JPWO2012105150A1 - Resin composition and use thereof - Google Patents

Abstract

An object of the present invention is to provide a resin composition excellent in near-infrared absorptivity, comprising an ionomer resin and a copper phosphonate, which can be suitably used as an intermediate film for a structural material such as laminated glass. And The resin composition of the present invention contains a polyvalent metal ionomer resin of an ethylene / unsaturated carboxylic acid copolymer and a phosphonic acid copper salt represented by the general formula (1).

Description

  The present invention relates to a resin composition and use thereof, and more particularly to a resin composition containing a polyvalent metal ionomer resin and a phosphonic acid copper salt and use thereof.

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

  In particular, ionomer resins are superior in 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 in 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 fully studied to impart near-infrared absorbing ability to an ionomer resin that can be suitably used as an interlayer film for laminated glass.

2009-242650

  This invention is made | formed in view of the said prior art, and aims at providing the resin composition excellent in the near-infrared absorptivity containing an ionomer resin and a phosphonic acid copper salt.

  The inventors of the present invention have made extensive studies in order to achieve the above problems. In the research, the present inventors mixed an ionomer resin and a phosphonic acid copper salt which is a near-infrared absorber, and depending on the type of the ionomer resin, the obtained resin composition is colored and inferior in near-infrared absorbing ability. I found out. 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 by using a polyvalent metal ionomer resin as the ionomer resin, it is possible to provide a resin composition having excellent visible light transmittance and excellent near-infrared absorption ability. As a result, the present invention was completed.

  That is, the resin composition of the present invention comprises a polyvalent metal ionomer resin of an ethylene / unsaturated carboxylic acid copolymer and a phosphonic acid copper salt represented by the following general formula (1).

[In General Formula (1), R ¹ is a monovalent group represented by —CH ₂ CH ₂ —R ¹¹ , and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 carbon atom. Represents -20 fluorinated alkyl groups. ]
The polyvalent metal is preferably a divalent metal, and more preferably at least one divalent metal selected from zinc, magnesium and calcium.

  The resin composition of the present invention preferably contains 0.05 to 30 parts by mass of the copper phosphonate per 100 parts by mass of the polyvalent metal ionomer resin.

  The resin film and the interlayer film for laminated glass of the present invention are formed from the resin composition.

  The interlayer film for laminated glass of the present invention has a layer formed from the resin composition, and layers formed from other resin compositions on both sides of the layer, and is formed from the other resin composition. At least one of the layers is preferably an ultraviolet cut layer.

  The laminated glass of the present invention has the glass interlayer film.

  The resin composition of the present invention contains a specific polyvalent metal ionomer resin and a copper phosphonate, and is excellent in visible light transmittance and 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 spectral transmittance of the sheet | seat formed from the resin composition of Example 1 is shown. The spectral transmittance of the sheet | seat formed from the resin composition of Example 2 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 the comparative example 2 is shown.

  Next, the present invention will be specifically described.

  The resin composition of the present invention comprises a polyvalent metal ionomer resin of an ethylene / unsaturated carboxylic acid copolymer and a phosphonic acid copper salt represented by the general formula (1).

[Polyvalent metal ionomer resin]
As the polyvalent metal ionomer resin used in the present invention, a polyvalent metal ionomer resin of an ethylene / unsaturated carboxylic acid copolymer can be used.

  The resin composition of the present invention is made of an interlayer film formed from a resin composition obtained by using a polyvalent metal ionomer resin of an ethylene / unsaturated carboxylic acid copolymer among ionomer resins. When manufactured, it is excellent in strength, hardness, durability, transparency and adhesiveness.

  In the present specification, the polyvalent metal ionomer resin of the ethylene / unsaturated carboxylic acid copolymer is also simply referred to as a polyvalent metal ionomer resin. The polyvalent metal ionomer resin used in the present invention is an ionomer resin obtained by neutralizing at least part of the carboxyl group of the ethylene / unsaturated carboxylic acid copolymer with a divalent or higher metal ion.

  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.

  As said unsaturated carboxylic acid, acrylic acid, methacrylic acid, maleic acid, etc. are mentioned, Acrylic acid and methacrylic acid are preferable, and methacrylic acid is especially preferable.

  Examples of the other monomer include 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%, derived from unsaturated carboxylic acid. It is preferable to have 1-25 mol% of the structural unit.

  The polyvalent metal ionomer resin 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. However, the neutralization degree of the carboxyl group is usually 1 to 90%, preferably 5 to 85%.

