), those in which R ¹¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms are preferred. Examples of the phosphonic acid compound represented by the general formula (2) 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 (2), 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 from the viewpoint of solubility and removal of by-products.

When producing fine particles comprising a phosphonic acid copper salt, a dispersant is preferably used. It is preferable to use a dispersant because the dispersibility of the phosphonic acid copper salt represented by the general formula (1) is improved. 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. Examples of the base used for neutralization include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, and calcium hydroxide.

[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 ⁵ , and n is 4 to 35 R ⁵ is an integer, and R ⁵ represents an alkyl group having 6 to 25 carbon atoms or an alkylphenyl group having 6 to 25 carbon atoms. However, R ²¹ , R ²² and R ²³ may be the same or different. ]
When the near-infrared absorber used in the present invention is a powder in which fine particles made of the specific copper phosphonate salt are coated with the resin (A), the n is preferably 4 to 25, More preferably, it is 6-15.

Further, when the near-infrared absorber used in the present invention is a powder in which the fine particles comprising the specific copper phosphonate salt are coated with polysiloxane (B), the n is preferably 6 to 25. .

When n is less than 4, transparency may be insufficient when a laminated glass or the like is produced. Moreover, when n exceeds the said range, the quantity of a phosphoric acid ester compound required in order to obtain the laminated glass etc. which have sufficient transparency will increase, and there exists a tendency which becomes a cause of high cost.

R ⁵ is an alkyl group having 6 to 25 carbon atoms or an alkylphenyl group having 6 to 25 carbon atoms, preferably an alkyl group having 6 to 25 carbon atoms, and preferably an alkyl group having 12 to 20 carbon atoms. Is more preferable. When R ⁵ is a group having less than 6 carbon atoms, transparency may be insufficient when a laminated glass or the like is produced. Further, if R ⁵ is a group having more than 25 carbon atoms, the amount of the phosphoric acid ester compound required to obtain a laminated glass having sufficient transparency tends to increase, leading to high costs. .

When obtaining fine particles comprising the phosphonic acid copper salt, at least one of the phosphoric acid ester compound represented by the general formula (3a) and the phosphoric acid ester compound represented by the general formula (3b) is used. However, it is more preferable to use both the phosphoric acid ester compound represented by the general formula (3a) and the phosphoric acid 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-8, DLP-10, DDP-8, DDP-10, TDP-8, TDP-10 (above, manufactured by Nikko Chemicals), Prisurf A219B, Prisurf A210B (above, No. 1) Ichikogaku Kagaku Co., Ltd.) 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 lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide and the like.

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 (2) per 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, it is preferably used in an amount of 0.02 to 0.40 mol per mol of the copper salt.

Examples of the solvent include alcohols such as methanol and ethanol, tetrahydrofuran (THF), dimethylformamide (DMF), water and the like, and ethanol, THF or DMF is preferable from the viewpoint of satisfactory reaction. The reaction step is preferably carried out at room temperature to 60 ° C., more preferably 20 to 40 ° C., preferably for 0.5 to 50 hours, more preferably for 1 to 30 hours.

In the reaction step, the phosphonic acid compound represented by the general formula (2) 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 (2) 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.

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

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.

The near-infrared absorber used in the present invention is a powder in which the fine particles comprising the phosphonic acid copper salt are coated with at least one selected from the resin (A) and the polysiloxane (B) as described above. The near-infrared absorber is preferably a powder in which the fine particles comprising the phosphonic acid copper salt are coated with the resin (A) or the polysiloxane (B) as described above.

As the fine particles comprising the phosphonic acid copper salt constituting the near-infrared absorber used in the present invention, fine particles comprising a phosphonic acid copper salt 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.

First, the case where the near-infrared absorber is a powder in which fine particles made of the copper phosphonate are coated with the resin (A) will be described.

The resin (A) constituting the near-infrared absorber is not particularly limited as long as it is a resin that can disperse the fine particles of the phosphonic acid copper salt and can be dispersed with respect to the ionomer resin. Absent.

The resin (A) is preferably formed using a crosslinking agent as at least a part of the monomer from the viewpoint of heat resistance when kneaded with the ionomer resin.

A cross-linking agent is a compound having at least two functional groups capable of radical polymerization in one molecule, and examples thereof include polyfunctional aromatic vinyl compounds and polyfunctional (meth) acrylic esters. It may be used or two or more kinds may be used.

In the present invention, “(meth) acrylic acid” means “methacrylic acid” and “acrylic acid”.

Examples of the polyfunctional aromatic vinyl compound include divinylbenzene, diisopropenylbenzene, and trivinylbenzene.

Examples of the polyfunctional (meth) acrylic acid ester include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 2,2-bis (4-methacryloxyethoxyphenyl) propane, tricyclodecane dimethanol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate .

As the crosslinking agent, ethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate and the like are preferable.

The resin (A) is preferably formed using a monofunctional monomer as at least a part of the monomer from the viewpoint of moldability. Examples of the monofunctional monomer include a monofunctional aromatic vinyl compound. , Monofunctional (meth) acrylic acid esters, and α-olefins. These may be used alone or in combination of two or more.

Examples of the monofunctional aromatic vinyl compound include styrene, α-methylstyrene, ethylstyrene, tert-butylstyrene, chlorostyrene, dibromostyrene, methoxystyrene, vinylbenzoic acid, and hydroxymethylstyrene.

