JP2013209234A - Interlayer for laminated glass and laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an interlayer for laminated glass having excellent heat resistance and laminated glass using the same.SOLUTION: An interlayer for laminated glass includes a near infrared (NIR) photosensitive dye that is a compound represented by general formula (1) and polyvinyl acetal resin. Laminated glass using the interlayer has excellent heat resistance and excellent permeability in visible light over a long period.

Description

  The present invention relates to an interlayer film for laminated glass comprising a near-infrared absorbing dye and a polyvinyl acetal resin, and a laminated glass using the interlayer film.

  In recent years, an infrared shielding glass is used for a window glass for a vehicle for the purpose of suppressing a temperature rise in an automobile and reducing a cooling load. The infrared shielding glass has a structure in which an intermediate film containing a metal, a metal oxide, and a near infrared absorbing dye is sandwiched between the glasses.

  Further, in order to prevent the glass fragments from scattering even if the object is difficult to penetrate when subjected to an external impact, polyvinyl acetal resin is preferably used as the resin used for the intermediate film.

  As disclosed in Patent Document 1, as near-infrared absorbing dyes, phthalocyanine compounds, naphthalocyanine compounds, imonium compounds, diimonium compounds, polymethine compounds, diphenylmethane compounds, triphenylmethane compounds, quinone compounds, azo compounds, pentadiene compounds Azomethine compounds, squarylium compounds, and the like. However, the interlayer film for laminated glass and the laminated glass produced using these near-infrared dyes have a drawback of poor heat resistance.

  Therefore, an interlayer film for laminated glass excellent in heat resistance and a laminated glass using the same are desired.

JP 2007-045636 A

  The objective of this invention is providing the intermediate film for laminated glasses excellent in heat resistance, and a laminated glass using the same.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention include a near-infrared absorbing dye, which is a compound represented by the general formula (1), and a polyvinyl acetal resin. The present inventors have found that an interlayer film and a laminated glass produced using the interlayer film can solve the above problems, and have completed the present invention.

  That is, the present invention is as follows.

  1st invention is a near-infrared absorption pigment | dye which is a compound represented by following General formula (1), and the intermediate film for laminated glasses characterized by containing polyvinyl acetal resin.

（式（１）中、Ｒ_１〜Ｒ_８は、それぞれ同一でも異なってもよい有機基を示し、Ｘ⁻は、ビス（トリフルオロメタンスルホニル）イミド酸イオン、ビス（ペンタフルオロエタンスルホニル）イミド酸イオン、シクロ−ヘキサフルオロプロパン−１，３−ビス（スルホニル）イミド酸イオン、トリス（トリフルオロメタンスルホニル）メチド酸イオンからなる群より選ばれる１種である。）

(In the formula (1), R _{1 to} R ₈ each represent an organic group which may be the same or different, and X ⁻ represents a bis (trifluoromethanesulfonyl) imidate ion or a bis (pentafluoroethanesulfonyl) imidate ion. , Cyclo-hexafluoropropane-1,3-bis (sulfonyl) imidoate ion, and tris (trifluoromethanesulfonyl) methidoate ion.

In the second invention, in general formula (1), R _{1 to} R ₈ are cycloalkyl-alkyl groups represented by the following general formula (2), phenylalkyl groups represented by the following general formula (3), The interlayer film for laminated glass according to the first invention, wherein the interlayer film is an alkyl ester group represented by the following general formula (4).

（式（２）中、Ａは炭素数１〜１０の直鎖又は分岐状のアルキル基を示し、ｍは３〜１２の整数を示す。）

(In Formula (2), A shows a C1-C10 linear or branched alkyl group, m shows the integer of 3-12.)

（式（３）中、Ｂは炭素数１〜１０の直鎖又は分岐状のアルキル基を示し、Ｒ_９は炭素数１〜４のアルキル基又はハロゲン原子を示す。）

(In formula (3), B represents a linear or branched alkyl group having 1 to 10 carbon atoms, and R ₉ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom.)