  The ion source in the polyvalent metal ionomer resin used in the present invention may be a polyvalent metal, that is, a divalent or higher metal. The polyvalent metal is preferably a divalent metal, more preferably at least one divalent metal selected from zinc, magnesium and calcium, and at least one divalent metal selected from zinc and magnesium. Particularly preferred is zinc.

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

  For example, radical copolymerization of ethylene and an unsaturated carboxylic acid under high temperature and high pressure to produce an ethylene / unsaturated carboxylic acid copolymer, the ethylene / unsaturated carboxylic acid copolymer, and the ion source A polyvalent metal ionomer resin of an ethylene / unsaturated carboxylic acid copolymer can be produced by reacting with a metal compound containing.

  In addition, as the polyvalent metal ionomer resin used in the present invention, a commercially available product may be used. 1650 or the like.

[Phosphonic acid copper salt represented by general formula (1)]
The resin composition of the present invention contains a phosphonic acid copper salt represented by the following general formula (1).

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

When a copper salt containing a fluorine atom, that is, a phosphonic acid copper salt in which R ¹¹ is a fluorinated alkyl group having 1 to 20 carbon atoms is used as the phosphonic acid copper salt, the phosphonic acid relative to the polyvalent metal ionomer resin is used. There exists a tendency for the dispersibility of acid copper salt to improve.

In addition, when R ¹¹ is a fluorinated alkyl group having 1 to 20 carbon atoms, the refractive index of the phosphonic acid copper salt is higher than that when R ¹¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Can be lowered. By employing a copper phosphonate having a small difference in refractive index from the polyvalent metal ionomer resin, the transparency of the resin composition of the present invention can be further improved.

  Although there is no limitation in particular as a manufacturing method of the phosphonic acid copper salt used for this invention, For example, it can manufacture with the following method.

  As a method for producing the phosphonic acid copper salt, a phosphonic acid compound represented by the following general formula (2) and a copper salt are mixed in a solvent in the presence of a dispersant as required, and a reaction mixture is prepared. Examples of the method include a step of obtaining (hereinafter also referred to as a reaction step) and a step of obtaining a copper salt of phosphonic acid 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 preferable. 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. 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.

  In producing the phosphonic acid copper salt, a dispersant may be 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 (P-OH) 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 25 It is an integer and R ⁵ represents an alkyl group having 6 to 25 carbon atoms or an alkylphenyl group having 6 to 25 carbon atoms. However, R ²¹ , R ²² and R ²³ may be the same or different. ]
The n is more preferably an integer of 6 to 15. When n is less than 4, transparency may be insufficient when a laminated glass or the like is produced. On the other hand, when n exceeds 25, the amount of the phosphoric ester compound necessary for obtaining laminated glass having sufficient transparency tends to increase, resulting in high costs.

R ⁵ is an alkyl group having 6 to 25 carbon atoms or an alkylphenyl group having 6 to 25 carbon atoms, preferably an alkyl group having 6 to 25 carbon atoms, and is 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) 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 (manufactured by Nikko Chemicals Co., Ltd.), Prisurf A219B, Prisurf A210B (all 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.

  In addition, when manufacturing a phosphonic acid copper salt, it is preferable to use 0.5-1.5 mol of phosphonic acid compounds represented by the general formula (2) per mol of the copper salt. It is more preferable to use -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 When the phosphoric acid ester compound is a phosphoric acid 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 performed at room temperature to 60 ° C, more preferably 20 to 40 ° C, and preferably 0.5 to 50 hours, more preferably 1 to 30 hours.

  In the reaction step, the phosphonic acid compound represented by the general formula (2) reacts with the copper salt, and fine phosphonic acid copper salt that does not dissolve in the solvent is generated by the reaction. When 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) is used, the reaction is good. 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 addition, when manufacturing the said phosphonic acid copper salt, a phosphonic acid copper salt is normally obtained as microparticles | fine-particles by removing at least one part of the said solvent from the said 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, for example, a method of filtering the reaction mixture to obtain a solid content, and drying the solid content to obtain a copper phosphonate salt can be mentioned. As conditions for the drying, the temperature is usually room temperature to 230 ° C., preferably 60 to 200 ° C. The drying may be performed under normal pressure or under reduced pressure. When drying under reduced pressure, there is a case where heating may not be performed or a temperature during drying may be low. Moreover, as drying time, it is 0.5 to 3 hours normally.

  Moreover, as another method of a solvent removal process, the method of obtaining the phosphonic acid copper salt by removing at least one part of the said solvent by heating a reaction mixture is mentioned. 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, a step of removing the dispersion medium after the phosphonic acid copper salt is dispersed in the dispersion medium may be provided. .