Examples of the monofunctional (meth) acrylic acid ester include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate. 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isodecyl acrylate, isodecyl methacrylate, n-lauryl acrylate, n-lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate, n-stearyl acrylate, n-stearyl methacrylate, isobornyl Acrylate, isobornyl methacrylate, benzyl acrylate, benzyl meta Relate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate. As the monofunctional (meth) acrylic acid ester, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and the like are preferable.

As the α-olefin, an α-olefin having 4 to 18 carbon atoms is usually used, and examples thereof include 1-butene, 1-propene, 1-hexene, 1-octene and 1-decene.

The resin (A) is usually preferably formed using a crosslinking agent and a monofunctional (meth) acrylate as monomers, from the viewpoint of obtaining the effect of suppressing ion exchange.

The crosslinking agent is preferably used in an amount of 1 part by mass or more and the monofunctional monomer of 99 parts by mass or less per 100 parts by mass of the monomer used for producing the resin (A), and the crosslinking agent is used in an amount of 5 to 99 parts by mass. It is more preferable to use 1 to 95 parts by mass of the functional monomer, and it is particularly preferable to use 10 to 90 parts by mass of the crosslinking agent and 10 to 90 parts by mass of the monofunctional monomer.

When the resin composition of the present invention is the embodiment A, the near-infrared absorber is a powder in which the fine particles comprising the phosphonic acid copper salt are coated with the resin (A) as described above, and The production method is not particularly limited. For example, the monomer is polymerized in the presence of the fine particles composed of the aforementioned phosphonic acid copper salt to obtain a polymer composed of the fine particles composed of the phosphonic acid copper salt and the resin (A). If necessary, the near-infrared absorber can be obtained by pulverizing the polymer.

The polymerization method of the monomer is not particularly limited, and the polymerization is performed by a polymerization method such as bulk polymerization, suspension polymerization, emulsion polymerization or the like. Among these, bulk polymerization that allows easy polymerization is preferable. In addition, since the polymer obtained by bulk polymerization is obtained in the form of a bulk (lumb), the near-infrared absorber used for this invention is obtained by grind | pulverizing this polymer.

As a specific example of the method for producing a near-infrared absorber used in the present invention, fine particles comprising a phosphonic acid copper salt represented by the general formula (1) are dispersed in a monomer to obtain a copper salt-containing monomer, The copper salt-containing monomer is bulk polymerized to obtain a polymer, and the polymer is pulverized to obtain a near-infrared absorber, that is, fine particles composed of a phosphonic acid copper salt represented by the general formula (1) are resin ( A method for obtaining the powder coated with A) is mentioned.

As a method for obtaining the copper salt-containing monomer, fine particles composed of copper phosphonate are dispersed in a dispersion medium to obtain a dispersion, and after adding the monomer to the dispersion, the dispersion medium is removed to remove the copper salt. The method of obtaining a containing monomer is mentioned.

As the dispersion medium, those capable of dispersing fine particles made of the phosphonic acid copper salt are used, and usually low-boiling organic substances are used. For example, methylene chloride, acetone, methanol, chloroform and the like are used.

As a method of dispersing the fine particles composed of the phosphonic acid copper salt in a dispersion medium, for example, the dispersion medium is added to the fine particles composed of the phosphonic acid copper salt, and by a method such as ultrasonic irradiation, homogenizer, stirring, heating and stirring, Examples thereof include a method of dispersing fine particles comprising the phosphonic acid copper salt in a dispersion medium.

Next, the monomer is preferably dissolved by adding the aforementioned monomer to the dispersion. Next, by removing the dispersion medium, it is possible to obtain a copper salt-containing monomer in which fine particles composed of the phosphonic acid copper salt are dispersed.

The method for removing the dispersion medium is not particularly limited, and examples thereof include removal of the dispersion medium by reduced pressure and removal by a combination of heating and reduced pressure.

In addition, when adding a monomer to a dispersion liquid, after adding a part of monomer to a dispersion liquid and removing a dispersion medium, the remaining monomer may be further added and mixed.

In this way, a copper salt-containing monomer in which fine particles made of copper phosphonate are dispersed in the monomer can be obtained. In addition, as a ratio of the usage-amount of the microparticles | fine-particles which consist of phosphonic acid copper salt, and a monomer, in the resin composition of this invention, the metal ion which ionomer resin has, and the copper ion contained in a near-infrared absorber From the viewpoint of sufficiently suppressing ion exchange, the monomer is preferably used in an amount of 0.01 to 20 parts by mass, and more preferably 0.1 to 15 parts by mass with respect to 1 part by mass of the fine particles made of copper phosphonate. If the amount of the monomer is less than 0.01 parts by weight, it may not be possible to coat the fine particles made of phosphonic acid copper salt, ion exchange may not be sufficiently suppressed, and if the amount of monomer is more than 20 parts by weight, When a near infrared absorber is introduced into the ionomer resin, the physical properties such as strength of the ionomer resin may be greatly changed.

In addition, when manufacturing a near-infrared absorber, the method of carrying out bulk polymerization of a copper salt containing monomer as mentioned above is mentioned, but in bulk polymerization, in order to polymerize a monomer suitably, it is usually a radical polymerization initiator. Is preferably added at the same time as or after the monomer is added to the dispersion to obtain a copper salt-containing monomer containing a radical polymerization initiator.

