JP2014106309A - Near-infrared absorbing resin composition and near-infrared absorbing film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a near-infrared absorbing resin composition which can provide a near-infrared absorbing film having excellent absorbance and light resistance in haze, and a near-infrared absorbing film made using the same.SOLUTION: In a near-infrared absorbing composition, a near-infrared absorbing agent is dispersed in a polymerizable binder composed of two or more compounds, in which at least one polymerizable binder is a compound having a carboxyl group and an ethylenically unsaturated group represented by general formula (1) or (2). A near-infrared absorbing film is made using the same.

Description

  The present invention relates to a near-infrared absorbing resin composition and a near-infrared absorbing film using the same.

  In recent years, plasma display panels (hereinafter, abbreviated as “PDP”) have become widespread as demands for larger and thinner displays have increased. Since near infrared rays are emitted from the PDP and an electronic device using a near infrared remote controller malfunctions, it is necessary to shield the near infrared rays with a filter containing a near infrared absorber. Moreover, since the optical semiconductor element used for a CCD camera etc. has high sensitivity in the near infrared region, it is necessary to remove the near infrared ray. Furthermore, near-infrared absorbers are used as heat-ray shielding materials that shield sunlight from the viewpoint of energy saving, and are used as heat-ray shielding agents and heat-ray shielding film materials for multilayer glass such as automotive glass and building glass. Has been. In addition, a heat ray shielding agent is a useful material for maintaining the characteristics because the temperature rise of the module in the solar cell lowers the conversion efficiency. The near-infrared shielding filter used for these applications can absorb the near-infrared light region effectively while transmitting the visible light region.

  Near-infrared absorbers that absorb near-infrared include conventional organic dyes such as cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, metal dithiol complex dyes, phthalocyanine dyes, diimonium dyes and inorganic oxides Particles and the like are used (Patent Documents 1 and 2).

  In the configuration of a normal optical filter using such a near-infrared absorber, a near-infrared absorption layer and a hard coat layer are provided separately. For example, since the near-infrared absorbing layer disclosed in Patent Document 2 is not a hard coat layer, it is necessary to prepare a near-infrared absorbing layer and a hard coat layer separately when obtaining an optical filter with high scratch resistance. is there. However, since such a configuration requires two layers, further simplification of the configuration is required. In recent years, a near-infrared absorbing film used as one layer has been developed by including a near-infrared absorber in a hard coat layer.

Patent Document 3 discloses a resin molded product having a hard coat layer containing a near infrared absorber. An ultraviolet curable acrylic resin is used for the hard coat layer, and specific examples thereof include acrylates such as polyurethane acrylate and epoxy acrylate.
However, even when the above-mentioned ultraviolet curable acrylic resin is used, there is a problem inferior in light resistance in the absorbance and haze of the obtained near-infrared absorbing film due to the influence of the resin.

  Then, the near-infrared absorption film which is excellent in the light resistance in the light absorbency and haze of a near-infrared absorption film, and the near-infrared absorption resin composition which can manufacture it were calculated | required.

JP 2003-96040 A JP 2004-309655 A Japanese Patent Laid-Open No. 10-193522

  The objective of this invention is providing the near-infrared absorption resin composition which can provide the near-infrared absorption film excellent in the light resistance in a light absorbency and a haze, and the near-infrared absorption film produced using it.

  As a result of intensive studies, the present inventors have found that a near-infrared absorbing resin composition in which a near-infrared absorber is dispersed in a polymerizable binder composed of two or more compounds, at least one of the polymerizable binders is generally A near-infrared absorbing resin composition characterized by being a compound having a carboxyl group represented by formula (1) or (2) and an ethylenically unsaturated group, and a near-infrared absorbing film produced using the same The inventors have found that the problem can be solved and have reached the present invention.

  That is, the present invention is as follows.

The first invention is a near-infrared absorbing resin composition in which a near-infrared absorber is dispersed in a polymerizable binder composed of two or more compounds.
A near-infrared absorbing resin composition, wherein at least one of the polymerizable binders is a compound having a carboxyl group and an ethylenically unsaturated group represented by the following general formula (1) or (2): .

（式（１）中、ｎは、１〜６の整数であり、ｍは１〜５の数である。）

(In Formula (1), n is an integer of 1-6, m is a number of 1-5.)

（式（２）中、ｐは、１〜６の整数であり、ｑは１〜５の数である。）

(In Formula (2), p is an integer of 1-6, q is a number of 1-5.)