  As the phosphonic acid copper salt used in the present invention, fine particles composed of a phosphonic acid copper salt having an average particle diameter of 1 to 1000 nm are usually used. If the average particle diameter is 1 to 1000 nm, a resin composition in which fine particles composed of a phosphonic acid copper salt are present unevenly can be obtained. As an average particle diameter, in order to ensure the transparency of a resin composition, it is more preferable that it is 5-300 nm.

(Resin composition)
The resin composition of the present invention may be a composition containing the above-described polyvalent metal ionomer resin and a phosphonic acid copper salt. Usually, the above-mentioned polyvalent metal ionomer resin and a phosphonic acid copper salt are included. Manufactured by melt-kneading. 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. Moreover, melt kneading is normally performed in the range of 100-230 degreeC.

  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 phosphonic acid copper salt per 100 parts by mass of the polyvalent metal 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 visible light transmittance and near-infrared absorbing ability, and since it contains a polyvalent metal ionomer resin as a resin, it is excellent in both strength and hardness, and in durability, transparency and adhesiveness. Since it is excellent, it can be suitably used as an intermediate film for structural materials such as laminated glass.

  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 polyvalent metal ionomer resin and the phosphonic acid copper salt when the above-mentioned melt-kneading is performed. When producing the phosphonic acid copper salt, the polyvalent metal ionomer resin is produced. It may be added at the time.

[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 is excellent in visible light transmittance and near-infrared absorptivity, excellent in strength and hardness, and excellent in durability, transparency, and adhesiveness. It can be suitably used as an intermediate film for a structural material such as an intermediate film.

  The resin film of the present invention may be formed only from the resin composition of the present invention, or may be a laminate having a layer formed from the resin composition of the present invention and other layers.

  For example, the interlayer film for laminated glass may be a resin film formed only from the resin composition of the present invention. For example, another resin is formed on both sides of the layer formed from the resin composition of the present invention. An interlayer film for laminated glass having a layer formed from the composition may be used. When providing the layer formed from the said other resin composition, it is preferable that at least one layer of this layer is an ultraviolet-ray cut layer. Moreover, it is more preferable to provide an ultraviolet cut layer on both sides of the layer formed from the resin composition of the present invention. In addition, when providing a layer formed from another resin composition on both sides of a layer formed from the resin composition of the present invention, one layer is provided on each side of the layer formed from the resin composition of the present invention. The above layers may be provided.

  When the interlayer film for laminated glass is an interlayer film for laminated glass having a three-layer structure, the layer structure is preferably UV cut layer / layer formed from the resin composition of the present invention / UV cut layer.

  It is preferable to provide an ultraviolet cut layer because the visible light transmittance of the laminated glass tends to be maintained over a long period of time. Moreover, when not providing an ultraviolet cut layer, the effect similar to the case where an ultraviolet cut layer is provided can be acquired by adding a ultraviolet absorber to the resin composition of this invention.

  Although there is no limitation in particular as resin which comprises the layer formed from the said other resin composition, ionomer resin from a viewpoint of adhesiveness with the layer formed from the resin composition of this invention, or adhesiveness with glass Is preferred. The metal contained in the ionomer resin used in this case may be a polyvalent metal or a monovalent metal such as Na, Li, or K. By incorporating various additives into the other resin composition, desired physical properties can be imparted to a layer formed from the other resin composition. When the layer formed from the other resin composition is an ultraviolet cut layer, a composition containing an ultraviolet absorber is usually used as the other resin composition.

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

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

[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 light blue powder (copper ethylphosphonate).

(Manufacture of resin composition)
2 parts by weight of the ethylphosphonic acid copper salt and a Zn salt of an ethylene-methacrylic acid copolymer (29% of the carboxyl groups contained in the ethylene-methacrylic acid copolymer having 15 wt% of methacrylic acid units are Zn ions) 138 parts by weight of neutralized ionomer) is supplied to a plastograph (manufactured by Brabender), melt-kneaded at 190 ° C. and a screw speed of 30 rpm for 15 minutes, and a resin composition (1) containing a copper salt of ethylphosphonic acid Got.

[Example 2]
Zn salt of ethylene-methacrylic acid copolymer (ionomer in which 29% of carboxyl groups contained in ethylene-methacrylic acid copolymer having 15% by weight of methacrylic acid unit were neutralized with Zn ion) was converted into ethylene-methacrylic acid. Example 1 except that the copolymer was replaced with a Zn salt (an ionomer in which 13% of the carboxyl groups contained in the ethylene-methacrylic acid copolymer having 15 wt% methacrylic acid units were neutralized with Zn ions). To obtain a resin composition (2).