The radical polymerization initiator is not particularly limited, and for example, an organic peroxide polymerization initiator or an azo radical polymerization initiator can be used. Examples of the organic peroxide polymerization initiator include tert-butyl peroctanoate, tert-butyl peroxyneodecanate, tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, Use of non-aromatic peroxyesters such as tert-butylperoxylaurate, diacyl peroxides such as lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, etc. It is preferable in that it is less colored. As the azo radical polymerization initiator, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) 1,1′-azobis (cyclohexane-2-carbonitrile) ) Etc. can be used. The radical polymerization initiator is used in an amount of 0.3 to 5.0 parts by mass with respect to 100 parts by mass of the monomer.

When bulk polymerization of the copper salt-containing monomer is performed to obtain a polymer, for example, the copper salt-containing monomer is injected into a mold, a test tube, or the like, and the polymerization temperature is usually 20 to 200 ° C. and the polymerization time is 1 to 40 hours. Polymerization takes place at

The near-infrared absorber used in the present invention can be obtained by pulverizing the polymer obtained by the bulk polymerization. A method for pulverizing the polymer is not particularly limited, and for example, a sand mill, a jet mill, a ball mill, an attritor, a vibration mill or the like can be used.

The near-infrared absorber used in the present invention can be produced, for example, by the above-described method, and is a powder in which fine particles comprising a phosphonic acid copper salt represented by the general formula (1) are coated with a resin (A) It is. The average particle size of the obtained near-infrared absorber is preferably 0.05 to 100 μm, more preferably 0.05 to 50 μm. Within the said range, since the resin composition of this invention is excellent in transparency, it is preferable.

In the present invention, the fine particles made of copper phosphonate are covered with the resin (A) means that at least a part of the surface of the fine particles made of copper phosphonate is covered with the resin (A). As a near-infrared absorber, it is preferable that the entire surface of fine particles made of phosphonic acid copper salt is covered with the resin (A).

Next, the case where the near-infrared absorber is a powder in which fine particles made of the copper phosphonate are coated with polysiloxane (B) will be described.

The polysiloxane (B) constituting the near-infrared absorber is not particularly limited as long as it can coat fine particles made of the phosphonic acid copper salt and can be dispersed in the ionomer resin.

The polysiloxane (B) is preferably formed from at least one silicon-based compound selected from alkoxysilane, a hydrolyzate of alkoxysilane, and a condensate thereof.

The alkoxysilane may be used alone or in combination of two or more. Alkoxysilane generally has a structure in which an alkoxy group is bonded to a silicon atom, but as an alkoxysilane, a quaternary alkoxysilane in which four alkoxy groups are bonded to a silicon atom, or a tertiary in which three alkoxy groups are bonded. Any of these alkoxysilanes and secondary alkoxysilanes in which two alkoxy groups are bonded may be used. Further, primary alkoxysilane bonded with one alkoxy group may be used as a part of alkoxysilane.

Specific examples of the alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, octyltriethoxysilane. , Phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, 2-cyanoethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycid Xylpropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-acryloylio Examples include xylpropyltrimethoxysilane, γ-acryloyloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane. As the alkoxysilane, tetramethoxysilane or the like is preferable.

Generally, alkoxysilane easily undergoes hydrolysis / condensation reaction in the presence of acid or alkali. Further, when the hydrolyzate of alkoxysilane or alkoxysilane is heated, a condensation reaction occurs. As the silicon compound, alkoxysilane, a hydrolyzate of alkoxysilane, and a mixture of these condensates may be used.

In particular, it is preferable to use a condensate because it is easy to handle.

A commercially available product may be used as the condensate. Examples of commercially available products include methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48 (manufactured by Colcoat Co.), M silicate 51, silicate 40, silicate 45 (manufactured by Tama Chemical Industry Co., Ltd.), and the like. It is done.

When the resin composition of the present invention is the embodiment B, the near-infrared absorber is a powder in which the fine particles of the phosphonic acid copper salt are coated with the polysiloxane (B) as described above, and the production thereof The method is not particularly limited. For example, the polyphosphoric acid (B) can be obtained by hydrolyzing and condensing the silicon compound in the presence of fine particles comprising the above-described copper phosphonate. A near-infrared absorber can be obtained by obtaining a reaction product comprising the fine particles comprising polysiloxane (B) and pulverizing the reaction product.

The reaction conditions for the hydrolysis / condensation are usually 10 to 250 ° C., more preferably room temperature to 100 ° C. for implementation. In order to accelerate the reaction, a catalyst such as an acid or a base may be used. The drying is usually performed at 10 to 250 ° C., preferably 50 to 200 ° C.

The method of pulverizing the reaction product is not particularly limited, but the reaction product can be pulverized using an agate mortar, sand mill, jet mill, ball mill, attritor, vibration mill or the like.

As a ratio of the amount of the fine particles composed of the phosphonic acid copper salt and the silicon compound used for obtaining the near infrared absorber, the silicon compound is 1 part by mass of copper in the fine particles composed of the phosphonic acid copper salt. On the other hand, 0.3 to 20 parts by mass in terms of SiO ₂ is preferably used, and more preferably 0.5 to 15 parts by mass. If the amount of the silicon-based compound used is less than the above range, the coating is insufficient and may not be obtained as a solid and may not be suitable for implementation. If it exceeds the above range, it is necessary to obtain a workability reduction and an infrared absorption effect. The amount added may be unsuitable for implementation.