  In the second invention, the content of the compound having a carboxyl group and an ethylenically unsaturated group represented by the general formula (1) or (2) in the polymerizable binder is 0.1 to 20% by mass. The near-infrared absorbing resin composition according to the first invention, characterized in that

  3rd invention is a near-infrared absorptive resin composition as described in 1st or 2nd invention, wherein a near-infrared absorber is a diimonium salt compound represented by following General formula (3). .

（式（３）中、Ｒ_１〜Ｒ_８はそれぞれ同一でも異なっていても良い有機基を表し、Ｘ⁻はアニオンを示す。）

(In Formula (3), R _{1 to} R ₈ each represents an organic group which may be the same or different, and X ⁻ represents an anion.)

According to a fourth invention, X ⁻ in the diimonium salt compound represented by the general formula (3) is hexafluorophosphate ion, hexafluoroantimonate ion, bis (trifluoromethanesulfonyl) imidate ion, bis (fluorosulfonyl). ) A near-infrared absorbing resin composition according to the third invention, which is a kind selected from the group consisting of imido ion.

  A fifth invention is the near-infrared absorbing resin composition according to any one of the first to fourth inventions, wherein the near-infrared absorber has an average particle size of 2 μm or less.

  A sixth invention is a near-infrared absorbing layer obtained by applying the near-infrared absorbing resin composition according to any one of the first to fifth inventions on a transparent substrate and then curing it by light irradiation. It is a near-infrared absorption film characterized by laminating | stacking.

  According to the present invention, it is possible to provide a near-infrared absorbing resin composition capable of providing a near-infrared absorbing film excellent in light resistance in absorbance and haze, and a near-infrared absorbing film produced using the same.

  In the near-infrared absorbing composition in which a near-infrared absorber is dispersed in a polymerizable binder composed of two or more kinds of compounds, at least one of the polymerizable binders is represented by the general formula (1) or (2 A near-infrared absorbing resin composition characterized by being a compound having a carboxyl group and an ethylenically unsaturated group, and a near-infrared absorbing film produced using the same.

  First, the near-infrared absorbing resin composition will be described.

[Polymerizable binder]
Among the polymerizable binders composed of two or more kinds of compounds used in the present invention, at least one kind contains a compound having a carboxyl group and an ethylenically unsaturated group represented by the following general formula (1) or (2). It is a near-infrared absorbing resin composition characterized by doing.

  In said general formula (1), n is an integer of 1-6 and m is a number of 1-5.

  In the general formula (2), p is an integer of 1 to 6, and q is a number of 1 to 5.

  Specific examples of the compound having a carboxyl group and an ethylenically unsaturated group represented by the general formula (1) include the following compounds (A) to (N).

  Among these, the compound (D) or (M) is preferable because it is particularly excellent in light resistance.

  Specific examples of the compound having a carboxyl group and an ethylenically unsaturated group represented by the general formula (2) include the following compounds (O) to (U).

  Among these, the compound (P) or (S) is preferable because it is particularly excellent in light resistance.

  The present invention is characterized by mixing with a compound (monomer or polymer) having an ethylenically unsaturated group in addition to the compound described above.

  Specific examples of the compound (monomer) having an ethylenically unsaturated group include pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, isocyanuric acid EO-modified triacrylate, trimethylolpropane EO-modified triacrylate, dipentaerythritol. Hexaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, trimethyl Roll propane EO modified tri (meth) acrylate, dipentaerythritol pen Data (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and acrylic monomers such as pentaerythritol tetra (meth) acrylate.

  Specific examples of the compound (polymer) having an ethylenically unsaturated group include acrylic monomers such as hydroxyethyl acrylate, hydroxyethyl (meth) acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, and the like. Polyester, polyether, polyacrylic, polycarbonate and other polyols such as hexamethylene diisocyanate, pentamethylene diisocyanate, propylene diisocyanate, butylene diisocyanate and other aliphatic isocyanates, cyclohexane diisocyanate, methylene (biscyclohexyl isocyanate), isophorone diisocyanate, etc. Isocyanate curing agents such as aromatic isocyanates such as alicyclic isocyanate and tolylene diisocyanate Combined fabricated urethane acrylate resins.

  By using a compound having a carboxyl group and an ethylenically unsaturated group as at least one kind of the polymerizable binder, the ethylenically unsaturated group contributes to the polymerization, and the carboxyl group remains to the end. Since the carboxyl group is present in the resin, the near-infrared absorber can be prevented from deteriorating, and as a result, a near-infrared absorbing film excellent in light resistance in absorbance and haze can be produced.