[Comparative Example 1]
Zn salt of ethylene-methacrylic acid copolymer (ionomer in which 29% of carboxyl groups contained in ethylene-methacrylic acid copolymer having 15% by weight of methacrylic acid unit were neutralized with Zn ion) was converted into ethylene-methacrylic acid. Same as Example 1 except that Na salt of copolymer (ionomer in which 30% of carboxyl groups contained in ethylene-methacrylic acid copolymer having 15 wt% methacrylic acid unit were neutralized with Na ion) was replaced To obtain a resin composition (c1).

[Comparative Example 2]
Zn salt of ethylene-methacrylic acid copolymer (ionomer in which 29% of carboxyl groups contained in ethylene-methacrylic acid copolymer having 15% by weight of methacrylic acid unit were neutralized with Zn ion) was converted into ethylene-methacrylic acid. Example 1 except that Na salt of copolymer (ionomer in which 54% of carboxyl groups contained in ethylene-methacrylic acid copolymer having 15% by weight of methacrylic acid unit were neutralized with Na ion) was replaced. To obtain a resin composition (c2).

[Analysis of ionomers]
An ionomer resin is dissolved in a mixed solvent of xylene / butanol = 1/1 (vol%) under heating, 6M hydrochloric acid / methanol solution is added dropwise, cooled to room temperature, reprecipitated with methanol, filtered, and measured. A sample was used. The obtained sample was made into a press sheet, and a part of the sheet was separated and measured by the KBr wafer method (microscopic FT-IR transmission method: 300 μm × 300 μm). The total amount of methacrylic acid in the ionomer resin was determined from the ratio of absorption derived from polymethacrylic acid: 1698 cm ⁻¹ and absorption derived from polyethylene: 1467 cm ⁻¹ .

  Next, 20 mg of ionomer resin was accurately weighed, wet-decomposed with 2 ml of sulfuric acid and 2 ml of hydrogen peroxide, and fixed to 100 ml, and the amount of each ion was quantified by ICP-AES.

[Spectral characteristic evaluation]
The spectral transmittance of the resin compositions obtained in Examples and Comparative Examples was measured by the following method.

  Each of the resin compositions obtained in Examples and Comparative Examples was preheated for 5 minutes with a 150 ° C. press (“WF-50”, manufactured by Shindo Metal Industry Co., Ltd.), and then heated and pressurized at a pressure of 15 MPa for 5 minutes. This produced a 0.76 mm thick sheet.

  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. 1 is a spectral transmittance of a sheet formed from the resin composition of Example 1, FIG. 2 is a spectral transmittance of a sheet formed from the resin composition of Example 2, and FIG. 3 is a comparison. FIG. 4 shows the spectral transmittance of a sheet formed from the resin composition of Example 1, and FIG. 4 shows the spectral transmittance of the sheet formed from the resin composition of Comparative Example 2.

  As apparent from FIGS. 1 to 4, a sheet formed from a resin composition containing a polyvalent metal ionomer resin and a copper phosphonate has a wide absorption band in the near infrared region of 800 to 1200 nm. On the other hand, a sheet formed from a resin composition containing a monovalent metal ionomer resin and a phosphonic acid copper salt has a weak absorption band in the vicinity of 600 to 1200 nm.

  That is, the sheet formed from the resin composition of the present invention is formed from a resin composition containing a monovalent metal ionomer resin and a copper phosphonate, while being excellent in visible light transmission and infrared absorption. The sheet is inferior in visible light transmission and near infrared absorption.

Example 3
(Preparation of UV cut layer sheet)
100 parts by weight of an Na salt of an ethylene-methacrylic acid copolymer (an ionomer obtained by neutralizing 54% of carboxyl groups contained in an ethylene-methacrylic acid copolymer having 15 wt% of methacrylic acid units with Na ions), ultraviolet rays 2 parts by weight of 2- (2′-hydroxy-5′-octylphenyl) benzotriazole as an absorbent is supplied to a plastograph (manufactured by Brabender) and melt-kneaded at 190 ° C. and a screw rotation speed of 30 rpm for 15 minutes. A resin composition (a) containing an ultraviolet absorber was obtained.

  The resin composition (a) was preheated for 5 minutes with a 150 ° C. press (“WF-50”, manufactured by Shindo Metal Industry Co., Ltd.), and then heated and pressurized at a pressure of 15 MPa for 5 minutes to obtain a thickness of 1 A sheet for UV cut layer of 0.0 mm was prepared.

