JP2010134457A - Infrared ray blocking film and infrared ray blocking laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thin film excellent in an infrared ray blocking property and a visible ray transmissivity. <P>SOLUTION: An infrared ray blocking film includes (1) a first infrared ray blocking resin obtained by adding a compound of at least one kind of metal chosen from a group composed of Li, Ca, V, Co, Ni, Cu, Zn and In to a polymer of a reactant of (meth)acrylamide with phosphoric acid or its hydrolyzate, (2) a second infrared ray blocking resin obtained by adding the metal compound to a copolymer composed of the reactant or its hydrolyzate and a compound having an ethylenic unsaturated bond or (3) a third infrared ray blocking resin consisting a mixture of these. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a thin film excellent in infrared shielding properties and visible light transmittance.

  A film-like material that transmits visible light but reflects or absorbs infrared rays is used to suppress the heat rays of sunlight and to correct the visibility of digital cameras in buildings and vehicles. As such a film-like material, a material made of a composition in which a copper ion is added as an infrared absorber to an acrylic resin and a phosphate ester is added to increase the dispersibility of the copper ion is known. However, since this composition has poor compatibility of the phosphate ester with the acrylic resin, the dispersibility of the copper ions is insufficient, and sufficient infrared shielding properties cannot be obtained.

（Xは水素原子又はメチル基を示し、mは１〜５の整数である）を示し、nは１又は２である］により表されるリン酸基含有単量体と、アルキルアクリレートとの共重合体、及び銅塩を含む光学フィルタを提案している。 Japanese Patent Laid-Open No. 6-118228 (Patent Document 1) describes an optical filter for efficiently cutting near infrared rays as follows: PO (OH) _n R _3-n [where R is

(X represents a hydrogen atom or a methyl group, m is an integer of 1 to 5 and n is 1 or 2), and a phosphate group-containing monomer represented by An optical filter containing a polymer and a copper salt is proposed.

  However, in the filter of Patent Document 1, since the phosphoric acid group-containing monomer has only one phosphoric acid group in the molecule, the dispersion of the copper salt cannot be said to be sufficient, and sufficient infrared shielding properties are obtained. Needs to be thick, and therefore has a problem of lack of visible light transmittance and lightness.

JP-A-6-118228

  Accordingly, an object of the present invention is to provide a thin film excellent in infrared shielding properties and visible light transmittance.

  As a result of intensive studies in view of the above object, the present inventors have found that when a resin in which a metal compound is added to a polymer having a reaction product of (meth) acrylamide and phosphoric acid or a hydrolyzate thereof as an essential component is used, infrared rays are used. The inventors have found that a thin film excellent in blocking property and visible light transmittance can be obtained, and have arrived at the present invention.

  That is, the infrared shielding film of the present invention comprises (1) a polymer of a reaction product of (meth) acrylamide and phosphoric acid or a hydrolyzate thereof, lithium, calcium, vanadium, cobalt, nickel, copper, zinc and indium. A first infrared ray shielding resin comprising at least one metal compound selected from the group consisting of: (2) a co-reaction of the reactant or a hydrolyzate thereof with a compound having an ethylenically unsaturated bond; The polymer contains a second infrared shielding resin obtained by adding the metal compound, or (3) a third infrared shielding resin comprising a mixture thereof.

  The infrared shielding laminated film of the present invention having an infrared shielding layer and a transparent resin film, wherein the infrared shielding layer comprises (1) a reaction product of (meth) acrylamide and phosphoric acid or a hydrolyzate thereof. A first infrared ray shielding resin obtained by adding a compound of at least one metal selected from the group consisting of lithium, calcium, vanadium, cobalt, nickel, copper, zinc and indium to the polymer; (2) the reaction Or a hydrolyzate thereof and a copolymer of a compound having an ethylenically unsaturated bond, a second infrared blocking resin obtained by adding the metal compound, or (3) a third mixture comprising a mixture thereof. The infrared shielding resin is included. A metal oxide semiconductor thin film may be provided on the transparent resin film.

  The metal compound is preferably an organic acid salt, inorganic acid salt, halide, alkoxide or acetylacetonate of the metal. The polymer and copolymer preferably have a (poly) phosphonic acid group. The compound having an ethylenically unsaturated bond may be an unsaturated compound having an acidic group and / or an unsaturated compound having no acidic group. The unsaturated compound having an acidic group is preferably an unsaturated compound having a sulfonic acid group.

  The first infrared blocking resin has a structure in which the metal compound is dispersed in the polymer, a structure in which the metal ions form a salt with the (poly) phosphonic acid group of the polymer, or both of these structures. It is preferable to have. The second infrared ray blocking resin has a structure in which the metal compound is dispersed in the copolymer, a structure in which ions of the metal form a salt with the (poly) phosphonic acid group of the copolymer, or both of them. It preferably has a structure. The second infrared blocking resin has a structure in which the metal compound is dispersed in the copolymer, a structure in which ions of the metal form a salt with the (poly) phosphonic acid group and the acidic group of the copolymer, Or it is more preferable to have both of these structures.

（ただしR¹は水素基又はメチル基である）により表されるN, N-ジホスホン酸（メタ）アクリルアミド、及び式(2)：

（ただしR¹は水素基又はメチル基であり、nは０〜２の整数である）により表される（ポリ）ホスホン酸基含有（メタ）アクリルアミドのいずれか又はこれらの両方を含むのが好ましい。 The hydrolyzate has the formula (1):

(Wherein R ¹ is a hydrogen group or a methyl group) N, N-diphosphonic acid (meth) acrylamide represented by formula (2):

(Wherein R ¹ is a hydrogen group or a methyl group, and n is an integer of 0 to 2) It is preferable to include either or both of (poly) phosphonic acid group-containing (meth) acrylamides represented by .

（ただしR²は水素基又はメチル基であり、R³及びR⁴は水素基又は炭素数１〜３のアルキル基であり、R⁵は炭素数１〜３のアルキレン基である）により表されるアクリルアミドアルカンスルホン酸及び／又はビニルスルホン酸との共重合体に、前記金属化合物を添加してなるのが好ましい。 The second infrared blocking resin includes the reaction product or a hydrolyzate thereof, and the formula (3):

Wherein R ² is a hydrogen group or a methyl group, R ³ and R ⁴ are a hydrogen group or an alkyl group having 1 to 3 carbon atoms, and R ⁵ is an alkylene group having 1 to 3 carbon atoms. It is preferable to add the metal compound to a copolymer of acrylamide alkane sulfonic acid and / or vinyl sulfonic acid.

  In order to obtain a more excellent blocking property against near infrared rays, it is preferable to use a monovalent or divalent copper organic acid salt, inorganic acid salt, halide, alkoxide or acetylacetonate as the metal compound.