（式（４）中、Ｒ_１０は炭素数１〜１０のアルキル基を示し、ｎは１〜１０の整数である。）

(In the formula _{(4), R 10} represents an alkyl group having 1 to 10 carbon atoms, n represents an integer of 1 to 10.)

  The third invention is the interlayer film for laminated glass according to the first or second invention, wherein the content of the near infrared ray absorbing dye in the interlayer film for laminated glass is 0.01 to 10% by mass. is there.

  A fourth invention is the interlayer film for laminated glass according to any one of the first to third inventions, wherein the polyvinyl acetal resin is a polyvinyl butyral resin.

  A fifth invention is a laminated glass characterized in that the interlayer film for laminated glass according to any one of the first to fourth inventions is bonded between two transparent glass plates.

  The present invention is a glass interlayer film excellent in heat resistance and a laminated glass produced using the same.

  First, the interlayer film for laminated glass of the present invention will be described.

  The interlayer film for laminated glass of the present invention is characterized by containing a near-infrared absorbing dye, which is a compound represented by the general formula (1), and a polyvinyl acetal resin.

[Near-infrared absorbing dye]
The near-infrared absorbing dye used in the present invention is a near-infrared dye that is a compound represented by the following general formula (1). In the present invention, near infrared means light in the wavelength range of 750 to 2000 nm.

R _{1 to} R ₈ in the general formula (1) each represents an organic group which may be the same or different, and X ⁻ represents a bis (trifluoromethanesulfonyl) imidate ion, bis (pentafluoroethanesulfonyl) imidic acid. Examples include ions, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imidic acid ion that is the following compound (I), and tris (trifluoromethanesulfonyl) methydic acid ion that is the following compound (II).

R _{1 to} R ₈ in the general formula (1) each represents an organic group which may be the same or different, and examples thereof include an alkyl group having 1 to 10 carbon atoms and a cycloalkyl represented by the following general formula (2). -An alkyl group, a phenylalkyl group represented by the following general formula (3), an alkyl ester group represented by the following general formula (4), and the like.

  Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

In the general formula (2), A represents a linear or branched alkyl group having 1 to 10 carbon atoms, and m represents an integer of 3 to 12.
The number of carbon atoms of A is preferably 1 to 4, and m is preferably 5 to 8, and particularly preferably 5 or 6.

  Specifically, cyclopentylmethyl group, 2-cyclopentylethyl group, 2-cyclopentylpropyl group, 3-cyclopentylpropyl group, 4-cyclopentylbutyl group, 2-cyclohexylmethyl group, 2-cyclohexylethyl group, 3-cyclohexylpropyl group 4-cyclohexylbutyl group, etc., among them, cyclopentylmethyl group, cyclohexylmethyl group, 2-cyclohexylethyl group, 2-cyclohexylpropyl group, 3-cyclohexylpropyl group, 4-cyclohexylbutyl group are preferable, and more preferable. Are a cyclopentylmethyl group and a cyclohexylmethyl group, and the cyclohexylmethyl group is particularly preferred because of its low solubility and excellent heat resistance.

In the general formula (3), B represents a linear or branched alkyl group having 1 to 10 carbon atoms, and R ₉ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom.
B preferably has 1 to 4 carbon atoms, and R ₉ preferably has 1 or 2 carbon atoms.

  Examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom.

  Specific examples include a methylbenzyl group, an ethylbenzyl group, a propylbenzyl group, and a butylbenzyl group. Among these, a methylbenzyl group is preferable because it is excellent in heat resistance.

上記一般式（４）中、Ｒ_１０は炭素数１〜１０のアルキル基を示し、ｎは１〜１０の整数である。

In the general formula _{(4), R 10} represents an alkyl group having 1 to 10 carbon atoms, n represents an integer of 1 to 10.

  Specifically, methoxycarbonylmethyl group, methoxycarbonylethyl group, methoxycarbonylpropyl group, methoxycarbonylbutyl group, ethoxycarbonylmethyl group, ethoxycarbonylethyl group, ethoxycarbonylpropyl group, ethoxycarbonylbutyl group, propoxycarbonylmethyl group, Propoxycarbonylethyl group, propoxycarbonylpropyl group, propoxycarbonylbutyl group, butoxycarbonylmethyl group, butoxycarbonylethyl group, butoxycarbonylpropyl group, butoxycarbonylbutyl group, and the like, among these, from the point of excellent heat resistance, Preferred examples include methoxycarbonylpropyl group and methoxycarbonylbutyl group.