  The content of the compound having a carboxyl group and an ethylenically unsaturated group represented by the general formula (1) or (2) in the polymerizable binder is preferably 0.1 to 20% by mass, and 0.3 to 15% by mass. Is more preferable, and 0.5 to 10% by mass is particularly preferable. By setting it as this content, a near-infrared absorbing film excellent in light resistance particularly in haze and absorbance can be produced.

[Near infrared absorber]
As the near-infrared absorber used in the present invention, known near-infrared absorbers can be used. Specific examples include diimonium salt compounds, phthalocyanine salt compounds, cyanine salt compounds, anthraquinone salt compounds, and dithiol salt compounds. . The near infrared ray means light having a wavelength in the range of 750 to 2000 nm.

  As a near-infrared absorber used for this invention, it is mentioned preferably using the diimonium salt compound represented by following General formula (3).

In the general formula (3), the organic groups represented by R _{1 to} R ₈ may be the same or different, and preferred organic groups are linear or branched optionally substituted with a halogen atom. C _1-10 alkyl group, cyclohexyl alkyl group, phenylalkyl group and the like.

As the C _1-10 alkyl group, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-amyl group, iso-amyl group, 1-methylbutyl group, 2-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 2-dimethylpropyl group, 1,1-dimethylpropyl group, n-pentyl group, neopentyl group, n-hexyl Groups and the like. Among these, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an iso-butyl group are preferable.

The C _1-10 alkyl group substituted with a halogen atom includes a 2-halogenoethyl group, a 2,2-dihalogenoethyl group, a 2,2,2-trihalogenoethyl group, a 3-halogenopropyl group, 3 , 3-dihalogenopropyl group, 3,3,3-trihalogenopropyl group, 4-halogenobutyl group, 4,4-dihalogenobutyl group, 4,4,4-trihalogenobutyl group, 5-halogenopentyl group And halogenated alkyl groups such as 5,5-dihalogenopentyl group and 5,5,5-trifluoropentyl group. Specific examples include monofluoroalkyl groups such as a 2-fluoroethyl group, a 3-fluoropropyl group, a 4-fluorobutyl group, and a 5-fluoropentyl group. A 3-fluoropropyl group, a 4-fluorobutyl group, and a 5-fluoropentyl group are more preferable, and a 3-fluoropropyl group is particularly preferable.

  The cyclohexylalkyl group can be represented by the following general formula (4).

In General Formula (4), A represents an 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. More preferably, A is an alkyl group having 1 to 4 carbon atoms.
Cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, cyclohexylbutyl group, methyl 2-ethylcyclohexylmethyl group, 3-methylcyclohexylmethyl group, 4-methylcyclohexylmethyl group, 4-methylcyclohexylethyl group, 4-methylcyclohexylpropyl Group, 4-methylcyclohexylbutyl group, 4-fluorocyclohexylmethyl group and the like. Among these, cyclohexylmethyl group is preferable.

  The phenylalkyl group can be represented by the following general formula (5).

In General Formula (5), B represents an alkyl group having 1 to ₁₀ carbon atoms, and R ₁₀ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom. B is preferably an alkyl group having 1 to 4 carbon atoms.
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 dispersibility in the polymerizable binder.

Moreover, X < ^- > in the diimonium salt compound represented by General formula (3) is an anion required in order to neutralize the electric charge of a diimonium salt compound cation, and an inorganic anion, an organic acid anion, etc. can be used. Specific examples of anions include halogen ions such as fluorine ion, chlorine ion, bromine ion and iodine ion, perchlorate ion, periodate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion bis. (Trifluoromethanesulfonyl) imidate ion, bis (fluorosulfonyl) imidate ion, etc. are mentioned.
Among these, hexafluorophosphate ion, hexafluoroantimonate ion, bis (trifluoromethanesulfonyl) imidate ion, and bis (fluorosulfonyl) imidate ion are more preferable, and hexafluorophosphate ion or bis (trifluoromethane). Particularly preferred is a sulfonyl) imido ion.

  Although details will be described later regarding the diluent, a diluent may be added to the near-infrared absorbing resin composition for the purpose of adjusting the viscosity. As the diluent, an organic solvent or / and a reaction diluent or the like can be used. The near-infrared absorber can be dispersed in a part or all of the diluent and then mixed with the polymerizable binder and dispersed. .

  The average particle diameter of the near-infrared absorber is preferably smaller in order to obtain more excellent transparency, preferably 2 μm or less, and more preferably 1 μm or less.

  The apparatus for dispersing the near-infrared absorber in the polymerization binder may be a commonly used apparatus, and examples thereof include a magnetic stirrer, a bladed stirrer, a homogenizer, an ultrasonic homogenizer, and a bead mill. However, an ultrasonic homogenizer and a bead mill are more suitable as a stirring device for obtaining high transparency.