In addition, although it is possible to use compounds having various structures as the silicon compound, the mass part in terms of SiO ₂ is obtained. The amount of silicon atoms of the silicon compound is determined, and the silicon compound It is a mass part when it is assumed that it is a silicon dioxide which has a silicon atom.

The near-infrared absorber used in the present invention can be produced, for example, by the above-described method, and the fine particles comprising the phosphonic acid copper salt represented by the general formula (1) are coated with the polysiloxane (B). It is a powder. The average particle size of the obtained near infrared absorber is preferably 0.01 to 100 μm, more preferably 0.03 to 50 μm, and particularly preferably 0.05 to 1 μm. Within the said range, since the resin composition of this invention is excellent in transparency, it is preferable.

In the present invention, the fine particles made of phosphonic acid copper salt are covered with polysiloxane (B). At least a part of the surface of fine particles made of phosphonic acid copper salt is covered with polysiloxane (B). As a near-infrared absorber, it is preferable that the entire surface of fine particles made of phosphonic acid copper salt is covered with polysiloxane (B).

[Ionomer resin]
The ionomer resin used in the present invention is not particularly limited, and various ionomer resins can be used.

Examples of the ionomer resin include an ethylene ionomer, a styrene ionomer, a perfluorocarbon ionomer, a telechelic ionomer, a polyurethane ionomer, and the like, and a laminated glass was manufactured using an interlayer film formed from the resin composition of the present invention. In this case, it is preferable to use an ethylene ionomer that is excellent in strength, hardness, durability, transparency, and adhesiveness.

As the ethylene ionomer, an ionomer of an ethylene / unsaturated carboxylic acid copolymer is preferably used because of its excellent transparency and toughness.

The ethylene / unsaturated carboxylic acid copolymer is a copolymer having at least a structural unit derived from ethylene and a structural unit derived from unsaturated carboxylic acid, and may have a structural unit derived from another monomer.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid and the like. Acrylic acid and methacrylic acid are preferable, and methacrylic acid is particularly preferable.

Examples of the other monomers include acrylic acid esters, methacrylic acid esters, and 1-butene.

The ethylene / unsaturated carboxylic acid copolymer preferably has 75 to 99 mol% of structural units derived from ethylene, assuming that the total structural units of the copolymer are 100 mol%, and derived from unsaturated carboxylic acid. It is preferable to have 1 to 25 mol% of the structural unit.

The ionomer of the ethylene / unsaturated carboxylic acid copolymer is an ionomer resin obtained by neutralizing or crosslinking at least a part of the carboxyl group of the ethylene / unsaturated carboxylic acid copolymer with a metal ion, The neutralization degree of the carboxyl group is usually 1 to 90%, preferably 5 to 85%.

Examples of the ion source in the ionomer resin used in the present invention include alkali metals such as lithium, sodium, potassium, rubidium and cesium, and polyvalent metals such as magnesium, calcium and zinc, and sodium and zinc are preferable.

The production method of the ionomer resin used in the present invention is not particularly limited, and can be produced by a conventionally known production method.

For example, when an ionomer of an ethylene / unsaturated carboxylic acid copolymer is used as the ionomer resin, for example, ethylene and an unsaturated carboxylic acid are subjected to radical copolymerization at a high temperature and high pressure to obtain an ethylene / unsaturated carboxylic acid. An ionomer of an ethylene / unsaturated carboxylic acid copolymer can be produced by producing a copolymer and reacting the ethylene / unsaturated carboxylic acid copolymer with the metal compound containing the ion source. .

(Resin composition)
The resin composition of the present invention is a resin composition comprising the above-mentioned near infrared absorber and ionomer resin.

The resin composition of the present invention may be a composition comprising the above-mentioned near-infrared absorber and ionomer resin, but is usually produced by melt-kneading the above-mentioned near-infrared absorber and ionomer resin. . The melt kneading can be performed using a known kneader such as a plastograph, a single screw extruder, a twin screw extruder, a Banbury mixer, and the like. The melt-kneading is usually performed in the range of 100 to 230 ° C.

The resin composition of the present invention preferably contains 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass of the near infrared absorber per 100 parts by mass of the ionomer 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 30 parts by mass, the transparency and adhesiveness of the resin may be significantly reduced.

The resin composition of the present invention is excellent in near-infrared absorbing ability, and includes an ionomer resin as a resin. Therefore, the resin composition has excellent strength and hardness, and is excellent in durability and adhesiveness. Therefore, it is an intermediate film for structural materials such as laminated glass. Can be suitably used.

Moreover, various additives may be contained in the resin composition of the present invention. Examples of the additive include a dispersant, an antioxidant, an ultraviolet absorber, and a light stabilizer. These additives may be kneaded together with the near-infrared absorber and the ionomer resin when the above-mentioned melt-kneading is performed, or may be added when the near-infrared absorber is manufactured or the ionomer resin is manufactured. Good.

[Use of resin composition]
The resin composition of the present invention can be used in various applications in which an ionomer resin is used, but is usually used in applications where it is desired to absorb near infrared rays.

The resin film formed from the resin composition of the present invention has excellent near-infrared absorptivity, excellent strength and hardness, and excellent durability and adhesion. It can be suitably used as a film.