  Specific examples of the near-infrared absorbing dye comprising the compound represented by the general formula (1) used in the present invention include bis (trifluoromethanesulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p- Di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium, bis (pentafluoroethanesulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylene Diimonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imidic acid-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium, tris (trifluoromethanesulfonyl) methidoic acid-tetrakis {p-di (Cyclohexylmethyl) aminophenyl} -p-fe Range imonium, bis (trifluoromethanesulfonyl) imidic acid-tetrakis {p-di (methylbenzyl) aminophenyl} -p-phenylenediimonium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imidic acid-tetrakis {p -Di (methylbenzyl) aminophenyl} -p-phenylenediimonium, tris (trifluoromethanesulfonyl) methidoic acid-tetrakis {p-di (methylbenzyl) aminophenyl} -p-phenylenediimonium, bis (trifluoromethanesulfonyl) imidic acid -N, N, N ', N'-tetrakis {p-di (3-methoxycarbonylpropyl) aminophenyl} -p-phenylenediimonium, bis (pentafluoroethanesulfonyl) imidic acid-N, N, N', N '-Tetra Su {p-di (3-methoxycarbonylpropyl) aminophenyl} -p-phenylenediimonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imidic acid-tetrakis {p-di (3-methoxycarbonylpropyl) amino Preferable examples include phenyl} -p-phenylene dimonium, tris (trifluoromethanesulfonyl) methido acid-tetrakis {p-di (3-methoxycarbonylpropyl) aminophenyl} -p-phenylene dimonium.

  The near infrared absorbing dye used in the present invention may be a crystalline material or an amorphous material. In the interlayer film for laminated glass, an amorphous material is preferable because it is excellent in being uniformly dispersed in the resin.

  A crystalline material is one that has a crystalline state in which atoms or molecules are regularly arranged periodically. When measured with a powder X-ray diffractometer, a distinct diffraction peak showing crystallinity is detected.

  An amorphous body is a state in which atoms or molecules are in a solid state without forming a crystal having a regular periodic arrangement. The presence or absence of solid crystallinity is determined by measuring a diffraction pattern with a powder X-ray diffractometer. That is, the amorphous body is in a state where a clear diffraction peak showing crystallinity is not detected in a diffraction pattern obtained by a powder X-ray diffractometer.

  The content of the near infrared ray absorbing dye in the interlayer film for laminated glass is preferably 0.01 to 10% by mass, more preferably 0.1 to 7% by mass, and 0.5 to 5% by mass. It is particularly preferably mentioned.

[Adhesive]
Polyvinyl acetal resin is mentioned as an adhesive used for the interlayer film for laminated glass of the present invention.

  The average degree of polymerization of the polyvinyl acetal resin is preferably about 800 to 3000. When the average degree of polymerization is less than 800, there is a problem that the strength of the resin becomes weak, and when it exceeds 3000, there is a problem that molding of the resin film becomes difficult.

  The butyralization degree is preferably 60 to 75 mol% or more. If the degree of acetalization is less than 60 mol%, there is a drawback that the hygroscopicity of the resin is high, and if it exceeds 75 mol%, the strength of the resin film is weakened, so that the penetration resistance of the resulting laminated glass is reduced. There is.

  The acetalization degree is preferably 1 mol% or less. When the degree of acetalization exceeds 1 mol%, there is a problem that the hygroscopicity of the resin is increased.

  Among the polyvinyl acetal resins, a polyvinyl butyral resin is preferable because it has excellent adhesive strength to glass, transparency, and durability.

The manufacturing method of the said polyvinyl acetal resin is demonstrated below. Polyvinyl alcohol is dissolved in warm water, an acid catalyst and an aldehyde are added, and the mixture is reacted with stirring. After completion of the reaction, a polyvinyl acetal resin can be obtained by neutralization, washing with water and drying.
As the aldehyde, an aldehyde having 1 to 10 carbon atoms is used, and n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, n-nonylaldehyde, Examples include n-decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Particularly preferred is butyraldehyde. Polyvinyl butyral can be obtained by using butyraldehyde.