On the other hand, the content of the near-infrared absorber with respect to the polymerizable binder is not particularly limited, and may be adjusted so that desired properties, particularly efficient near-infrared absorption ability, and excellent transparency in the visible light region can be achieved. Good.
For example, when the dry film thickness of the resin is set to 1 to 20 μm, the preferable blending ratio of the near infrared absorber is 0.1 to 100 parts by mass with respect to 100 parts by mass of the polymerizable binder composed of two or more compounds. More preferably, it is 0.5-50 mass parts, Most preferably, it is 1-30 mass parts. When this blending ratio is less than 0.1 parts by mass, the near infrared ray absorbing ability is slightly inferior, and conversely, when the blending ratio exceeds 100 parts by mass, the above-mentioned improvement in performance corresponding to the content is not recognized and it is not economical. There is.
In addition, the mixture ratio of a near-infrared absorber can be changed with the setting of the transmittance | permeability of visible and a near-infrared region, and the thickness of the laminated body of a near-infrared absorption composition.

  The near-infrared absorbing resin composition may contain a neon cut pigment. A neon cut pigment | dye is a pigment | dye which absorbs the orange neon light which has a wavelength of 580-600 nm. Specifically, cyanine compounds, polymethine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quinone compounds, azaporphyrin compounds, azo compounds, azo chelate compounds, indonaphthol chelate compounds, dithiols Examples thereof include metal complex compounds, azomethine compounds, xanthene compounds, and the like.

Further, for the purpose of adjusting the color, a color correcting dye having a maximum absorption wavelength in the range of 380 to 780 nm may be contained in the near-infrared absorbing resin composition.
Examples of color correction dyes include phthalocyanine compounds, azaporphyrin compounds, polymethine compounds, cyanine compounds, squarylium compounds, azomethine compounds, polymethine compounds, xanthene compounds, pyromethene compounds, isoindolinone compounds, Examples include quinacridone compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, and dioxazine compounds.

  In addition, for the purpose of adjusting the color and transmittance, carbon black having a particle diameter of 200 nm or less that does not impair the transparency may be contained in the near-infrared absorbing resin composition.

[Inorganic fine particles]
In the present invention, inorganic fine particles may be used in the near infrared absorbing resin composition. As the inorganic fine particles, long-wavelength near infrared rays that cannot be absorbed by the near-infrared absorber and inorganic fine particles that absorb light having a wavelength of 1300 nm to 2000 nm are suitable. Specifically, tin-doped indium oxide (ITO) fine particles and antimony-doped tin oxide ( ATO) fine particles are preferred.

  As the particle size, the primary average particle size is preferably 200 nm or less, more preferably 100 nm or less, and still more preferably 80 nm or less. When the primary average particle system exceeds 200 nm, visible light scattering is likely to occur, and the haze of the near-infrared absorbing resin composition and the near-infrared absorbing film in which the near-infrared absorbing resin composition is laminated on the transparent substrate is increased, which may impair transparency. There is.

  The inorganic fine particles are dispersed in an organic solvent of the diluent used for the purpose of adjusting the viscosity of the near-infrared absorbing resin composition and / or part or all of the reaction diluent, and then mixed with a polymerizable binder for polymerization. It is also possible to disperse in a functional binder, and additives such as dispersants and dispersion stabilizers can be used as necessary.

In addition, the inorganic fine particles can be pretreated for improving dispersion stability, near-infrared absorption efficiency, and reducing haze. For example, the ITO fine particles can be produced by reacting a mixed aqueous solution of an indium chloride aqueous solution (InCl ₃ aqueous solution) and a tin chloride aqueous solution (SnCl ₄ aqueous solution) with an alkali, and firing the generated precipitate. When the ITO fine particles produced in this way are heated in an inert atmosphere in the presence of alcohol and the powder surface is reduced, the ITO fine particles turn slightly yellowish to a slightly blue color and are well-familiar with alcohol solvents. Thus, near infrared absorption efficiency can be improved and haze can be reduced.