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.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

[Comparative Example 1]
(Synthesis of copper ethylphosphonate)
In a reaction vessel, 32.34 g of ethylphosphonic acid was dissolved in 500 ml of methanol, and 58.67 g of copper acetate monohydrate was added thereto, followed by heating under reflux for 4 hours to obtain a suspension.

The obtained suspension was filtered, and the residue was dried at 200 ° C. for 2 hours to obtain 49.79 g (yield 98%) of a pale blue powder (ethylphosphonic acid copper salt).

(Manufacture of resin composition)
0.69 g of the ethylphosphonic acid copper salt and 47.61 g of an ethylene-methacrylic acid copolymer Na salt (Himiran 1605, manufactured by Mitsui DuPont Polychemical Co., Ltd.) were supplied to a plastograph (manufactured by Brabender Co., Ltd.). The resin composition (c1) containing ethylphosphonic acid copper salt was obtained by melt-kneading for 15 minutes at a temperature of 30 ° C. and a screw speed of 30 rpm.

[Example A1]
(Synthesis of resin-coated copper salt)
In a reaction vessel, 3.49 g of copper acetate monohydrate and 135 g of ethanol were added and stirred to completely dissolve the copper acetate monohydrate. Thereto was added a solution prepared by dissolving 1.92 g of ethylphosphonic acid and 1.50 g of a phosphate ester dispersant (Pricesurf A219B, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in 15 g of ethanol, followed by stirring at room temperature for 4 hours. Reacted. After the reaction, by-products and the solvent were distilled off from the obtained reaction mixture with a rotary evaporator to obtain 4.44 g of a solid content containing ethylphosphonic acid copper salt.

100 g of methylene chloride was added to the obtained solid content, ultrasonic irradiation was performed, and the solid content was dispersed in methylene chloride to obtain a dispersion. The average particle size of the copper salt in the dispersion was 79 nm. The average particle size was measured using ELSZ-2 (manufactured by Otsuka Electronics Co., Ltd.).

Methylene chloride was extracted and removed by adding 4.50 g of methyl methacrylate (MMA) and 4.50 g of ethylene glycol dimethacrylate (EDMA) to the dispersion, and then reducing the pressure with a rotary evaporator. Subsequently, 0.09 g of tert-butyl peroxy-2-ethylhexanoate (Perbutyl O, manufactured by Nippon Oil & Fats Co., Ltd.) was added and mixed as a polymerization initiator to obtain a copper salt-containing monomer A1.

The copper salt-containing monomer A1 was poured into a test tube, heated in an oven at 50 ° C. for 8 hours, then heated to 70 ° C. over 4 hours, then heated to 110 ° C. over 2 hours and then 110 ° C. The polymerization was carried out by holding for 1 hour.

After completion of the polymerization, the oven temperature was lowered to 70 ° C. over 1.5 hours, and then removed from the oven to remove the reaction product in the test tube.

The reaction product taken out was annealed in an oven at 120 ° C. for 1 hour, and then pulverized for 6 minutes in a small pulverizer sample mill (SK-M2 type, manufactured by Kyoritsu Riko Co., Ltd.) to obtain a gray resin-coated copper salt powder ( 1) was obtained.

(Manufacture of resin composition)
2.15 g of resin-coated copper salt powder (1) and 46.15 g of ethylene-methacrylic acid copolymer Na salt (Himiran 1605, manufactured by Mitsui DuPont Polychemical Co., Ltd.) were supplied to a plastograph (manufactured by Brabender). The resin composition (1) containing resin-coated copper salt powder was obtained by melt-kneading for 15 minutes at 190 ° C. and a screw rotation speed of 30 rpm.

[Example A2]
(Synthesis of resin-coated copper salt)
To the reaction vessel, 1.05 g of copper acetate monohydrate and 54 g of ethanol were added and stirred to completely dissolve the copper acetate monohydrate. A solution prepared by dissolving 0.88 g of hexylphosphonic acid and 0.60 g of a phosphate ester dispersant (Pricesurf A219B, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in 6 g of ethanol was added thereto and stirred at room temperature for 7 hours. Reacted. After the reaction, by-products and the solvent were distilled off from the obtained reaction mixture with a rotary evaporator to obtain 1.81 g of a solid content containing hexylphosphonic acid copper salt.

100 g of methylene chloride was added to the obtained solid content, ultrasonic irradiation was performed, and the solid content was dispersed in methylene chloride to obtain a dispersion. The average particle size of the copper salt in the dispersion was 75 nm. The average particle size was measured using ELSZ-2 (manufactured by Otsuka Electronics Co., Ltd.).

Methylene chloride was extracted and removed by adding 6.02 g of methyl methacrylate (MMA) and 6.01 g of ethylene glycol dimethacrylate (EDMA) to the dispersion, and then reducing the pressure with a rotary evaporator. Next, 0.12 g of tert-butyl peroxy-2-ethylhexanoate (Perbutyl O, manufactured by NOF Corporation) was added and mixed as a polymerization initiator to obtain a copper salt-containing monomer A2.

Copper salt-containing monomer A2 was poured into a test tube, heated in an oven at 50 ° C. for 8 hours, then heated to 70 ° C. over 4 hours, then heated to 110 ° C. over 2 hours, and then 110 ° C. The polymerization was carried out by holding for 1 hour.