<Organic solvent>
The interlayer film for laminated glass of the present invention may contain an organic solvent. In the case of this invention, since it is excellent in the dispersibility of a near-infrared absorption pigment | dye, the intermediate film for laminated glasses can be manufactured even if it does not use an organic solvent.
The organic solvent is not particularly limited, and alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol: glycols such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene copolymer Solvents: Ether alcohol solvents such as the glycol solvents monomethyl ether, monoethyl ether, monopropyl ether, monoisopropyl ether, monobutyl ether, etc .: The glycol solvents dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, di Butyl ether, methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, methyl butyl ether Polyether solvents such as ethyl propyl ether, ethyl isopropyl ether, and ethyl butyl ether: ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone: ester solvents such as methyl acetate, ethyl acetate, and butyl acetate: hexane, heptane, and octane , Hydrocarbon solvents such as cyclopentane, cyclohexane, toluene and xylene. The organic solvent can also be used as a plasticizer.
These organic solvents may be used alone or as a mixed solvent of two or more. An organic solvent having a boiling point of 200 ° C. or lower is preferable.

<Additives>
The interlayer film for laminated glass of the present invention may contain an appropriate additive depending on the purpose. Specific examples of additives include curing agents, leveling agents, pigments, pigment dispersants, UV absorbers, antioxidants, viscosity modifiers, light stabilizers, metal deactivators, peroxide decomposing agents, and fillers. Agent, reinforcing material, plasticizer, lubricant, anticorrosive agent, rust preventive agent, emulsifier, mold demolding agent, fluorescent whitening agent, organic flameproofing agent, inorganic flameproofing agent, anti-dripping agent, melt flow modifier , Antistatic agents, slipping agents, adhesion promoters, antifouling agents, surfactants, antifoaming agents, polymerization inhibitors, photosensitizers, surface modifiers, silane coupling agents, and the like. Among these, a plasticizer and an ultraviolet absorber are preferable.

  Examples of the plasticizer include triethylene glycol-di-2-ethylbutyrate (3GH), triethylene glycol-di-2-ethylenehexanoate (3GO), tetraethylene glycol-di-2-ethylenehexanoate ( 4GO) and tetraethylene glycol-di-2-butyl sebagate are preferred. Among these, triethylene glycol-di-2-ethylenehexanoate (3GO) is particularly preferable. Plasticizers may be used alone or in combination of two or more.

  The content of the plasticizer is preferably 15 to 40% by mass and more preferably 20 to 35% by mass with respect to the interlayer film for laminated glass. If it is less than 15% by mass, the strength of the obtained interlayer film or laminated glass becomes insufficient, and if it exceeds 40% by mass, the plasticizer bleeds out and the adhesiveness of the resulting interlayer film or laminated glass is impaired. is there.

  Examples of the ultraviolet absorber include ultraviolet absorbers such as malonic acid ester compounds, oxalic acid anilide compounds, benzotriazole compounds, benzophenone compounds, triazine compounds, hindered amine compounds, and the like.

The interlayer film for laminated glass of the present invention may contain any appropriate organic fine particles or inorganic fine particles. These organic fine particles or inorganic fine particles are used for imparting a function (refractive index adjustment, etc.) according to the purpose.
Specific examples of fine particles useful for increasing the refractive index of interlayer films for laminated glass include zinc oxide, titanium oxide, zirconium oxide, aluminum oxide, tin oxide, tin-doped indium oxide, antimony-doped tin oxide, indium-doped zinc oxide, and indium oxide. And antimony oxide.
Specific examples of the fine particles useful for reducing the refractive index of the interlayer film for laminated glass include magnesium fluoride, silica, and hollow silica. Specific examples of fine particles useful for imparting antiglare properties include inorganic particles such as calcium carbonate, barium sulfate, talc, and kaolin in addition to the fine particles described above: silicon resin, melamine resin, benzoguanamine resin, acrylic resin, polystyrene resin, and these Organic fine particles such as a copolymer resin. These fine particles may be used alone or in combination of two or more.