On the other hand, the content of ITO fine particles and ATO fine particles with respect to the polymerizable binder is not particularly limited, and is adjusted so that desired properties, particularly efficient near-infrared absorption ability, and excellent transparency in the visible light region can be achieved. That's fine.
For example, when the dry film thickness of the resin is set to 1 to 20 μm, the preferable blending ratio of the ITO fine particles is 1 to 100 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the polymerizable binder. . If this blending ratio is less than 1 part by mass, it is difficult to obtain an excellent near-infrared absorptivity. Conversely, when the blending ratio exceeds 100 parts by mass, the above-described improvement in performance corresponding to the content is not recognized and it is economical. In addition, transparency in the visible region may be lost.
The mixing ratio of the ITO fine particles and the ATO fine particles can be changed by setting the transmittance in the visible and near infrared regions and the thickness of the laminate of the near infrared absorbing composition.

[Polymerization initiator]
Regarding the polymerizable binder composed of two or more kinds of compounds used in the present invention, it is preferable to perform radical polymerization by adding an energy ray-sensitive radical polymerization initiator. Examples of the polymerization initiator include 2,2-dimethoxy-1,2 -Diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzophenone, 1- [4- (2-hydroxyethoxy)- Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2 -Methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (methyl Thio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl-) Benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl- Diphenyl-phosphine oxide, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), ethyl-4-dimethylaminobenzoate, 2-ethylhexyl- - it can be used dimethylaminobenzoate, but the present invention is not limited thereto.

  These polymerization initiators can be used alone or in combination of two or more according to the desired performance. Moreover, as a compounding quantity of a polymerization initiator, it is 0.05-20 mass% with respect to polymerizable binder whole quantity, Preferably it is 0.1-20 mass%. When the blending amount of the polymerization initiator is less than 0.05% by mass, the composition may not be cured sufficiently. On the other hand, if the blending amount of the polymerization initiator exceeds 20% by mass, the physical properties of the cured product will not be further improved, and there is a disadvantage that the economy is inferior.

[Diluent]
A diluent may or may not be added to the near-infrared absorbing resin composition of the present invention. The diluent is not particularly limited as long as it can dissolve the polymerizable binder and disperse the diimonium salt compound, and various organic solvents can be used. Examples of the organic solvent include alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; glycol solvents such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene copolymer; Monomethyl ether, monoethyl ether, monopropyl ether, monoisopropyl ether, monobutyl ether, 2-methoxyethanol, 2-ethoxyethanol, 2-methoxypropanol, 2-ethoxypropanol, 3-methoxybutanol, 3-methoxy-3-methyl Ether alcohol solvents such as butanol; dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibu Polyether solvents such as ether, methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, methyl butyl ether, ethyl propyl ether, ethyl isopropyl ether and ethyl butyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; methyl acetate, Examples include ester solvents such as ethyl acetate and butyl acetate; hydrocarbon solvents such as hexane, heptane, octane, cyclopentane, cyclohexane, methylcyclohexane, toluene, and xylene. These solvent may be used by 1 type and may be used as 2 or more types of mixed solvents. An organic solvent having a boiling point of 200 ° C. or lower is preferable. The water content of the solvent is desirably 5% by mass or less.

  Moreover, you may use a reactive diluent as a diluent. A monofunctional polymerizable compound can also be used as the reactive diluent. Specific examples of the monofunctional polymerizable compound include acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth). Acrylate, isobutoxymethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl diethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (Meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl ( Acrylate), N, N-dimethyl (meth) acrylamide, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2- Tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidonephenoxyethyl (meth) acrylate, brooxyethyl (meth) acrylate, pentachlorophenyl (me ) Acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyltriethylene diglycol (meth) acrylate, etc. Two or more kinds may be used by mixing with the above solvent.

  As for the diluent, it can be used as a dispersion medium in which a diimonium salt compound or inorganic fine particles are dispersed in a polymerizable binder. The diluent may be a dispersion medium alone. In addition to the dispersion medium, the viscosity of the near-infrared absorbing resin composition may be used. In order to adjust the viscosity, a diluent may be further mixed. Further, it is possible to disperse the diimonium salt compound in the polymerizable binder without using a diluent.

[Additive]
The near-infrared absorbing resin composition of the present invention may contain an appropriate additive depending on the purpose. Specific examples of additives include leveling agents, pigment dispersants, UV absorbers, antioxidants, viscosity modifiers, light stabilizers, metal deactivators, peroxide decomposing agents, fillers, reinforcing materials, Plasticizers, lubricants, anticorrosives, rust inhibitors, emulsifiers, mold demolding agents, fluorescent whitening agents, organic flameproofing agents, inorganic flameproofing agents, anti-dripping agents, melt flow modifiers, antistatic agents , Slip imparting agent, adhesion imparting agent, antifouling agent, surfactant, antifoaming agent, polymerization inhibitor, photosensitizer, surface improver, silane coupling agent, polymerization catalyst and the like.