  The infrared blocking (laminated) film of the present invention has a high dispersion of metal compounds and / or metal ions thereof, so that even at a thickness of about 500 μm, it has excellent blocking properties for at least medium and far infrared rays. Have Moreover, it is highly permeable to visible light and is lightweight. Such an infrared shielding (laminated) film is useful as a heat ray shielding film or the like. In particular, infrared blocking (laminated) films using copper compounds are also excellent in blocking near-infrared, so they can be used as camera photometric filters, visibility correction filters, near-red line cut filters for plasma displays, etc. Useful.

It is an infrared measurement chart of acrylamide. It is an infrared measurement chart of a phosphonic acid group containing hydrolyzate. It is a graph showing the spectral transmittance of the visible light region and the near-infrared region of the infrared shielding film of Examples 1 and 2. It is a graph showing the spectral transmittance of the visible light region and the near-infrared region of the infrared shielding laminated film of Examples 3 and 4. It is a graph showing the spectral transmittance of the visible light region and the near-infrared region of the infrared shielding laminated film of Examples 5 and 6. It is a graph showing the spectral transmittance of the visible light region and the near-infrared region of the infrared shielding laminated films of Examples 7 and 8. It is a graph showing the spectral transmittance of the visible light region and the near-infrared region of the infrared ray shielding laminated film of Example 9. It is a graph showing the spectral transmittance of the middle / far infrared region of the infrared ray shielding laminated film of Example 9. 10 is a graph showing the spectral transmittance in the middle / far infrared region of the infrared blocking multilayer film of Example 10. FIG. It is a graph showing the spectral transmittance of the visible light region and the near-infrared region of the infrared shielding laminated film of Examples 11-13. 6 is a graph showing spectral transmittances in a visible light region and a near-infrared region of the infrared blocking multilayer films of Examples 15 and 16. 4 is a graph showing spectral transmittances in a visible light region and a near infrared region of the infrared ray shielding laminated films of Examples 16 and 17. 4 is a graph showing spectral transmittances in a visible light region and a near infrared region of the infrared blocking multilayer films of Examples 18 and 19. It is a graph showing the spectral transmittance of the visible light region and the near-infrared region of the infrared shielding laminated film of Examples 20-22. It is a graph showing the spectral transmittance | permeability of the mid-far-infrared area | region of the infrared-shielding laminated film of Examples 20-22. It is a graph showing the spectral transmittance of the visible light region and the near-infrared region of the infrared shielding laminated film of Examples 23-26. It is a graph showing the spectral transmittance | permeability of the mid-far-infrared area | region of the infrared shielding multilayer film of Examples 23-26. 4 is a graph showing spectral transmittances in a visible light region and a near infrared region of the infrared ray shielding laminated films of Examples 27 and 28. FIG. It is a graph showing the spectral transmittance of the visible light region and the near-infrared region of the laminated film of Comparative Examples 1 and 2.

[1] First infrared blocking resin The first infrared blocking resin is a polymer of a reaction product of (meth) acrylamide and phosphoric acid or a hydrolyzate thereof, lithium, calcium, vanadium, cobalt, nickel, It is formed by adding at least one metal compound selected from the group consisting of copper, zinc and indium.

(1) Reaction product of (meth) acrylamide and phosphoric acid and hydrolyzate thereof The first infrared ray blocking resin matrix is formed from a reaction product of (meth) acrylamide and phosphoric acid or a polymer of the hydrolyzate thereof. Become. (Meth) acrylamide may be acrylamide, methacrylamide or a mixture thereof. The phosphoric acid may be either orthophosphoric acid or phosphoric anhydride (phosphorus pentoxide = P ₂ O ₅ ), but phosphoric anhydride is preferred. Hereinafter, the case of using phosphoric anhydride will be described. The polymer is preferably formed by polymerizing a hydrolyzate of a reaction product of (meth) acrylamide and phosphoric anhydride. However, the hydrolysis may be performed before polymerizing the reactants, may be performed while polymerizing the reactants, may be performed after polymerizing the reactants, or may be performed in combination. , Preferably before polymerization.

（ただしR¹は水素基又はメチル基である）に示すように、中間生成物としてピロリン酸が（メタ）アクリルアミドにN, N-結合した化合物、及び／又はジピロリン酸を介して２つの（メタ）アクリルアミドが結合した化合物が生成する工程、及び中間生成物が加水分解される工程を経て、N, N-ジホスホン酸（メタ）アクリルアミドになる。 The reaction and hydrolysis procedures and conditions are described in, for example, WO2005-080454, and thus detailed description thereof is omitted. However, when (meth) acrylamide is reacted with phosphoric anhydride and hydrolyzed, (meth) When acrylamide and phosphoric anhydride are reacted at a molar ratio of 1: 1, (meth) acrylamide is, for example, formula (4):

(Wherein R ¹ is a hydrogen group or a methyl group), a compound in which pyrophosphate is N, N-bonded to (meth) acrylamide as an intermediate product and / or two (meta) via dipyrophosphate. ) N, N-diphosphonic acid (meth) acrylamide is obtained through a process in which an acrylamide-bound compound is formed and an intermediate product is hydrolyzed.

（ただしR¹は水素基又はメチル基であり、x及びyは０〜２の整数である）に示すように、N-（ポリ）ホスホン酸（メタ）アクリルアミドになる。 When (meth) acrylamide and phosphoric anhydride are reacted at a molar ratio of 2: 1, (meth) acrylamide is represented by, for example, formula (5):

(Wherein R ¹ is a hydrogen group or a methyl group, x and y is an integer from 0 to 2) as shown in, the N- (poly) phosphonic acid (meth) acrylamide.

  Therefore, when N, N-diphosphonic acid (meth) acrylamide is mainly produced, the molar ratio of phosphoric anhydride to (meth) acrylamide is preferably in the range of 0.9 to 1.2. When N- (poly) phosphonic acid (meth) acrylamide is mainly produced, the molar ratio of phosphoric anhydride to (meth) acrylamide is preferably in the range of 0.5 to 0.8. The molar ratio of N, N-diphosphonic acid (meth) acrylamide to N- (poly) phosphonic acid (meth) acrylamide is preferably (50/50) or more, more preferably (60/40) or more, (70 / 30) or more is most preferable.

(2) Metal compound The metal compound is an organic acid salt, inorganic acid salt, halide, alkoxide or acetyl of at least one metal selected from the group consisting of lithium, calcium, vanadium, cobalt, nickel, copper, zinc and indium. Acetonate. Among them, a copper compound is preferable because a film having excellent blocking properties not only for the middle and far infrared rays but also for the near infrared rays can be obtained. Copper may be either monovalent or divalent, but divalent is preferred. Examples of the organic acid include formic acid, oxalic acid, acetic acid, lactic acid, propionic acid, butyric acid, tartaric acid, sorbic acid, and gluconic acid. Examples of inorganic acids include sulfuric acid, amidosulfuric acid, phosphoric acid, nitric acid and the like.