<Laminated glass>
The laminated glass of the present invention is characterized in that the interlayer film for laminated glass described above is bonded between two transparent glass plates.
The laminated glass of this invention can be manufactured by the method similar to the manufacturing method of a normal laminated glass. A laminated glass can be produced by sandwiching the interlayer film for laminated glass described above between two glass plates and passing it through a pressing roll, followed by pressure bonding while heating.

  The interlayer film for laminated glass of the present invention may be a single-layer interlayer film for laminated glass, or may be an interlayer film for laminated glass having a multilayer structure in which two or more resin films are laminated.

  As the transparent glass plate, a commonly used transparent glass plate can be used. Examples of such a transparent glass plate include various inorganic glasses such as float glass, heat ray absorbing glass and mold glass, and organic glasses such as polycarbonate and polymethyl methacrylate. Among these, it is preferable to use heat ray shielding glass.

  Examples of the use of laminated glass include automobile windshields, side glasses, rear glasses, roof glasses, architectural window glasses, and the like.

  EXAMPLES Hereinafter, an Example is given and this invention is demonstrated in detail. In addition, this invention is not limited at all by this Example. “Parts” in the examples are “parts by mass”.

(Production Example 1)
To 100 parts of DMF, 10 parts of N, N, N ′, N′-tetrakis (p-aminophenyl) -p-phenylenediamine, 63 parts of cyclohexylmethyl iodide and 30 parts of potassium carbonate were added and reacted at 120 ° C. for 10 hours. . Next, the reaction solution is added to 500 parts of water, and the resulting precipitate is filtered, washed with 500 parts of methyl alcohol, dried at 100 ° C., and N, N, N ′, N′-tetrakis {p-di ( 24.1 parts of (cyclohexylmethyl) aminophenyl} -p-phenylenediamine were obtained.
To 24.1 parts of the obtained N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediamine, 200 parts of acetonitrile and silver bis (trifluoromethanesulfonyl) imidate 7 .9 parts were added and reacted at 60 ° C. for 3 hours, and the resulting silver was filtered off. Next, 200 parts of water was added to the filtrate, and the resulting precipitate was filtered and dried, and bis (trifluoromethanesulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p-di (cyclohexyl). 27.0 parts of (methyl) aminophenyl} -p-phenylenediimonium (Compound 1) were obtained.

(Production Example 2)
Bis (pentafluoroethanesulfonyl) imide is prepared in the same manner as in Production Example 1 except that silver bis (pentafluoroethanesulfonyl) imidate is used in place of the silver bis (trifluoromethanesulfonyl) imidate described in Production Example 1. Acid-N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium (compound 2) was obtained.

(Production Example 3)
Cyclohexafluoropropane-1,3-bis (sulfonyl) imidate silver was used instead of the silver bis (trifluoromethanesulfonyl) imidate described in Production Example 1 in the same manner as in Production Example 1, except that -Hexafluoropropane-1,3-bis (sulfonyl) imidic acid-N, N, N ', N'-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium (compound 3) was obtained. .

(Production Example 4)
Tris (trifluoromethanesulfonyl) methido acid in the same manner as in Production Example 1 except that silver tris (trifluoromethanesulfonyl) methidoate was used instead of the silver bis (trifluoromethanesulfonyl) imidate described in Production Example 1. -N, N, N ', N'-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium (compound 4) was obtained.

(Production Example 5)
Instead of N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediamine described in Production Example 1, N, N, N ′, N′-tetrakis {p -Bis (trifluoromethanesulfonyl) imidic acid-N, N, N ', N'-tetrakis {p- in the same manner as in Production Example 1 except that -di (methylbenzyl) aminophenyl} -p-phenylenediamine was used. Di (methylbenzyl) aminophenyl} -p-phenylenediamine (Compound 5) was obtained.