(Preparation of near-infrared absorbing layer sheet)
The resin composition (1) containing the ethylphosphonic acid copper salt obtained in Example 1 was preheated for 5 minutes with a press machine (“WF-50”, manufactured by Shindo Metal Industry Co., Ltd.) at 150 ° C., and then at a pressure of 15 MPa. By heating and pressing for 5 minutes, a near-infrared absorbing layer sheet having a thickness of 0.75 mm was produced.

(Production of laminated glass)
The ultraviolet cut layer sheet was cut out with a scissors to prepare two 25 × 75 mm ultraviolet cut layer sheets.

  The near-infrared absorbing layer sheet was cut out using a scissors to prepare a 25 × 75 mm near-infrared absorbing layer sheet.

  The cut-out ultraviolet cut layer sheet, near-infrared absorbing layer sheet, and ultraviolet cut layer sheet are stacked in this order, and preheated for 5 minutes by a 150 ° C. press (“WF-50”, manufactured by Shindo Metal Industry Co., Ltd.) Then, a resin sheet having a thickness of 2.7 mm was formed by heating and pressurizing at a pressure of 15 MPa for 5 minutes, in which an ultraviolet cut layer sheet, a near infrared absorption layer sheet, and an ultraviolet cut layer sheet were laminated in this order.

  A laminated resin sheet is placed on a glass plate (25 × 75 mm, thickness 1 mm) heated to 90 ° C., and a glass plate (25 × 75 mm, thickness 1 mm) heated to 90 ° C. is further used to use a roller. Was temporarily bonded.

  The glass set subjected to the temporary pressure bonding was subjected to heat pressure bonding at 130 ° C. and 15 MPa for 30 minutes using an autoclave to produce a laminated glass.

  In addition, the layer structure of the obtained laminated glass is glass plate / ultraviolet ray cut layer / near infrared absorption layer / ultraviolet ray cut layer / glass plate.

Example 4
(Preparation of near-infrared absorbing layer sheet)
The resin composition (1) containing the ethylphosphonic acid copper salt obtained in Example 1 was preheated for 5 minutes with a press machine (“WF-50”, manufactured by Shindo Metal Industry Co., Ltd.) at 150 ° C., and then at a pressure of 15 MPa. By heating and pressing for 5 minutes, a near-infrared absorbing layer sheet having a thickness of 0.75 mm was produced.

(Production of laminated glass)
The near-infrared absorbing layer sheet was cut out using a scissors to prepare a 25 × 75 mm near-infrared absorbing layer sheet.

  After stacking the cut-out near-infrared absorbing layer sheet on a glass plate heated to 90 ° C. (25 × 75 mm, thickness 1 mm), and further stacking a glass plate heated to 90 ° C. (25 × 75 mm, thickness 1 mm) Temporary pressure bonding was performed using a roller.

  The glass set subjected to the temporary pressure bonding was subjected to heat pressure bonding at 130 ° C. and 15 MPa for 30 minutes using an autoclave to produce a laminated glass.

  In addition, the layer structure of the obtained laminated glass is glass plate / near infrared absorption layer / glass plate.

(Light resistance test)
The light resistance test of the laminated glass produced in Example 3 and Example 4 was performed.

The light resistance test was conducted for 200 hours under the conditions of 180 W / m ² (black panel temperature 63 ° C., humidity 50%, no rain) using a Super Xenon Weather Meter SX75 manufactured by Suga Test Instruments Co., Ltd. The results are shown in Table 1.

  In addition, the visible light transmittance in Table 1 was calculated based on JIS R 3106 from spectral transmittance data measured using a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.).

Claims (8)

A resin composition comprising a polyvalent metal ionomer resin of an ethylene / unsaturated carboxylic acid copolymer and a phosphonic acid copper salt represented by the following general formula (1).

[In General Formula (1), R ¹ is a monovalent group represented by —CH ₂ CH ₂ —R ¹¹ , and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 carbon atom. Represents -20 fluorinated alkyl groups. ]   The resin composition according to claim 1, wherein the polyvalent metal is a divalent metal.   The resin composition according to claim 1, wherein the polyvalent metal is at least one divalent metal selected from zinc, magnesium, and calcium.   The resin composition according to any one of claims 1 to 3, comprising 0.05 to 30 parts by mass of the copper phosphonate per 100 parts by mass of the polyvalent metal ionomer resin.   The resin film formed from the resin composition as described in any one of Claims 1-4.   The intermediate film for laminated glasses formed from the resin composition as described in any one of Claims 1-4. A layer formed from the resin composition according to any one of claims 1 to 4, and a layer formed from another resin composition on both sides of the layer,
An interlayer film for laminated glass, wherein at least one layer formed from the other resin composition is an ultraviolet cut layer.   Laminated glass having the interlayer film for laminated glass according to claim 6 or 7.

Images