[Near-infrared absorbing film]
The configuration of the near-infrared absorbing film of the present invention is a configuration in which a near-infrared absorbing layer is laminated on a transparent substrate. The method for producing the near-infrared absorbing film comprises applying the near-infrared absorbing composition on a transparent substrate, and then irradiating with light to cure the near-infrared absorbing resin composition, thereby absorbing near-infrared light on the transparent substrate. A near-infrared absorbing film in which layers are laminated can be produced.

Desired near-infrared absorption performance, in order to form a laminate of the near-infrared absorbing composition by a known method, the thickness of the laminate is preferably about 1 to 40 μm, considering the curing shrinkage of the resin 1-20 μm Is more desirable.
The light irradiation is about 50 to 1,500 mJ / cm ² by ultraviolet rays or the like.

  Various coating methods such as microgravure, gravure, die, curtain, lip, and slot can be used as a method for applying the near-infrared absorbing composition.

  Although it does not specifically limit as a transparent base material, As a shape, a sheet-like, film-like, or plate-like transparent base material can be used. Colors are also colorless and colored, and are not particularly limited. Examples of the material for the transparent substrate include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); triacetyl cellulose (TAC); acrylic resins such as methyl methacrylate copolymers; styrene resins; polysulfone resins Polyethersulfone resin; polycarbonate resin; vinyl chloride resin; polymethacrylimide resin, glass plate and the like.

The transparent substrate may be subjected to an easy adhesion treatment. For example, the PET film may be a film subjected to an easy adhesion treatment (easy adhesion PET film). The easy adhesion treatment is preferably performed on at least the surface on which the hard coat layer is provided. Examples of the easy adhesion treatment include a treatment for providing an easy adhesion layer and a treatment for applying a corona treatment to the substrate surface. Examples of the easy adhesion layer include a resin layer for easy adhesion.
Particularly preferred transparent substrates are polyethylene terephthalate (PET) films and triacetyl cellulose (TAC) films.

  In the near infrared absorbing film, a pressure-sensitive adhesive layer using a rubber-based, acrylic-based, or silicon-based pressure-sensitive adhesive can be formed to adhere to the adherend as needed. Depending on the situation, suitable additives may be contained. Specific examples of additives include polymerization catalysts, leveling agents, dyes, pigments, pigment dispersants, inorganic fine particles, ultraviolet absorbers, antioxidants, viscosity modifiers, light stabilizers, metal deactivators, anticorrosives. Antirust agent, organic flame retardant, inorganic flame retardant, anti-dripping agent, antistatic agent, slipping agent, adhesion promoter, antifouling agent, surfactant, antifoaming agent, polymerization inhibitor, surface Examples thereof include an improver, a silane coupling agent, and carbon black.

  In addition, heat ray shielding, electromagnetic wave shielding function, antireflection function, antiglare function can be added as necessary, and the function is a new heat ray shielding layer, electromagnetic wave cut on the transparent substrate of the near infrared absorbing film. It can be applied by forming a laminated body such as a layer, an antireflection layer, or an antiglare layer and / or separately preparing a film having this function and bonding it to a near-infrared absorbing film.

<Heat ray shielding layer>
A heat ray shielding layer prepared by dispersing inorganic fine particles in a polymerizable binder may be provided. As the inorganic fine particles, long-wavelength near infrared rays that cannot be absorbed by the near-infrared absorber and inorganic fine particles that absorb light having a wavelength of 1300 nm to 2000 nm are suitable. Specifically, tin-doped indium oxide (ITO) fine particles and antimony-doped tin oxide ( ATO) fine particles are preferred. As a base material, the near-infrared absorption film of this invention may be utilized as it is, and after providing a heat ray shielding layer on a resin film or glass, you may bond with the near-infrared absorption film of this invention.

<Electromagnetic wave cut layer>
For production of the electromagnetic wave cut layer, vapor deposition of metal oxide or the like, sputtering method or the like can be used. Light of 1000 nm or more can also be cut by alternately laminating dielectric layers and metal layers on a substrate by sputtering or the like. The dielectric layer is a transparent metal oxide such as indium oxide or zinc oxide, and the metal layer is generally silver or a silver-palladium alloy. Usually, about 3, 5, 7 or 11 layers are sequentially stacked from the dielectric layer. As a base material, you may use the near-infrared absorption film of this invention as it is, and after providing an electromagnetic wave cut layer by vapor deposition or sputtering on a resin film or glass, it bonds with the near-infrared absorption film of this invention. Also good.