(Production Example 6)
Instead of N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediamine described in Production Example 1, N, N, N ′, N′-tetrakis {p Example 1 except that -di (methylbenzyl) aminophenyl} -p-phenylenediamine was used, and silver bis (pentafluoroethanesulfonyl) imidate was used instead of silver bis (trifluoromethanesulfonyl) imidate Similarly, bis (pentafluoroethanesulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p-di (methylbenzyl) aminophenyl} -p-phenylenediamine (Compound 6) was obtained.

(Production Example 7)
Instead of N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediamine described in Production Example 1, N, N, N ′, N′-tetrakis {p -Di (methylbenzyl) aminophenyl} -p-phenylenediamine was used, and silver cyclo-hexafluoropropane-1,3-bis (sulfonyl) imidate was used instead of silver bis (trifluoromethanesulfonyl) imidate. Except that cyclo-hexafluoropropane-1,3-bis (sulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p-di (methylbenzyl) aminophenyl}- p-Phenylenediamine (Compound 7) was obtained.

(Production Example 8)
Instead of N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediamine described in Production Example 1, N, N, N ′, N′-tetrakis {p Similar to Production Example 1 except that -di (methylbenzyl) aminophenyl} -p-phenylenediamine was used and silver tris (trifluoromethanesulfonyl) methidoate was used instead of silver bis (trifluoromethanesulfonyl) imidate. Thus, tris (trifluoromethanesulfonyl) methydic acid-N, N, N ′, N′-tetrakis {p-di (methylbenzyl) aminophenyl} -p-phenylenediamine (Compound 8) was obtained.

(Production Example 9)
Bis (trifluoromethanesulfonyl) imidic acid-N, N, N ′, in the same manner as in Production Example 1 except that 3-methoxycarbonylpropyl iodide was used instead of the cyclohexylmethyl iodide described in Production Example 1. N′-tetrakis {p-di (3-methoxycarbonylpropyl) aminophenyl} -p-phenylenediamine (Compound 9) was obtained.

(Production Example 10)
Instead of cyclohexylmethyl iodide described in Production Example 1, 3-methoxycarbonylpropyl iodide was used, and instead of silver bis (trifluoromethanesulfonyl) imidate, bis (pentafluoroethanesulfonyl) imidate silver was used. Except for bis (pentafluoroethanesulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p-di (3-methoxycarbonylpropyl) aminophenyl} -p-phenylenediamine in the same manner as in Production Example 1. (Compound 10) was obtained.

(Production Example 11)
Instead of cyclohexylmethyl iodide described in Preparation Example 1, 3-methoxycarbonylpropyl iodide was used, and instead of silver bis (trifluoromethanesulfonyl) imidate, cyclo-hexafluoropropane-1,3-bis (sulfonyl) was used. ) Cyclo-hexafluoropropane-1,3-bis (sulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p-di (p) in the same manner as in Production Example 1 except that silver imidoate was used. 3-methoxycarbonylpropyl) aminophenyl} -p-phenylenediamine (Compound 11) was obtained.

(Production Example 12)
Other than using 3-methoxycarbonylpropyl iodide instead of cyclohexylmethyl iodide described in Production Example 1 and using silver tris (trifluoromethanesulfonyl) methidoate instead of silver bis (trifluoromethanesulfonyl) imidate In the same manner as in Production Example 1, tris (trifluoromethanesulfonyl) methic acid-N, N, N ′, N′-tetrakis {p-di (3-methoxycarbonylpropyl) aminophenyl} -p-phenylenediamine (compound 12) was obtained.

(Production Example 13)
Tetrafluoroboric acid-N, N, N ′, except that silver tetrafluoroborate was used instead of silver bis (trifluoromethanesulfonyl) imidate described in Production Example 1 in the same manner as Production Example 1. N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium (compound 13) was obtained.

(Production Example 14)
Tetrafluoroboric acid-N, N, N ′, except that silver tetrafluoroborate was used instead of silver bis (trifluoromethanesulfonyl) imidate described in Production Example 5 in the same manner as Production Example 5. N′-tetrakis {p-di (methylbenzyl) aminophenyl} -p-phenylenediimonium (compound 14) was obtained.