The reaction product taken out was annealed in an oven at 120 ° C. for 1 hour, then pulverized for 8 minutes in a small pulverizer sample mill (SK-M2 type, manufactured by Kyoritsu Riko Co., Ltd.), and gray resin-coated copper salt powder ( 2) was obtained.

The resin-coated copper salt powder (2) was subjected to TEM observation by the following method.

Resin-coated copper salt powder (2) was dispersed in methanol to obtain a suspension. A small amount of the obtained suspension was dropped on a mesh (manufactured by Nissin EM Co., Ltd.) on which a microgrid was pasted, dried naturally, and then observed with a transmission electron microscope (JEOL JEM2000EX). The obtained TEM photograph is shown in FIG.

As a result of TEM observation, a 10 to 40 nm copper salt (black part) was observed inside the particles of the resin-coated copper salt powder (2), and it was confirmed that the copper salt was coated with the resin.

(Manufacture of resin composition)
5.00 g of resin-coated copper salt powder (2) and 43.30 g of ethylene-methacrylic acid copolymer Na salt (Himiran 1605, manufactured by Mitsui DuPont Polychemical Co., Ltd.) were supplied to a plastograph (manufactured by Brabender). The resin composition (2) containing resin-coated copper salt powder was obtained by melt-kneading for 15 minutes at 190 ° C. and a screw rotation speed of 30 rpm.

[Example A3]
(Manufacture of resin composition)
Resin-coated copper salt powder (1) 1.40 g similar to Example A1 and ethylene-methacrylic acid copolymer Zn salt (High Milan 1706, manufactured by Mitsui DuPont Polychemical Co., Ltd.) 46.91 g The resin composition (3) containing resin-coated copper salt powder was obtained by melt-kneading for 15 minutes at 190 ° C. and a screw speed of 30 rpm.

[Example A4]
(Synthesis of resin-coated copper salt)
In a reaction vessel, 13.96 g of copper acetate monohydrate and 800 g of ethanol were added and stirred to completely dissolve the copper acetate monohydrate. Thereto was added a solution prepared by dissolving 7.71 g of ethylphosphonic acid and 6.00 g of a phosphate ester dispersant (Pricesurf A219B, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in 15 g of ethanol, followed by stirring at room temperature for 4 hours. Reacted. After the reaction, by-products and the solvent were distilled off from the obtained reaction mixture with a rotary evaporator to obtain 18.28 g of a solid content containing ethylphosphonic acid copper salt.

503.67 g of methylene chloride was added to the obtained solid content, and ultrasonic irradiation was performed to disperse the solid content in methylene chloride to obtain 521.95 g of a dispersion. The average particle size of the copper salt in the dispersion was 85 nm. The average particle size was measured using ELSZ-2 (manufactured by Otsuka Electronics Co., Ltd.).

Methylene chloride was extracted and removed by adding 10.80 g of methyl methacrylate (MMA) and 1.20 g of ethylene glycol dimethacrylate (EDMA) to 52.24 g of the dispersion, and then reducing the pressure with a rotary evaporator. Next, 0.12 g of tert-butyl peroxy-2-ethylhexanoate (Perbutyl O, manufactured by NOF Corporation) was added and mixed as a polymerization initiator to obtain a copper salt-containing monomer A3.

Copper salt-containing monomer A3 was poured into a test tube, heated in an oven at 50 ° C. for 8 hours, then heated to 70 ° C. over 4 hours, then heated to 110 ° C. over 2 hours and then 110 ° C. The polymerization was carried out by holding for 1 hour.

The reaction product taken out was annealed in an oven at 120 ° C. for 1 hour, then pulverized for 5 minutes with a small pulverizer sample mill (SK-M2 type, manufactured by Kyoritsu Riko Co., Ltd.), and gray resin-coated copper salt powder ( 3) was obtained.

(Manufacture of resin composition)
Resin-coated copper salt powder (3) (5.00 g) and ethylene-methacrylic acid copolymer Na salt (Himiran 1605, Mitsui DuPont Polychemical Co., Ltd.) (43.30 g) were supplied to Plastograph (Brabender Co., Ltd.) The resin composition (4) containing resin-coated copper salt powder was obtained by melt-kneading for 15 minutes at 190 ° C. and a screw rotation speed of 30 rpm.

[Spectral characteristic evaluation]
The spectral transmittances of the resin compositions obtained in Example A and Comparative Example were measured by the following method.

The resin compositions obtained in Example A and Comparative Example were each heated for 1 minute by a press machine at 150 ° C. (“WF-50”, manufactured by Kondo Metal Industry Co., Ltd.), and then pressurized at a pressure of 15 MPa for 5 minutes. The sheet was heated and then cold pressed for 3 minutes with a cooling press (Toyo Seiki Seisakusho No.288) to produce a sheet having a thickness of 0.76 mm.

The spectral transmittance of the sheet was measured using a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.). The measurement results of the spectral transmittance are shown in FIGS. 2 shows the spectral transmittance of the sheet formed from the resin composition of Comparative Example 1, FIG. 3 shows the spectral transmittance of the sheet formed from the resin composition of Example A1, and FIG. FIG. 5 shows the spectral transmittance of the sheet formed from the resin composition of Example A2, FIG. 5 shows the spectral transmittance of the sheet formed from the resin composition of Example A3, and FIG. 6 shows the resin composition of Example A4. It is the spectral transmittance of the sheet formed from.