  Specific examples of the metal compound include lithium acetate, calcium acetate, vanadium acetylacetonate, cobalt acetate, nickel acetate, cuprous acetate, cuprous sulfate, cuprous phosphate, cuprous nitrate, cuprous chloride, Cuprous bromide, cupric formate, cupric acetate, cupric gluconate, cupric sulfate, cupric phosphate, cupric nitrate, cupric chloride, cupric bromide, acetic acid Zinc and indium chloride are mentioned.

Content of the metal compound, (meth) of the polymer 1g of reactants or a hydrolyzate of acrylamide with phosphoric acid, is preferably 1 × 10 ^-4 ~3 × 10 ^-3 mol, 3 × 10 ^{- 4 to} 2 × 10 ⁻³ mol is more preferable. When this content is less than 1 × 10 ⁻⁴ mol / g, the infrared ray shielding property is insufficient. On the other hand, if it exceeds 3 × 10 ⁻³ mol / g, the visible light transmittance may be lowered.

(3) Preparation method The first infrared ray blocking resin is obtained by polymerizing a reaction product of (meth) acrylamide and phosphoric acid or a hydrolyzate thereof, hydrolyzing the above reaction product while polymerizing, or by reacting the above reaction product. The polymer is polymerized and then hydrolyzed or a combination thereof is prepared, and then a metal compound is added to the polymer. Hereinafter, the case of polymerizing the reaction product or the hydrolyzate thereof will be described.

The polymerization reaction is carried out in an inorganic or organic peroxide such as ammonium persulfate, potassium persulfate, acetyl peroxide, isopropyl hydroperoxide, etc. in a common solvent in which the reaction product or its hydrolyzate and the polymer produced are dissolved. Initiator, 2, 2'-azobisisobutyronitrile, 2, 2 '-Azobis (2,4-dimethylvaleronitrile), dimethyl 2, 2 '-Azobis (2-methylpropionate), dimethyl 2, 2 Using an azo initiator such as' -azobisisobutyrate, or a peroxide initiator such as lauryl peroxide, benzoyl peroxide or tert-butylperoxy pivalate, or a polymerization initiator such as hydrogen peroxide , By radical polymerization.

  As a solvent, water, alcohol, and an organic polar solvent are preferable. As the alcohol, an aliphatic lower alcohol is preferable. As the aliphatic lower alcohol, methanol, ethanol and isopropyl alcohol are preferable. Two or more of these may be used in combination. In addition, an ester, dioxane, ether or the like may be allowed to coexist within a range that does not impair the solubility. As the organic polar solvent, dimethylacetamide and dimethylsulfoxide are preferable. When water is used, it is preferable to use an aliphatic lower alcohol in combination.

  The polymerization procedure is described. A decomposition temperature of a polymerization initiator to be added after putting a solution consisting of (the above reaction product or a hydrolyzate thereof + solvent) into a reactor equipped with a stirrer and a reflux condenser and making the inside of the reactor a nitrogen gas atmosphere is 40 The temperature is raised to from 90 to 90 ° C. The preferred polymerization temperature is 50 ° C to 90 ° C. A polymerization initiator is added immediately after reaching the predetermined temperature. At this time, there is slight heat generation, and the start of polymerization can be confirmed. After reaching the predetermined temperature, the polymerization initiator is added 2 to 3 times at intervals of about 1 hour, and then the polymerization reaction is continued for about 1 to 8 hours. The reaction temperature does not need to be constant from the beginning to the end, and a method of increasing the temperature at the end of the polymerization to minimize the unreacted monomer may be used.

  The polymerization solution preferably has an initial solid content concentration of 10 to 80% by mass, and more preferably 10 to 70% by mass. The total amount of the polymerization initiator used is preferably 0.1 to 5 and more preferably 0.1 to 2 in terms of mass ratio when the above reaction product or its hydrolyzate is defined as 100.

  As a method for adding the metal compound to the polymer, a method in which the metal compound is added to the polymer solution obtained by the above method and stirred is preferable. This operation may be performed at room temperature, but may be heated as necessary. In order to improve the solubility of the metal compound, an inorganic acid such as sulfuric acid, hydrochloric acid, or nitric acid may be added. The addition amount of the inorganic acid is preferably 1 to 1.5 mol per mol of the metal compound. After the metal compound is dispersed or dissolved, it is preferable to stir for about 30 minutes. By evaporating the solvent from the obtained solution, the first infrared blocking resin is obtained. When the acid component (organic acid component and inorganic acid component) produced by the reaction between the polymer and the metal compound is volatile such as acetic acid, it may be evaporated together with the solvent.

(4) Structure The first infrared blocking resin has a structure in which a metal compound is dispersed in a polymer of a reaction product of (meth) acrylamide and phosphoric acid or its hydrolyzate, and a metal ion is a polymer (poly). You may have either the structure which formed the salt with the phosphonic acid group, and these both structures.

[2] Second infrared blocking resin The second infrared blocking resin is a copolymer of a reaction product of (meth) acrylamide and phosphoric acid or a hydrolyzate thereof and a compound having an ethylenically unsaturated bond. And the above metal compound. The compound having an ethylenically unsaturated bond is an unsaturated compound (1) having an ethylenically unsaturated bond and an acidic group in the molecule and / or a compound having an ethylenically unsaturated bond in the molecule but having no acidic group. Saturated compound (2) may be sufficient.

(1) Unsaturated compound containing an acidic group The unsaturated compound containing an acidic group preferably has a sulfonic acid group and / or a carboxylic acid group and an ethylenically unsaturated bond in the molecule. Examples of the skeleton having an ethylenically unsaturated bond include a (meth) acrylate skeleton and a (meth) allyl ester skeleton.

（ただしR²は水素基又はメチル基であり、R³及びR⁴は水素基又は炭素数１〜３のアルキル基であり、R⁵は炭素数１〜３のアルキレン基である）により表されるアクリルアミドアルカンスルホン酸、アリルスルホン酸、メタアリルスルホン酸、ビニルスルホン酸、p-スチレンスルホン酸、（メタ）アクリル酸ブチル-4-スルホン酸、（メタ）アクリロオキシベンゼンスルホン酸等が挙げられる。 (i) Unsaturated monomer containing sulfonic acid group As the unsaturated monomer containing sulfonic acid group, the formula (3):

Wherein R ² is a hydrogen group or a methyl group, R ³ and R ⁴ are a hydrogen group or an alkyl group having 1 to 3 carbon atoms, and R ⁵ is an alkylene group having 1 to 3 carbon atoms. Acrylamide alkane sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, p-styrene sulfonic acid, (meth) acrylic acid butyl-4-sulfonic acid, (meth) acrylooxybenzene sulfonic acid, etc. .

により表されるターシャリーブチルアクリルアミドスルホン酸が好ましい。 As acrylamide alkanesulfonic acid, the formula (6):

The tertiary butyl acrylamide sulfonic acid represented by is preferable.