<Antireflection layer>
The antireflection layer is a layer for suppressing reflection on the surface and improving the reflection of a fluorescent lamp or the like and the transmittance of the filter. As a production method, a metal oxide, fluoride, silicide, boride, carbide, Methods of laminating inorganic materials such as nitrides and sulfides in a single layer or multiple layers by vacuum deposition, sputtering, ion plating, ion beam assist, etc., and resins with different refractive indexes such as acrylic resins and fluororesins There is a method of laminating a single layer or multiple layers. Moreover, the film which gave the antireflection process can also be affixed on this filter.

<Anti-glare layer>
In addition to the above-described layers, an antiglare layer (antiglare layer) may be provided. Like the antireflection layer, the antiglare layer is a layer for reducing the reflection of fluorescent lamps, etc. In order to scatter reflected light, fine powders such as silica, melamine, and acrylic are dispersed in a resin to form ink. And a method of coating the surface can be used. The ink can be cured by thermal curing or photocuring. An antiglare-treated film can also be pasted on the filter.

  EXAMPLES Hereinafter, an Example is given and this invention is demonstrated in detail. In addition, this invention is not limited at all by the Example.

(Production of near-infrared absorber (diimonium salt compound))
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. N, N, N ′, N′-Tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediamine in an automatic mortar AMN-200 (manufactured by Nippon Ceramic Science Co., Ltd.) at a pestle of 100 rpm and a mortar of 6 rpm Dry pulverization was performed for 30 minutes to obtain a pulverized product.

  To 24.1 parts of the pulverized N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediamine obtained, 200 parts of acetonitrile and silver hexafluorophosphate 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 to give hexafluorophosphate-N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl. } -P-phenylene dimonium 27.0 parts were obtained.

(Manufacture of near-infrared absorbing resin composition 1)
50 ml of the obtained hexafluorophosphoric acid-N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium 0.5 part and 9.5 parts of methyl isobutyl ketone And stirred with a magnetic stirrer for 30 minutes to obtain a mixture of a diimonium salt compound and a diluent.
The particle size was measured by adding 0.8 part of the mixture to 100 parts of ethyl acetate, and measuring this with a laser particle size SALD-2000J manufactured by SHIMAZU.

  As a compound having a carboxyl group and an ethylenically unsaturated group, 0.05 part of acrylic acid dimer (Aronix M-5600, manufactured by Toa Gosei Co., Ltd.), urethane acrylate (Art Resin UN-906, manufactured by Negami Kogyo Co., Ltd.) as an acrylate monomer ) 49.95 parts, 48 parts of the mixture obtained in the production of the near-infrared absorbing resin composition 1 and 2 parts of Irgacure 184 (manufactured by BASF) as a photopolymerization initiator were mixed to obtain a near-infrared absorbing resin composition. 1 was obtained.

(Production of near-infrared absorbing resin compositions 2 to 7)
In the production of the near-infrared absorbing resin composition 1, as shown in Table 1, the near-infrared absorbing resin except that the content ratio of the compound having a hydroxyl group and an ethylenically unsaturated group and the acrylate monomer was changed. Near-infrared absorbing resin compositions 2 to 7 were obtained in the same manner as in the production of composition 1.

(Production of near-infrared absorbing resin composition 8)
In the production of the near-infrared absorbing resin composition 1, ω-carboxy-polycaprolactone monoacrylate (Aronix M-5300, manufactured by Toa Gosei Co.) was used instead of acrylic acid dimer (Aronix M-5600, manufactured by Toa Gosei Co., Ltd.). The near-infrared absorbing resin composition 8 was obtained by the same method as the production of the near-infrared absorbing resin composition 1 except that the mass ratios shown in Table 1 were used.

(Manufacture of near-infrared absorbing resin composition 9)
In the production of the near-infrared absorbing resin composition 1, instead of acrylic acid dimer (Aronix M-5600, manufactured by Toa Gosei Co.), phthalic acid monohydroxyethyl acrylate (Aronix M-5400, manufactured by Toa Gosei Co., Ltd.) was used. A near-infrared absorbing resin composition 9 was obtained in the same manner as in the production of the near-infrared absorbing resin composition 1 except that the mass ratio described in 1 was used.

(Production of near-infrared absorbing resin composition 10)
As a compound having a hydroxyl group and an ethylenically unsaturated group, 50 parts of acrylic acid dimer (Aronix M-5600, manufactured by Toa Gosei Co., Ltd.), 48 parts of the mixture obtained in the production of the near-infrared absorbing resin composition 1, A near-infrared absorbing resin composition 1 was obtained by mixing 2 parts of Irgacure 184 (manufactured by BASF) which is a photopolymerization initiator.