As is apparent from FIGS. 2 to 6, a sheet formed from a resin composition using a powder in which fine particles of a phosphonic acid copper salt are coated with a resin as a near-infrared absorber has a near-infrared region of 800 to 1200 nm. Have a wide absorption band. On the other hand, a sheet formed from a resin composition containing fine particles of phosphonic acid copper salt that is not coated with a resin has a weak absorption band in the vicinity of 600 to 1200 nm.

[Example B1]
(Synthesis of copper salt fine particles)
In a reaction vessel, 0.91 g of copper acetate monohydrate (in terms of copper, 0.29 g) was dissolved in 50 g of ethanol. A solution prepared by dissolving 0.50 g of ethylphosphonic acid and 0.80 g of a dispersant (Plysurf A219B (Daiichi Kogyo Seiyaku Co., Ltd.)) in 30 g of ethanol was added thereto and stirred at room temperature for 2 hours. After removing volatile components with an evaporator, 50 g of toluene was added and subjected to ultrasonic waves to prepare a copper salt fine particle dispersion.

(Synthesis of polysiloxane-coated copper salt)
A solution obtained by dissolving 3.60 g of methyl silicate 53A (manufactured by Colcoat Co., Ltd.) (1.21 g in terms of SiO ₂ ) in 1.2 g of ethanol was added to the copper salt fine particle dispersion and stirred at room temperature. Opened and dried. This was dried by vacuum drying at 100 ° C. for 2 hours to a hardness suitable for the next pulverization step, and the polysiloxane-coated copper salt was recovered. The yield was 3.36 g.

(Manufacture of resin composition)
The polysiloxane-coated copper salt was ground in an agate mortar to obtain a powder in which the copper salt, which is a near infrared absorber, was coated with polysiloxane.

2.5 g of the powder and 45.8 g of ethylene-methacrylic acid copolymer Zn salt (Himiran 1705, manufactured by Mitsui DuPont Polychemical Co., Ltd.) were supplied to a plastograph (manufactured by Brabender Co., Ltd.), set temperature 170 ° C., screw rotation Melting and kneading was performed at several 30 rpm for 15 minutes to obtain a resin composition composed of a near infrared absorber and an ionomer resin.

[Example B2]
(Synthesis of polysiloxane-coated copper salt)
To a copper salt fine particle dispersion synthesized in the same manner as in Example B1, a solution obtained by dissolving 0.72 g (SiO ₂ equivalent, 0.38 g) of methyl silicate 53A (manufactured by Colcoat Co., Ltd.) in 0.24 g of ethanol was added. After stirring at room temperature, it was opened in a Teflon bat and dried. This was dried at 100 ° C. for 3 hours to a hardness suitable for the next pulverization step by vacuum drying, and the polysiloxane-coated copper salt was recovered. The yield was 1.89 g.

1.42 g of the powder and 47.0 g of ethylene-methacrylic acid copolymer Na salt (Himiran 1707, manufactured by Mitsui DuPont Polychemical Co., Ltd.) are supplied to a plastograph (manufactured by Brabender Co.), set temperature is 170 ° C., screw rotation Melting and kneading was performed at several 30 rpm for 15 minutes to obtain a resin composition composed of a near infrared absorber and an ionomer resin.

[Example B3]
(Synthesis of polysiloxane-coated copper salt)
The copper salt fine particle dispersion was prepared in a manner similar to Example B1, (manufactured by Colcoat Co.) methyl silicate 53A 3.60 g (SiO ₂ conversion, 1.91 g) and dimethyldimethoxysilane 0.60 g (SiO ₂ converted , 0.29 g) in ethanol 1.20 g was added, stirred at room temperature, then placed in a Teflon vat and dried. This was dried by vacuum drying at 100 ° C. for 6 hours to a hardness suitable for the next pulverization step, and the polysiloxane-coated copper salt was recovered. The yield was 3.25 g.

2.43 g of the powder and 53.2 g of ethylene-methacrylic acid copolymer Na salt (Himiran 1707, manufactured by Mitsui DuPont Polychemical Co., Ltd.) are supplied to a plastograph (manufactured by Brabender Co.), set temperature is 170 ° C., screw rotation Melting and kneading was performed at several 30 rpm for 15 minutes to obtain a resin composition composed of a near infrared absorber and an ionomer resin.

[Example B4]
(Synthesis of polysiloxane-coated copper salt)
To a copper salt fine particle dispersion synthesized in the same manner as in Example B1, 3.60 g of methyl silicate 53A (manufactured by Colcoat Co., Ltd.) (1.91 g in terms of SiO ₂ ) and 0.21 g of 2-cyanoethyltriethoxysilane ( A solution obtained by dissolving 1.20 g of ethanol in terms of SiO _{2 in} 1.20 g of ethanol was added, stirred at room temperature, then opened in a Teflon vat and dried. This was dried by vacuum drying at 100 ° C. for 6 hours to a hardness suitable for the next pulverization step, and the polysiloxane-coated copper salt was recovered. The yield was 3.15 g.

2.36 g of the powder and 53.3 g of an ethylene-methacrylic acid copolymer Na salt (Himiran 1707, manufactured by Mitsui DuPont Polychemical Co., Ltd.) are supplied to a plastograph (manufactured by Brabender Co.), a set temperature of 170 ° C., screw rotation Melting and kneading was performed at several 30 rpm for 15 minutes to obtain a resin composition composed of a near infrared absorber and an ionomer resin.