(ii) Unsaturated monomer containing carboxylic acid group As unsaturated monomer containing carboxylic acid group, (meth) acrylic acid, crotonic acid, maleic acid and its anhydride, fumaric acid, itaconic acid, etc. Is mentioned. These may be used alone or in combination of two or more.

(2) Unsaturated compound containing no acidic group The second infrared ray shielding resin may contain an unsaturated compound containing no acidic group as a copolymer component for the purpose of improving the film forming property, water resistance and the like. (Meth) acrylamide is preferred as the unsaturated compound containing no acidic group.

(3) Mixing ratio In the case of a copolymer composed of a reaction product of (meth) acrylamide and phosphoric acid or a hydrolyzate thereof (a) and an acidic group-containing unsaturated compound (b), these mass ratios (a) / (B) is preferably (10/90) or more, more preferably (20/80) or more, and particularly preferably (20/80) to (70/30). When this ratio is (20/80) to (70/30), more excellent infrared shielding properties and film-forming properties can be obtained. In the case of a copolymer comprising the above reactant or its hydrolyzate (a) and an acidic group-free unsaturated compound (c), the mass ratio (a) / (c) is (50/50) or more. Preferably, (60/40) or more is more preferable. In the case of a copolymer comprising the reaction product or its hydrolyzate (a), an acidic group-containing unsaturated compound (b) and an acidic group-free unsaturated compound (c), the sum of (a) and (b) The mass ratio [(a) + (b)] / (c) is preferably (50/50) or more, and more preferably (60/40) or more. The mass ratio (a) / (b) in this copolymer may be the same as described above.

(4) Content of the metal compound The content of the metal compound is determined by the reaction product of (meth) acrylamide and phosphoric acid or its hydrolyzate, the acid group-containing unsaturated compound (1) and / or the acid group-free content. 1 × 10 ^{−4 to} 3 × 10 ⁻³ mol is preferable, and 3 × 10 ⁻⁴ to 2 × 10 ⁻³ mol is more preferable with respect to 1 g of the copolymer composed of the saturated compound (2).

(5) Preparation method The second infrared ray blocking resin comprises a reaction product of (meth) acrylamide and phosphoric acid or a hydrolyzate thereof, an acidic group-containing unsaturated compound (1) and / or an acidic group-free unsaturated material. It is preferably prepared by copolymerizing the compound (2) and adding a metal compound to the copolymer. Since the copolymerization method and the method of adding a metal compound to the copolymer may be essentially the same as in the case of the first infrared ray blocking resin, description thereof is omitted.

(6) Structure The second infrared ray blocking resin has a structure in which a metal compound is dispersed in the copolymer, and a structure in which metal ions form a salt with the (poly) phosphonic acid group and / or acidic group of the copolymer. , And both of these structures.

[3] Third infrared blocking resin The third infrared blocking resin is a mixture of the first and second infrared blocking resins. These blending ratios are not limited.

[4] Composition of infrared blocking film The infrared blocking film is composed mainly of any of the first to third infrared blocking resins (hereinafter sometimes referred to simply as “infrared blocking resin”). To do. The infrared shielding film is a metal oxide semiconductor fine powder, an infrared absorbing dye, a transparentizing agent, a crosslinking agent, an ultraviolet absorber, a plasticizer, an antioxidative agent, and an antistatic agent as long as the effects of the present invention are not impaired. Other additives such as a surfactant and an inorganic filler may be contained.

(1) Metal oxide semiconductor fine powder Metal oxide semiconductor fine powder has infrared absorptivity. Examples of the metal oxide semiconductor fine powder include fine powder composed of indium oxide and tin oxide composite oxide (ITO), antimony oxide and tin oxide composite oxide (ATO), and the like.

で示される化合物及びそのブチルアンモニウム塩、特開2005-325292号に記載の式(8)：

（R⁶〜R¹³のうち少なくとも一つは１以上の水素原子がハロゲン原子で置換されたハロゲン化アルキル基を示し、他は同一又は異なっていてもよいアルキル基、アルキレン基、シアノアルキル基、水酸基、スルホン酸基、アルキルスルホン酸基、ニトロ基、アミノ基、アルコキシ基、アリール基、ハロゲン原子及びフェニルアルキル基からなる群から選ばれる基を示し、A^-は同一又は異なっていてもよいアニオンを示す）で表されるジイモニウム塩、特開平8-3870号に記載の式(9)：

（Rは水素原子または炭素数が１〜12のアルキル基を表し、Ｘ^-はSbF₆ ^-、ClO₄ ^-、PF₆ ^-、BF₄ ^-、NO₃ ^-、CF₃COO^-、CF₃SO₃ ^-、F^-、Cl^-、Br^-又はI^-を示し、nは１又は２を示す）等が挙げられる。 (2) Infrared absorbing dye As the infrared absorbing dye, a phthalocyanine compound, a naphthalocyanine compound, an anthraquinone compound, formula (7) described in JP-A No. 9-188689:

And a butylammonium salt thereof represented by formula (8) described in JP-A-2005-325292:

(At least one of R ^{6 to} R ¹³ represents a halogenated alkyl group in which one or more hydrogen atoms are substituted with a halogen atom, and the others are the same or different alkyl group, alkylene group, cyanoalkyl group, A group selected from the group consisting of a hydroxyl group, a sulfonic acid group, an alkylsulfonic acid group, a nitro group, an amino group, an alkoxy group, an aryl group, a halogen atom and a phenylalkyl group, and A ⁻ may be the same or different A diimonium salt represented by formula (9) described in JP-A-8-3870:

(R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and X ⁻ represents SbF ₆ ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , NO ₃ ⁻ , CF ₃ COO ⁻ , CF ₃ SO ₃ ^{-, F -, Cl -,} Br - or I ^- indicates, n represents 1 or 2), and the like.

(3) Clearing agent Examples of the clearing agent include polyols such as glycerin, ethylene glycol, propylene glycol, and polyglycerin, and ion-dissolving solvents such as ethylene carbonate and propylene carbonate. The addition amount of the clarifying agent is not limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, and most preferably 30% by mass or less, based on 100% by mass of the infrared blocking resin.

(4) Crosslinking agent As the crosslinking agent, a melamine resin (for example, trimethoxymethylmelamine resin) is preferable. When the melamine resin is added, the (poly) phosphonic acid group of the infrared blocking resin becomes a catalyst, the crosslinking reaction of the melamine resin is promoted, and the mechanical strength of the infrared blocking film is further improved. The addition amount of the crosslinking agent is preferably 20% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less, based on 100% by mass of the infrared blocking resin.

[5] Configuration of infrared blocking multilayer film The infrared blocking multilayer film includes an infrared blocking layer containing one of the first to third infrared blocking resins as a main component and a transparent resin film. Infrared shielding layer is composed of the above metal oxide semiconductor fine powder, infrared absorbing dye, clearing agent, crosslinking agent, ultraviolet absorber, plasticizer, antioxidative agent, antistatic agent, surfactant, inorganic filler. Other additives such as these may be contained.