(Production Example 15)
Hexafluorophosphoric acid-N, N, N ′, except that silver hexafluorophosphate was used instead of silver bis (trifluoromethanesulfonyl) imidate described in Production Example 1, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium (compound 15) was obtained.

(Production Example 16)
Hexafluorophosphoric acid-N, N, N ′, except that silver hexafluorophosphate was used instead of silver bis (trifluoromethanesulfonyl) imidate described in Production Example 5 in the same manner as Production Example 5. N′-tetrakis {p-di (methylbenzyl) aminophenyl} -p-phenylenediimonium (compound 16) was obtained.

Example 1
As a near-infrared absorbing dye, bis (trifluoromethanesulfonyl) imidic acid-N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium obtained in Production Example 1 ( 3 parts of Compound 1) and 27 parts of triethylene glycol-di-2-ethylenehexanoate were added and dissolved to obtain a solution.
30 parts by mass of the above solution was added to 70 parts by mass of a polyvinyl butyral resin (average polymerization degree 1700, butyralization degree 85.5 mol%, acetylation degree 0.9 mol%, hydroxyl group content 13.6 mol%). After mixing, extrusion was performed with an extruder so that the film thickness became 0.76 mm, and an interlayer film for laminated glass was produced.
The obtained interlayer film for laminated glass was sandwiched between two transparent float glasses, put in a rubber bag, vacuum degassed, and pre-pressed at a temperature of 110 ° C. Next, using an autoclave, pressure bonding was performed for 20 minutes under the conditions of 135 ° C. and 1.2 MPa to produce a laminated glass.

(Examples 2 to 12, Comparative Examples 1 to 4)
Corresponding to Table 1, a laminated glass was produced in the same manner as in Example 1 except that compounds 2 to 16 were used as near-infrared absorbing dyes.

<Method for evaluating heat resistance>
The laminated glasses obtained from Examples 1 to 12 and Comparative Examples 1 to 4 were stored at 80 ° C. for 1 month and subjected to a heat resistance test. The transmittance of the laminated glass at the initial wavelength and after the test at wavelengths of 1000 nm and 550 nm was measured with a spectrophotometer. The measurement results are shown in Table 1.

  From Table 1, it can be seen from Comparative Examples 1 to 4 that Examples 1 to 12 have better heat resistance.

  Since the interlayer film for laminated glass of the present invention and the laminated glass using the same are excellent in heat resistance, it can be used for various applications.

Claims (5)

An interlayer film for laminated glass, comprising a near-infrared absorbing dye, which is a compound represented by the following general formula (1), and a polyvinyl acetal resin.

(In the formula (1), R _{1 to} R ₈ each represent an organic group which may be the same or different, and X ⁻ represents a bis (trifluoromethanesulfonyl) imidate ion or a bis (pentafluoroethanesulfonyl) imidate ion. , Cyclo-hexafluoropropane-1,3-bis (sulfonyl) imidoate ion, and tris (trifluoromethanesulfonyl) methidoate ion. In general formula (1), R _{1 to} R ₈ are cycloalkyl-alkyl groups represented by the following general formula (2), phenylalkyl groups represented by the following general formula (3), and the following general formula (4). The interlayer film for laminated glass according to claim 1, wherein the interlayer film is an alkyl ester group represented by the formula:

(In Formula (2), A shows a C1-C10 linear or branched alkyl group, m shows the integer of 3-12.)

(In formula (3), B represents a linear or branched alkyl group having 1 to 10 carbon atoms, and R ₉ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom.)

(In the formula _{(4), R 10} represents an alkyl group having 1 to 10 carbon atoms, n represents an integer of 1 to 10.)   Content of the near-infrared absorption pigment | dye in the intermediate film for laminated glasses is 0.01-10 mass%, The intermediate film for laminated glasses of Claim 1 or 2 characterized by the above-mentioned.   The interlayer film for laminated glass according to any one of claims 1 to 3, wherein the polyvinyl acetal resin is a polyvinyl butyral resin.   A laminated glass, wherein the interlayer film for laminated glass according to any one of claims 1 to 4 is bonded between two transparent glass plates.