(Production of near-infrared absorbing resin composition 11)
In the production of the near-infrared absorbing resin composition 10, in place of acrylic acid dimer (Aronix M-5600, manufactured by Toa Gosei Co., Ltd.), urethane acrylate (Art Resin UN-906, manufactured by Negami Kogyo Co., Ltd.) was used. A near-infrared absorbing resin composition 11 was obtained in the same manner as in the production of the infrared absorbing resin composition 1.

Example 1
(Near-infrared absorbing film)
Next, the prepared near-infrared absorbing resin composition 1 is bar-coated on a PET film A-4300 (100 μm thickness manufactured by Toyobo Co., Ltd.) using a coating rod # 24, dried at 100 ° C. for 1 minute, and then irradiated with ultraviolet light using a high-pressure mercury lamp. Irradiated with 200 mJ / cm ² to obtain a near-infrared absorbing film.

(Examples 2 to 9, Comparative Examples 1 and 2)
A near-infrared absorbing film was obtained in the same manner as in Example 1 except that the composition 1 described in Example 1 was replaced with the compositions 2 to 11.

(Measurement method of absorbance and haze in near-infrared absorbing film)
The near-infrared absorption films obtained in Examples 1 to 9 and Comparative Examples 1 and 2 were evaluated for their absorbance and heat resistance in haze.
As a method for measuring absorbance, a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation) was used, and the absorbance at 850 nm was measured. The haze measurement method used a haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.). The haze value is preferably 3% or less, and particularly preferably 2.50% or less.
In the light resistance test, the absorbance at 850 nm after 1000 hours at 640 W was measured, and the value divided by the absorbance at 850 nm before the test was judged as the dye residual ratio. Moreover, it measured also about the haze and calculated | required the haze after a test and before a test.

  Table 1 shows the absorbance and haze value of the near-infrared absorbing films obtained in Examples 1 to 9 and Comparative Examples 1 and 2.

Abbreviations in Table 1 are as follows.
Compound 1: Acrylic acid dimer (Aronix M-5600, manufactured by Toa Gosei Co., Ltd.)
Compound 2: ω-carboxy-polycaprolactone monoacrylate (Aronix M-5300, manufactured by Toa Gosei Co., Ltd.)
Compound 3: monohydroxyethyl acrylate phthalate (Aronix M-5400, manufactured by Toa Gosei Co., Ltd.)
Compound a: Urethane acrylate (Art Resin UN-906, manufactured by Negami Industrial Co., Ltd.)

  From Table 2, Examples 1-9 are compared with Comparative Examples 1 and 2, and it can be confirmed that Examples 1-9 are excellent in absorbance and light resistance in haze.

  The near-infrared absorbing resin composition of the present invention and the near-infrared absorbing film prepared using the same are excellent in light absorbency and light resistance in haze. Therefore, it can be used for various applications such as for PDP, automobile glass, and building glass.

Claims (6)

In the near-infrared absorbing resin composition in which the near-infrared absorber is dispersed in a polymerizable binder composed of two or more kinds of compounds,
A near-infrared absorbing resin composition, wherein at least one of the polymerizable binders is a compound having a carboxyl group and an ethylenically unsaturated group represented by the following general formula (1) or (2).

(In Formula (1), n is an integer of 1-6, m is a number of 1-5.)

(In Formula (2), p is an integer of 1-6, q is a number of 1-5.)   The content of the compound having a carboxyl group and an ethylenically unsaturated group represented by the general formula (1) or (2) in the polymerizable binder is 10 to 20% by mass. The near-infrared absorbing resin composition described. The near-infrared absorbing resin composition according to claim 1 or 2, wherein the near-infrared absorbing agent is a diimonium salt compound represented by the following general formula (3).

(In Formula (3), R _{1 to} R ₈ each represents an organic group which may be the same or different, and X ⁻ represents an anion.) X ⁻ in the diimonium salt compound represented by the general formula (3) is composed of a hexafluorophosphate ion, a hexafluoroantimonate ion, a bis (trifluoromethanesulfonyl) imidate ion, and a bis (fluorosulfonyl) imidate ion. The near-infrared absorbing resin composition according to claim 3, which is a kind selected from the group.   The near-infrared absorbing resin composition according to claim 1, wherein the near-infrared absorbent has an average particle size of 2 μm or less.   A near infrared absorbing layer obtained by applying the near infrared absorbing resin composition according to any one of claims 1 to 5 on a transparent substrate and then curing it by light irradiation is laminated. A near infrared absorbing film.