  By using a transparent resin film, the infrared shielding layer can be protected or the film strength can be improved. Examples of the transparent resin constituting the film include polyethylene terephthalate, polyethylene, polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, polyvinyl pyrrolidone, and a cellulose polymer. Of these, polyethylene terephthalate or polyethylene is preferred. The transparent resin film may appropriately contain additives such as a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a surfactant, and an inorganic filler. A metal oxide semiconductor thin film may be provided on the transparent resin film. As the metal oxide semiconductor thin film, an ITO film and an ATO film are preferable.

  Examples of laminated structures include infrared blocking layer / transparent resin film, infrared blocking layer / transparent resin film / metal oxide semiconductor thin film, transparent resin film / infrared blocking layer / transparent resin film, transparent resin film / Infrared shielding layer / transparent resin film / metal oxide semiconductor thin film. If necessary, a transparent adhesive layer may be provided between the infrared shielding layer and the transparent resin film.

[6] Method for producing infrared shielding film The infrared shielding film can be produced, for example, by a casting method in which a solution of an infrared shielding resin is cast on a horizontal glass plate or tray and the solvent is evaporated. The solution of the infrared blocking resin may be a solution obtained by dissolving the infrared blocking resin in a polar solvent such as water, alcohol, or a mixture thereof. The alcohol may be the same as above. When using the above-mentioned other additives, the additive may be mixed in the solution to be cast. The film (film) formed after evaporation of the solvent may be further heated at 40 to 150 ° C. for about 3 to 30 minutes under normal pressure or reduced pressure.

[7] Manufacturing method of infrared blocking multilayer film The infrared blocking multilayer film is, for example, cast or coated with a solution of an infrared blocking resin on a transparent resin film with or without a metal oxide semiconductor thin film. And can be produced by drying. If necessary, a transparent resin film with or without a metal oxide semiconductor thin film is further laminated on the infrared shielding layer.

[8] Characteristics of infrared blocking film (laminated) film The infrared blocking film and the infrared blocking layer of the infrared blocking multilayer film are mainly composed of an infrared blocking resin in which a metal compound or a metal ion thereof is highly dispersed. Even if the thickness is about 500 μm, it has an excellent barrier property against at least medium and far infrared rays. Moreover, it is highly permeable to visible light and is lightweight. In particular, an infrared ray shielding (laminated) film using a copper compound is excellent in the shielding property against near infrared rays. The thickness of the infrared ray shielding film and the infrared ray shielding layer of the infrared ray shielding laminated film is not limited, but is usually 100 to 2,000 μm, preferably about 100 to 1,200 μm.

  The infrared shielding (lamination) film as described above is useful as a heat ray shielding film or the like. In particular, an infrared shielding (laminated) film using a copper compound is useful as a camera photometric filter, a visibility correction filter, a near-red line cut filter for a plasma display, and the like.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1
(1) Preparation of hydrolyzate containing phosphonic acid group
In the same manner as in Example 4 of WO2005-080454, a hydrolyzate having a phosphonic acid group was prepared using acrylamide and phosphoric anhydride. A poor solvent was added to the reaction solution containing the phosphonic acid group-containing hydrolyzate, and the filtered phosphonic acid group-containing hydrolyzate was heated and dried at 100 ° C. for 1 hour. The acid value of the phosphonic acid group-containing hydrolyzate was measured and found to be 925 mg / g (theoretical acid value of N, N-diphosphonic acid acrylamide: 969.7 mg / g, the theoretical acid value of N-monophosphonic acid acrylamide: 741.7 mg / g).

(2) Elemental analysis The nitrogen content of the phosphonic acid group-containing hydrolyzate was measured by the CHN coder method, the phosphorus content was measured by ICP emission spectroscopy, and the mass ratio of nitrogen and phosphorus was determined. 4.4, which is the same as the theoretical ratio in N, N-diphosphonic acid acrylamide.

(3) Infrared spectrum measurement About the acrylamide and the phosphonic acid group containing hydrolyzate, the infrared spectrum measurement was performed using the Fourier-transform infrared spectroscopy apparatus (form: Nexus 670, the product made from a Nicolet company). The results are shown in FIGS. In acrylamide, a peak due to NH bond was detected in the vicinity of 3,170 cm ⁻¹ (FIG. 1), but this peak was not detected in the phosphonic acid group-containing hydrolyzate (FIG. 2). In the phosphonic acid group-containing hydrolyzate in the range of 700~1,300 cm ^-1, broad peak due to the phosphonic acid groups were detected (Figure 2). From these facts, it was confirmed that two phosphonic acid groups were introduced into most acrylamide nitrogen atoms.

(4) Liquid Chromatographic Analysis As a result of analyzing the phosphonic acid group-containing hydrolyzate by liquid chromatography, the area ratio of the N, N-diphosphonic acid acrylamide peak to the N-monophosphonic acid acrylamide peak was 80/20. [The analytical conditions for liquid chromatography are as follows. Measuring instrument: SPD-10A manufactured by Shimadzu Corporation (using UV detector), column temperature: room temperature, solvent: methanol / water = 7/3 (mass ratio), concentration: 0.01% by mass (injection amount: 2.5 μl), Column: PRP-1 manufactured by HAMILTON, solvent flow rate: 0.3 ml / min. ].

  Based on the results of elemental analysis, infrared spectrum measurement, and liquid chromatography analysis, the phosphonic acid group-containing hydrolyzate contains N, N-diphosphonic acid acrylamide and N-monophosphonic acid acrylamide, and N, N-diphosphonic acid acrylamide is the main component. It was confirmed that the mixture was a component.

(4) Preparation of copolymer 16.1 g of phosphonic acid group-containing hydrolyzate, 32.0 g (0.154 mol) of tertiary butyl acrylamide sulfonic acid (molecular weight) with reflux condenser, catalyst inlet, etc. 207.25) and 70.0 g of a 30% by mass methanol aqueous solution were added, stirred while introducing nitrogen gas, heated to 80 ° C., and then 2.5 g of 10% by mass ammonium persulfate (APS) aqueous solution was added. After 1 hour and 2 hours, 2.5 g of 10% by mass APS aqueous solution was further added. Thereafter, the mixture was kept at 80 ° C. for 3 hours to obtain a phosphonic acid group-containing hydrolyzate and tertiary butyl acrylamide sulfonic acid copolymer solution having a solid content concentration of 49.3 mass%. As a result of measuring the viscosity (18 ° C.) of the copolymer solution, it was 16,940 cps. The copolymer solution was diluted with water to give a 10% by mass solution.

(5) Preparation of infrared ray blocking resin 3.27 g (0.0180 mol) of cupric acetate per 10.0 g of copolymer was dissolved in a copolymer solution (10% by mass) at room temperature and stirred for 30 minutes.