[Spectral characteristic evaluation]
The spectral transmittances of the resin compositions obtained in Example B and Comparative Example were measured by the following method.

Each of the resin compositions obtained in Example B and Comparative Example was preheated at a pressure of 3 MPa for 1 minute by a press machine (“WF-50” manufactured by Shindo Metal Industry Co., Ltd.) at 150 ° C., and then 5 at a pressure of 10 MPa. The sheet was pressurized and heated for 3 minutes, and then cold-pressed for 3 minutes with a cooling press (Toyo Seiki Seisakusho No. 288) to produce a sheet having a thickness of 0.76 mm.

The spectral transmittance of the sheet was measured using a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.). The measurement results of the spectral transmittance are shown in FIGS. 7 shows the spectral transmittance of the sheet formed from the resin composition of Comparative Example 1 and Example B1, and FIG. 8 shows the spectral transmission of the sheet formed from the resin composition of Comparative Example 1 and Example B2. 9 is the spectral transmittance of the sheet formed from the resin composition of Comparative Example 1 and Example B3, and FIG. 10 is the sheet of the sheet formed from the resin composition of Comparative Example 1 and Example B4. Spectral transmittance.

As is apparent from FIGS. 7 to 10, a sheet formed from a resin composition using a powder in which fine particles of a phosphonic acid copper salt are coated with polysiloxane as a near infrared absorber has a near infrared wavelength of 800 to 1200 nm. It has a broad absorption band in the region (Examples B1 to B4). On the other hand, a sheet formed from a resin composition containing fine particles of phosphonic acid copper salt not coated with polysiloxane has only a weak absorption band in the vicinity of 600 to 1200 nm (Comparative Example 1).

That is, the sheet formed from the resin composition of the present invention is excellent in infrared absorption ability, whereas the sheet formed from a resin composition containing fine particles of phosphonic acid copper salt not coated with resin or polysiloxane. Is inferior in near infrared absorption ability.

Claims

A resin composition comprising a near-infrared absorber and an ionomer resin;
The near-infrared absorber is a powder in which fine particles comprising a phosphonic acid copper salt represented by the following general formula (1) are coated with at least one selected from a resin (A) and a polysiloxane (B). A resin composition characterized.

[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. ]
The resin composition according to claim 1, wherein at least one selected from the resin (A) and the polysiloxane (B) is a resin (A).
The resin composition according to claim 1 or 2, wherein the resin (A) is formed using a crosslinking agent as at least a part of the monomer.
The resin composition according to claim 3, wherein the cross-linking agent is at least one cross-linking agent selected from a polyfunctional aromatic vinyl compound and a polyfunctional (meth) acrylic acid ester.
The resin composition according to any one of claims 1 to 4, wherein the resin (A) is formed using a monofunctional monomer as at least a part of the monomer.
The resin composition according to claim 1, wherein at least one selected from the resin (A) and the polysiloxane (B) is a polysiloxane (B).
The resin composition according to claim 1 or 6, wherein the polysiloxane (B) is formed from at least one silicon-based compound selected from alkoxysilane, a hydrolyzate of alkoxysilane, and a condensate thereof.
The resin composition according to any one of claims 1 to 7, wherein the ionomer resin is an ionomer of an ethylene / unsaturated carboxylic acid copolymer.
The resin composition according to any one of claims 1 to 8, comprising 0.05 to 30 parts by mass of a near-infrared absorber per 100 parts by mass of the ionomer resin.
The near-infrared absorber is obtained by dispersing fine particles of a phosphonic acid copper salt represented by the general formula (1) in a monomer, obtaining a copper salt-containing monomer, bulk polymerizing the copper salt-containing monomer, 6. The resin composition according to claim 2, wherein the resin composition is obtained by pulverizing the polymer.
The resin composition according to claim 10, wherein the monomer is 0.01 to 20 parts by mass with respect to 1 part by mass of fine particles made of copper phosphonate.
The near-infrared absorber is at least one silicon type selected from fine particles comprising a copper phosphonate represented by the general formula (1), alkoxysilane, a hydrolyzate of alkoxysilane, and a condensate thereof. Mixing with the compound,
8. The resin composition according to claim 6, wherein the resin composition is obtained by obtaining polysiloxane (B) from the silicon-based compound and pulverizing the reaction product.
13. The resin composition according to claim 12, wherein the silicon-based compound is 0.3 to 20 parts by mass in terms of SiO 2 with respect to 1 part by mass of copper in fine particles made of a copper salt of phosphonic acid.
A resin composition comprising a near-infrared absorber and an ionomer resin;
The near-infrared absorber is at least one silicon type selected from fine particles comprising a phosphonic acid copper salt represented by the following general formula (1), alkoxysilane, a hydrolyzate of alkoxysilane, and a condensate thereof. Mixing with the compound,
A resin composition, which is a powdered near-infrared absorber obtained by obtaining polysiloxane (B) from the silicon-based compound and pulverizing the reaction product.

[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. ]
A resin film formed from the resin composition according to any one of claims 1 to 14.
An interlayer film for laminated glass formed from the resin composition according to any one of claims 1 to 14.
Laminated glass having the interlayer film for laminated glass according to claim 16.