(6) Production of infrared shielding film The obtained infrared shielding resin solution was cast on a glass plate and dried at 50 ° C. for 3 days to produce an infrared shielding film having a thickness of 500 μm.

Example 2
An infrared blocking film was produced in the same manner as in Example 1 except that 4% by mass of trimethoxymethylmelamine resin was added to the infrared blocking resin solution at 100% by mass.

Example 3
A phosphonic acid group-containing hydrolyzate having a solid content concentration of 37.0% by mass in the same manner as in Example 1 except that 348 g of a 60% by mass aqueous methanol solution was used to polymerize only 165.0 g of the phosphonic acid group-containing hydrolyzate. A polymer solution was obtained. It was 2,640 cps as a result of measuring the viscosity (28 degreeC) of the obtained polymer solution.

  3.09 g (0.0170 mol) of cupric acetate was dissolved in 30.00 g of a 7.0 mass% sulfuric acid aqueous solution. 33.09 g of the obtained cupric acetate solution was gradually added to 40.0 g of the phosphonic acid group-containing hydrolyzate polymer solution at room temperature, followed by stirring for 30 minutes.

  The obtained infrared blocking resin solution was cast into a polyethylene terephthalate (PET) film (thickness 100 μm) container (bottom surface: 10 cm × 10 cm), dried at 50 ° C. for 3 days, and 1 mm thick. An infrared blocking layer was formed. From this container, only the bottom portion provided with the infrared shielding layer was cut out, and a polyethylene film having a thickness of 45 μm was laminated on the infrared shielding layer to prepare an infrared shielding laminated film.

Example 4
An infrared blocking laminated film was produced in the same manner as in Example 3 except that the thickness of the infrared blocking layer was 500 μm.

Example 5
7.50 g of the phosphonic acid group-containing hydrolyzate prepared in the same manner as in Example 1 and 22.50 g of tertiary butyl acrylamide sulfonic acid were dissolved in 70.0 g of a 30% by mass methanol aqueous solution. The obtained mixed liquid was stirred while introducing nitrogen gas, heated to 80 ° C., and then 2.5 g of 10 mass% APS aqueous solution was added. After 1 hour and 2 hours, 2.5 g of 10% by mass APS aqueous solution was further added. Thereafter, the solution was kept at 80 ° C. for 3 hours to obtain a solution containing a phosphonic acid group-containing hydrolyzate and a tertiary butyl acrylamide sulfonic acid copolymer.

  5.99 g (0.0330 mol) of cupric acetate was dissolved in the copolymer solution at room temperature and stirred for 30 minutes. Using the obtained infrared blocking resin solution, an infrared blocking laminated film was prepared in the same manner as in Example 3, except that an infrared blocking layer having a thickness of 500 μm was formed.

Example 6
An infrared blocking multilayer film was prepared in the same manner as in Example 5 except that 10.0 g and 20.0 g of phosphonic acid group-containing hydrolyzate and tertiary butyl acrylamide sulfonic acid were used, respectively.

Example 7
An infrared blocking multilayer film was produced in the same manner as in Example 5 except that 15.0 g and 15.0 g of phosphonic acid group-containing hydrolyzate and tertiary butyl acrylamide sulfonic acid were used, respectively.

Example 8
An infrared blocking multilayer film was prepared in the same manner as in Example 5 except that 20.0 g and 10.0 g of phosphonic acid group-containing hydrolyzate and tertiary butyl acrylamide sulfonic acid were used, respectively.

Example 9
In the same manner as in Example 1 except that ion-exchanged water was used as the solvent and the solid content concentration was 10.0% by mass, the phosphonic acid group-containing hydrolyzate and tertiary butyl acrylamide sulfonic acid having a mass ratio of 1.00: 2.00 were used. A solution containing the polymer was prepared. In the copolymer solution, 3.09 g (0.0170 mol) of cupric acetate per 10.0 g of the copolymer was dissolved at room temperature and stirred for 30 minutes. The obtained infrared blocking resin solution was cast into the PET film container and dried at 50 ° C. for 3 days to form an infrared blocking layer having a thickness of 500 μm. Only the bottom part provided with the infrared shielding layer was cut out from this container, and a 100 μm thick PET film was laminated on the infrared shielding layer to produce an infrared shielding laminated film.

Example 10
One PET film was replaced with a PET film (100 μm thickness) having an ITO film having a thickness of 10 μm, and the laminated structure was changed to PET film / infrared shielding layer / PET film / ITO film as in Example 9. An infrared shielding laminated film was prepared.

Example 11
An infrared ray shielding laminated film was produced in the same manner as in Example 9 except that 3.27 g (0.0180 mol) of cupric acetate was added per 10.0 g of the copolymer.

Example 12
An infrared ray shielding laminated film was produced in the same manner as in Example 9 except that 8.17 g (0.0180 mol) of cupric gluconate was added per 10.0 g of the copolymer.

Example 13
An infrared ray shielding laminated film was produced in the same manner as in Example 9 except that 2.87 g (0.0180 mol) of cupric phosphate was added per 10.0 g of the copolymer.

Example 14
An infrared ray shielding laminated film was produced in the same manner as in Example 9 except that 4.06 g (0.0180 mol) of cupric formate was added per 10.0 g of the copolymer.

Example 15
An infrared ray shielding laminated film was produced in the same manner as in Example 9, except that 2.66 g (0.0110 mol) of cupric nitrate trihydrate per 10.0 g of the copolymer was added.

Example 16
An infrared ray shielding laminated film was produced in the same manner as in Example 9 except that 0.545 g (0.0055 mol) of cuprous chloride was added per 10.0 g of the copolymer.

Example 17
An infrared ray shielding laminated film was produced in the same manner as in Example 9 except that 0.297 g (0.0030 mol) of cuprous chloride was added per 10.0 g of the copolymer.

Example 18
An infrared ray shielding laminated film was produced in the same manner as in Example 9 except that 1.48 g (0.0110 mol) of cupric chloride was added per 10.0 g of the copolymer.

Example 19
An infrared ray shielding laminated film was produced in the same manner as in Example 9 except that 1.75 g (0.0110 mol) of cupric sulfate was added per 10.0 g of the copolymer.

Example 20
An infrared ray shielding laminated film was produced in the same manner as in Example 9 except that 2.02 g (0.0110 mol) of zinc acetate was added per 10.0 g of the copolymer.

Example 21
An infrared ray shielding laminated film was produced in the same manner as in Example 9 except that 0.726 g (0.0110 mol) of lithium acetate was added per 10.0 g of the copolymer.

Example 22
An infrared ray shielding laminated film was produced in the same manner as in Example 9 except that 2.74 g (0.0110 mol) of nickel acetate was added per 10.0 g of the copolymer.

Example 23
An infrared ray shielding laminated film was produced in the same manner as in Example 9 except that 1.94 g (0.0110 mol) of calcium acetate was added per 10.0 g of the copolymer.

Example 24
An infrared ray shielding laminated film was produced in the same manner as in Example 9 except that 1.95 g (0.0110 mol) of cobalt acetate was added per 10.0 g of the copolymer.

Example 25
An infrared ray shielding laminated film was produced in the same manner as in Example 9 except that 3.23 g (0.0110 mol) of indium chloride was added per 10.0 g of the copolymer.

Example 26
An infrared ray shielding laminated film was produced in the same manner as in Example 9, except that 3.83 g (0.0110 mol) of vanadium acetylacetonate per 10.0 g of the copolymer was added.

Example 27
A hydrolyzate having a phosphonic acid group was prepared using acrylamide and phosphoric anhydride in the same manner as in Example 1 of WO2005-080454. A poor solvent was added to the reaction solution containing the phosphonic acid group-containing hydrolyzate, and the phosphonic acid group-containing hydrolyzate separated by the separatory funnel was heated and dried at 100 ° C. for 1 hour. As a result of measuring the acid value of the phosphonic acid group-containing hydrolyzate, it was 635 mg / g, and it was confirmed that the main component of the product was N-monoacrylamidephosphonic acid (theoretical acid value: 741.7 mg / g). It was.

  23.3 parts by mass of the phosphonic acid group-containing hydrolyzate, 46.7 parts by mass of vinyl sulfonic acid (molecular weight 108.12), and 30 parts by mass of dimethylacetamide are placed in an automatic synthesis reactor having a reflux condenser, a catalyst inlet, and the like. The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 80 ° C., and then ammonium persulfate having a mass ratio of 1.5 was added with the total of the phosphonic acid group-containing hydrolyzate and vinyl sulfonic acid being 100. Thereafter, the mixture was kept at 80 ° C. for 6 hours to obtain a phosphonic acid group-containing hydrolyzate and vinylsulfonic acid copolymer solution having a solid concentration of 66.7% by mass. As a result of measuring the viscosity (25 ° C.) of the copolymer solution, it was 1,470 cps. The copolymer solution was diluted with water to give a 20% by mass solution.

  1 g (0.0055 mol) of cupric acetate per 10.0 g of the copolymer was dissolved in the diluted copolymer solution (20% by mass) and stirred. To the obtained infrared blocking resin solution (solid content: 23.0% by mass), 30% by mass of glycerin was added with the infrared blocking resin as 100% by mass.

  The obtained solution was cast into a PET film (thickness: 100 μm) container (bottom surface: 10 cm × 10 cm) and dried at 50 ° C. for 24 hours to form an infrared blocking layer having a thickness of 134 μm. From this container, only the bottom portion provided with the infrared shielding layer was cut out, and a polyethylene film having a thickness of 50 μm was laminated on the infrared shielding layer to produce an infrared shielding laminated film.

Example 28
In an automatic synthesis reaction apparatus having a reflux condenser, a catalyst inlet, etc., 23.3 parts by mass of the same phosphonic acid group-containing hydrolyzate as the main component of N, N-diphosphonic acid acrylamide as in Example 1, 46.7 parts by mass of vinyl After adding sulfonic acid and 30 parts by mass of dimethylacetamide, stirring while introducing nitrogen gas, and heating up to 80 ° C., the total of the phosphonic acid group-containing hydrolyzate and vinyl sulfonic acid was set to 100 and the mass ratio was 1.5. Of ammonium persulfate was added. Thereafter, the mixture was kept at 80 ° C. for 6 hours to obtain a phosphonic acid group-containing hydrolyzate and vinylsulfonic acid copolymer solution having a solid content concentration of 70% by mass. As a result of measuring the viscosity (25 ° C.) of the copolymer solution, it was 230 cps. The copolymer solution was diluted with water to give a 20% by mass solution.

  1 g (0.0055 mol) of cupric acetate per 10.0 g of the copolymer was dissolved in the diluted copolymer solution (20% by mass) and stirred. To the obtained infrared blocking resin solution (solid content: 21.3% by mass), 30% by mass of glycerin was added with the infrared blocking resin as 100% by mass.

  The obtained solution was cast into the above PET film container and dried at 50 ° C. for 24 hours to form an infrared shielding layer having a thickness of 100 μm. From this container, only the bottom portion provided with the infrared shielding layer was cut out, and a polyethylene film having a thickness of 50 μm was laminated on the infrared shielding layer to produce an infrared shielding laminated film.

Comparative Example 1
Polyethylene film (45 μm) / Phosphonic acid group-containing hydrolyzate polymer layer (1 mm) in the same manner as in Example 3 except that a polymer layer of phosphonic acid group-containing hydrolyzate was provided instead of the infrared ray blocking layer. A film having a laminated structure composed of / PET film (100 μm) was produced.

Comparative Example 2
A film having a laminated structure composed of a polyethylene film (45 μm) / PET film (100 μm) was produced.

  For the infrared blocking (laminated) films of Examples 1 to 28 and the laminated films of Comparative Examples 1 and 2, a spectrophotometer (type: U-2900, manufactured by Hitachi High-Technologies Corporation) and the above-described Fourier transform infrared spectrometer Spectral transmittance of 300-1100 nm wavelength range (Examples 1-9, 11-28, Comparative Examples 1 and 2) and 2,500-20,000 nm wavelength range (Examples 9, 10, 20-26) Was measured. The results are shown in FIGS.

  From FIGS. 3 to 7, 10 to 13 and 18, the infrared blocking (laminated) films containing the copper compounds of Examples 1 to 9, 11 to 19, 27 and 28 are in the near infrared in the wavelength range of 780 to 1,100 nm. And an excellent blocking property of 40% or less and a wavelength range of 380 to 600 nm (a wavelength range of about 480 nm to about 620 nm in Examples 16 to 18 and about 410 nm to about 600 in Example 27) It was found that the film had excellent transmittance of 60% or more with respect to visible light in the wavelength range of nm. In particular, Examples 3, 9, 13, 14, 18, 27, and 28 were found to have a further excellent blocking property of 10% or less with respect to near infrared rays in the above wavelength range. 8 and 9, it was found that the infrared shielding (laminated) film containing cupric acetate has an excellent shielding property of 1% or less with respect to the middle and far infrared rays in the wavelength range of 2,500 to 20,000 nm. .

  From FIGS. 14 to 17, the infrared blocking multilayer film containing each compound of zinc, lithium, nickel, calcium, cobalt, indium and vanadium in the order of Examples 20 to 26 is not good in blocking against near infrared rays, but the above It has an excellent blocking property of 2% or less for mid- and far-infrared rays in the wavelength range, and for visible light in the wavelength range of 380 to 780 nm (in Example 24, the wavelength range of about 480 nm to about 560 nm). It was found to have excellent permeability of 60% or more.

  From FIG. 19, the laminated film of Comparative Example 1 uses a polymer of a phosphonic acid group-containing hydrolyzate that does not have a metal compound, and the laminated film of Comparative Example 2 does not have an infrared shielding layer. None of them had a blocking property against near infrared rays.

Claims (21)

(1) At least one metal selected from the group consisting of lithium, calcium, vanadium, cobalt, nickel, copper, zinc and indium as a polymer of a reaction product of (meth) acrylamide and phosphoric acid or a hydrolyzate thereof. A first infrared shielding resin obtained by adding the above compound, (2) the metal compound is added to a copolymer of the reaction product or a hydrolyzate thereof and a compound having an ethylenically unsaturated bond. An infrared blocking film comprising: a second infrared blocking resin comprising: (3) a third infrared blocking resin comprising a mixture thereof. The infrared shielding film according to claim 1, wherein the metal compound is an organic acid salt, inorganic acid salt, halide, alkoxide, or acetylacetonate of the metal. The infrared shielding film according to claim 1 or 2, wherein the polymer and the copolymer have a (poly) phosphonic acid group. The infrared ray shielding film according to claim 1, wherein the compound having an ethylenically unsaturated bond is an unsaturated compound having an acidic group and / or an unsaturated compound having no acidic group. Infrared shielding film characterized by The infrared shielding film according to claim 4, wherein the unsaturated compound having an acidic group is an unsaturated compound having a sulfonic acid group. The infrared shielding film according to any one of claims 3 to 5, wherein the first infrared shielding resin has a structure in which the metal compound is dispersed in the polymer, and the ion of the metal is a polymer (polyethylene). ) A structure in which a salt is formed with a phosphonic acid group, or both of these structures. The second infrared ray blocking resin has a structure in which the metal compound is dispersed in the copolymer, and the metal ions are in the same structure. An infrared shielding film having a structure in which a salt is formed with a (poly) phosphonic acid group of a polymer, or both of these structures. The infrared ray shielding film according to any one of claims 4 to 6, wherein the second infrared ray shielding resin has a structure in which the metal compound is dispersed in the copolymer, and the metal ions are formed of the copolymer. An infrared blocking film having a structure in which a salt is formed with a (poly) phosphonic acid group and the acidic group, or both of these structures. The infrared shielding film according to any one of claims 1 to 7, wherein the hydrolyzate has the formula (1):

(Wherein R ¹ is a hydrogen group or a methyl group) N, N-diphosphonic acid (meth) acrylamide represented by formula (2):

(Wherein R ¹ is a hydrogen group or a methyl group, n represents an integer of 0 to 2), comprising either or both of these represented by (poly) phosphonic acid group-containing (meth) acrylamide by Infrared shielding film. The infrared ray shielding film according to any one of claims 1 to 8, wherein the second infrared ray shielding resin includes the reactant or a hydrolyzate thereof, and the formula (3):

Wherein R ² is a hydrogen group or a methyl group, R ³ and R ⁴ are a hydrogen group or an alkyl group having 1 to 3 carbon atoms, and R ⁵ is an alkylene group having 1 to 3 carbon atoms. An infrared shielding film comprising: a copolymer of acrylamide alkanesulfonic acid and / or vinylsulfonic acid added with the metal compound. The infrared ray shielding film according to any one of claims 1 to 9, wherein the metal compound is a monovalent or divalent copper organic acid salt, inorganic acid salt, halide, alkoxide, or acetylacetonate. Infrared shielding film characterized. An infrared blocking laminated film having an infrared blocking layer and a transparent resin film, wherein the infrared blocking layer comprises (1) a reaction product of (meth) acrylamide and phosphoric acid or a hydrolyzate thereof. A first infrared ray shielding resin obtained by adding a compound of at least one metal selected from the group consisting of lithium, calcium, vanadium, cobalt, nickel, copper, zinc and indium to the coalescence, (2) the reactant Or a second infrared-blocking resin obtained by adding the metal compound to a copolymer of a hydrolyzate thereof and a compound having an ethylenically unsaturated bond, or (3) a third infrared-blocking resin comprising a mixture thereof. An infrared shielding laminated film comprising an infrared shielding resin. 12. The infrared blocking multilayer film according to claim 11, wherein the metal compound is an organic acid salt, inorganic acid salt, halide, alkoxide or acetylacetonate of the metal. 13. The infrared blocking multilayer film according to claim 11 or 12, wherein the polymer and copolymer have a (poly) phosphonic acid group. 14. The infrared ray shielding laminated film according to claim 11, wherein the compound having an ethylenically unsaturated bond is an unsaturated compound having an acidic group and / or an unsaturated compound having no acidic group. Infrared shielding laminated film characterized by the above. 15. The infrared ray shielding laminated film according to claim 14, wherein the unsaturated compound having an acidic group is an unsaturated compound having a sulfonic acid group. 16. The infrared ray shielding laminated film according to any one of claims 13 to 15, wherein the first infrared ray shielding resin has a structure in which the metal compound is dispersed in the polymer, and the metal ions are ( A structure in which a salt is formed with a poly) phosphonic acid group, or both of these structures, and the second infrared blocking resin has a structure in which the metal compound is dispersed in the copolymer, and the metal ions are An infrared blocking multilayer film having a structure in which a (poly) phosphonic acid group and a salt of a copolymer are formed, or both of these structures. 17. The infrared ray shielding laminated film according to claim 14, wherein the second infrared ray shielding resin has a structure in which the metal compound is dispersed in the copolymer, and the metal ions are the copolymer. An infrared blocking multilayer film having a structure in which a salt is formed with the (poly) phosphonic acid group and the acidic group, or both of these structures. The infrared ray shielding laminated film according to any one of claims 11 to 17, wherein the hydrolyzate has the formula (1):

(Wherein R ¹ is a hydrogen group or a methyl group) N, N-diphosphonic acid (meth) acrylamide represented by formula (2):

(Wherein R ¹ is a hydrogen group or a methyl group, and n is an integer of 0 to 2), and includes (poly) phosphonic acid group-containing (meth) acrylamide or both of them. Infrared shielding laminated film. The infrared ray shielding laminated film according to any one of claims 11 to 18, wherein the second infrared ray shielding resin comprises the reactant or a hydrolyzate thereof, and the formula (3):

Wherein R ² is a hydrogen group or a methyl group, R ³ and R ⁴ are a hydrogen group or an alkyl group having 1 to 3 carbon atoms, and R ⁵ is an alkylene group having 1 to 3 carbon atoms. An infrared ray shielding laminated film obtained by adding the metal compound to a copolymer of acrylamide alkanesulfonic acid and / or vinylsulfonic acid. 20. The infrared ray shielding laminated film according to claim 11, wherein the metal compound is a monovalent or divalent copper organic acid salt, inorganic acid salt, halide, alkoxide, or acetylacetonate. Infrared shielding laminated film characterized by 21. The infrared shielding multilayer film according to claim 11, wherein a metal oxide semiconductor thin film is provided on the transparent resin film.

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